WO2018034093A1 - 非水系二次電池機能層用組成物、非水系二次電池用機能層及び非水系二次電池 - Google Patents
非水系二次電池機能層用組成物、非水系二次電池用機能層及び非水系二次電池 Download PDFInfo
- Publication number
- WO2018034093A1 WO2018034093A1 PCT/JP2017/025765 JP2017025765W WO2018034093A1 WO 2018034093 A1 WO2018034093 A1 WO 2018034093A1 JP 2017025765 W JP2017025765 W JP 2017025765W WO 2018034093 A1 WO2018034093 A1 WO 2018034093A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- functional layer
- secondary battery
- particulate polymer
- aqueous secondary
- weight
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
-
- 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
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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 non-aqueous secondary battery functional layer composition, a non-aqueous secondary battery functional layer, and a non-aqueous secondary battery.
- Secondary battery is a generic term for batteries having the characteristic that they can be repeatedly charged and discharged.
- a secondary battery generally includes a positive electrode, a negative electrode, a separator, an electrolytic solution, and an exterior material. The electrolytic solution is filled in the space formed by the exterior material.
- a secondary battery using a non-aqueous electrolyte as an electrolyte is generally referred to as a non-aqueous secondary battery.
- the separator is provided between the positive electrode and the negative electrode.
- a separator what has a separator base material and the functional layer for non-aqueous secondary batteries formed on the said separator base material is known (for example, refer patent documents 1 and 2).
- the functional layer for a non-aqueous secondary battery may include a particulate polymer having an adhesive ability.
- the functional layer for a non-aqueous secondary battery can be formed using a composition for a non-aqueous secondary battery functional layer containing such a particulate polymer.
- the functional layer for a non-aqueous secondary battery may have an adhesive ability. Adhesion between the separator substrate and the electrode can be achieved by interposing a functional layer for a non-aqueous secondary battery having adhesive ability between the separator substrate and the electrode (positive electrode, negative electrode, or both).
- non-aqueous secondary batteries are required to have further improved performance, and therefore further improved adhesion of the functional layer is required.
- the replacement liquid to the electrode that is, the distribution of the electrolyte in the secondary battery to the electrode becomes insufficient, and the performance of the battery may be deteriorated.
- life characteristics life in repeated use
- low-temperature output characteristics characteristics capable of outputting a voltage close to normal temperature even at low temperatures
- the present invention can provide a non-aqueous secondary battery that can express high adhesive ability, has excellent performance such as life characteristics and low-temperature output characteristics, and is easy to handle.
- An object of the present invention is to provide a non-aqueous secondary battery with improved performance.
- the present inventor has intensively studied for the purpose of solving the above problems. As a result, the inventor adopts a specific one as a monomer unit in the particulate polymer constituting the composition for a non-aqueous secondary battery functional layer, and their ratio falls within a specific range. In addition, by adjusting the particle diameter of the particulate polymer to fall within a specific range and having a specific degree of swelling, the adhesiveness of the functional layer for the non-aqueous secondary battery is improved, and the non-aqueous secondary battery It has been found that the performance of the non-aqueous secondary battery can be suppressed and that blocking of the functional layer for a non-aqueous secondary battery can also be suppressed. The present invention has been completed based on such findings. That is, the present invention is as follows.
- a composition for a non-aqueous secondary battery functional layer containing a particulate polymer is A copolymer comprising 20% by weight or more and 80% by weight or less of an aromatic monovinyl monomer unit; and 0.01% by weight or more and 2% by weight or less of a polyethylenically unsaturated crosslinkable monomer unit,
- the volume average particle diameter D of the particulate polymer is 0.5 ⁇ m or more and 5 ⁇ m or less
- a non-aqueous secondary battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte solution
- a functional layer for a non-aqueous secondary battery containing a particulate polymer is A copolymer comprising 20% by weight or more and 80% by weight or less of an aromatic monovinyl monomer unit; and 0.01% by weight or more and 2% by weight or less of a polyethylenically unsaturated crosslinking monomer.
- the volume average particle diameter of the particulate polymer is 0.5 ⁇ m or more and 5 ⁇ m or less, and A functional layer for a non-aqueous secondary battery, wherein the degree of swelling of the particulate polymer with respect to a predetermined electrolytic solution is more than 1 time and 3 times or less.
- non-aqueous secondary battery that can exhibit high adhesive ability, is excellent in performance such as life characteristics and low-temperature output characteristics, and is easy to handle.
- a non-aqueous secondary battery with improved performance.
- (meth) acryl means acryl, methacryl or a combination thereof.
- (meth) acrylic acid means acrylic acid, methacrylic acid or a combination thereof.
- (Meth) acrylate means acrylate, methacrylate or a combination thereof.
- (meth) acrylonitrile means acrylonitrile, methacrylonitrile or a combination thereof.
- “monomer unit” refers to a structural unit having a structure formed by polymerization.
- a (meth) acrylic acid ester monomer unit refers to a structural unit having a structure formed by polymerizing a (meth) acrylic acid ester monomer.
- the (meth) acrylonitrile monomer unit means a structural unit having a structure formed by polymerizing (meth) acrylonitrile.
- Nonaqueous secondary battery functional layer composition contains a specific particulate polymer.
- the particulate polymer is a polymer having a particulate shape.
- the particulate polymer can maintain a particulate shape in the functional layer composition and the functional layer formed using the functional layer composition.
- the particulate polymer is a copolymer containing an aromatic monovinyl monomer unit and a polyethylenically unsaturated crosslinkable monomer unit.
- the structure of the copolymer is not particularly limited and may be any of a block copolymer, a graft copolymer, a random copolymer, and the like, but is preferably a random copolymer.
- aromatic monovinyl monomer unit examples include styrene, styrene sulfonic acid and salts thereof (for example, sodium styrene sulfonate), ⁇ -methylstyrene, vinyl toluene, 4- (tert -Butoxy) styrene and the like.
- styrene and sodium styrenesulfonate are preferable, and styrene is more preferable. These can be used alone or in combination of two or more.
- the content of the aromatic monovinyl monomer unit in the particulate polymer is 20% by weight or more, preferably 40% by weight or more, more preferably 60% by weight or more, and 80% by weight or less, preferably 77% by weight. % Or less, more preferably 75% by weight or less.
- the polyethylenically unsaturated crosslinkable monomer capable of forming the polyethylenically unsaturated crosslinkable monomer unit is a compound having two or more ethylenically unsaturated bonds.
- polyethylenically unsaturated crosslinking monomers include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Polyfunctional (meth) acrylates such as di (meth) acrylate and trimethylolpropane-tri (meth) acrylate; dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane And polyfunctional allyl / vinyl ethers such as divinylbenzene.
- ethylene glycol di (meth) acrylate and allyl (meth) acrylate are preferable, and ethylene glycol di (meth) acrylate is more preferable. These can be used alone or in combination of two or more.
- the content ratio of the polyethylenically unsaturated crosslinkable monomer unit in the particulate polymer is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and further preferably 0.1% by weight. Above, preferably 2% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.
- the blocking of the functional layer can be suppressed while developing the strength of the particulate polymer, thereby increasing the adhesive force.
- the content ratio of the polyethylenically unsaturated crosslinkable monomer unit in the particulate polymer to be equal to or less than the above upper limit value, the adhesiveness due to the particulate polymer can be expressed.
- the particulate polymer may contain an arbitrary unit in addition to the aromatic monovinyl monomer unit and the polyethylenically unsaturated crosslinkable monomer unit.
- arbitrary units include (meth) acrylic acid alkyl ester monomer units and acidic group-containing monomer units.
- the (meth) acrylic acid alkyl ester monomer capable of forming a (meth) acrylic acid alkyl ester monomer unit is a (meth) acrylic acid alkyl ester monomer having one polymerizable unsaturated group per molecule. Can be used.
- Examples of (meth) acrylic acid alkyl ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate
- Acrylic acid alkyl esters such as hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate Me
- methyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, And butyl acrylate are preferred, and methyl methacrylate and butyl acrylate are more preferred.
- desired physical properties can be imparted to the particulate polymer.
- the (meth) acrylic acid alkyl ester monomer can be used alone or in combination of two or more.
- the content ratio of the (meth) acrylic acid alkyl ester monomer unit in the particulate polymer is preferably 5% by weight or more, more preferably 7% by weight or more, still more preferably 10% by weight or more, and preferably 70% by weight. % Or less, more preferably 60% by weight or less, still more preferably 50% by weight or less.
- the content ratio of the (meth) acrylic acid alkyl ester monomer unit in the particulate polymer is equal to or more than the lower limit, the amount of the particulate polymer eluted into the electrolyte solution can be reduced. The low-temperature characteristics of the water-based secondary battery can be made excellent.
- the content ratio of the (meth) acrylic acid alkyl ester monomer unit in the particulate polymer is not more than the above upper limit value. Adhesiveness can be expressed.
- acidic group-containing monomers that can form acidic group-containing monomer units include carboxylic acid group-containing monomers, sulfonic acid group-containing monomers, and phosphoric acid group-containing monomers. Of these, carboxylic acid group-containing monomers are preferred.
- carboxylic acid group-containing monomer examples include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
- Examples of ethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
- Examples of derivatives of ethylenically unsaturated monocarboxylic acids include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E monomethoxyacrylic acid, And ⁇ -diaminoacrylic acid.
- Examples of ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, and mesaconic acid.
- Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
- ethylenically unsaturated dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, diphenyl maleate, nonyl maleate, decyl maleate, maleate
- examples include dodecyl acid, octadecyl maleate, and fluoroalkyl maleate.
- the acidic group-containing monomer is preferably a carboxylic acid group-containing monomer, more preferably acrylic acid, methacrylic acid, or itaconic acid. Acrylic acid and methacrylic acid are more preferred, and methacrylic acid is particularly preferred. These acidic group-containing monomers can be used alone or in combination of two or more.
- the content ratio of the acidic group-containing monomer unit in the particulate polymer is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.5% by weight or more, preferably Is 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less.
- the volume average particle diameter D of the particulate polymer is preferably 0.5 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, and even more preferably 1.5 ⁇ m or less.
- the volume average particle diameter D is preferably 0.5 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, and even more preferably 1.5 ⁇ m or less.
- the volume average particle diameter D is the volume average particle diameter D50 in the particle size distribution (volume basis).
- the volume average particle diameter D50 represents a particle diameter (median diameter) at which the cumulative volume from the small diameter side becomes 50% in the particle size distribution (volume basis).
- the particle size distribution can be measured by a commercially available particle size distribution measuring device. Specifically, the measurement can be performed using a laser diffraction particle size distribution measuring apparatus described in the evaluation items of the examples of the present application.
- the glass transition temperature of the particulate polymer is preferably higher than a certain level. Specifically, the glass transition temperature of the particulate polymer is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and still more preferably 35 ° C. or higher.
- the upper limit of the glass transition temperature of the particulate polymer is not particularly limited, but can usually be 65 ° C. or lower.
- the glass transition temperature can be measured using a commercially available differential scanning calorimeter or the like according to JIS K7121. Specifically, it can be measured by the following procedure. First, a measurement object is formed into a film having a thickness of 1 ⁇ 0.3 mm. The film is dried in a hot air oven at 120 ° C. for 1 hour. Then, using the dried film as a sample, a differential scanning calorimeter (DSC6220SII, manufactured by Nanotechnology Co., Ltd.) was used in accordance with JIS K7121 at a measurement temperature of ⁇ 100 ° C. to 180 ° C. and a heating rate of 5 ° C./min. To measure the glass transition temperature (° C.).
- a differential scanning calorimeter DSC6220SII, manufactured by Nanotechnology Co., Ltd.
- the measured glass transition temperature is determined at one point.
- the particulate polymer is a copolymer other than a random copolymer, for example, a block copolymer or a graft copolymer
- the measured glass transition temperature is indicated by a plurality of values. Since the particulate polymer is a random copolymer, the polymer can be homogenized, and the durability of the particulate polymer with respect to the electrolytic solution can be improved.
- the composition for a non-aqueous secondary battery functional layer The dispersibility of can also be improved.
- the particulate polymer has a degree of swelling with respect to the electrolyte within a specific range.
- the degree of swelling with respect to the electrolytic solution is a ratio of a change in weight caused by forming a particulate polymer into a film and immersing it in a predetermined electrolytic solution at 60 ° C. for 72 hours.
- a specific method for measuring the degree of swelling is as follows. That is, about 0.2 g of the dried particulate polymer is pressed at 200 ° C. and 5 MPa for 2 minutes to form a film. The obtained film is cut into 1 cm squares to form test pieces, and the weight W0 of the test pieces is measured.
- the predetermined electrolytic solution a nonaqueous electrolytic solution obtained by dissolving the supporting electrolyte in a predetermined mixed solvent at a concentration of 1 mol / L is used.
- the swelling degree S of the particulate polymer is more than 1 time, preferably 1.5 times or more, more preferably 1.75 times or more, 3 times or less, preferably 2.5 times or less, more preferably 2. 25 times or less.
- a polymer having such a desired degree of swelling can be obtained by appropriately adjusting the composition of the monomer units.
- the particulate polymer preferably has an elution amount into the electrolyte within a specific range.
- the amount of elution into the electrolyte is the amount of particulate polymer that elutes into the electrolyte as a result of swelling.
- the amount of elution can be determined by drying the test piece after measuring the degree of swelling described above, measuring the dry weight, and comparing it with the weight before immersion.
- the elution amount X of the particulate polymer is preferably 0.01% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less.
- the low temperature characteristic of a secondary battery can be improved by making the elution amount X of a particulate polymer below the said upper limit.
- the electrode mixture layer can be covered and the life characteristics of the secondary battery can be improved.
- the content ratio of the particulate polymer in the solid content of 100% by weight of the functional layer composition is preferably 3% by weight or more, more preferably 4% by weight or more, particularly preferably 5% by weight or more, preferably 95%. % By weight or less, more preferably 90% by weight or less, particularly preferably 85% by weight or less.
- the solid content of the functional layer composition refers to a component remaining in the functional layer after the formation of the functional layer including the drying step using the functional layer composition, and usually other than the solvent. The sum of all ingredients.
- the particulate polymer can be prepared by copolymerizing a plurality of monomers described above.
- the proportion of the monomer can usually be the same as the proportion of the monomer unit in the particulate polymer.
- the polymerization mode of the particulate polymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used.
- a solution polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method
- addition polymerization such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
- emulsifiers, dispersants, polymerization initiators, polymerization aids and the like used for the polymerization can be used, and the amount used can also be a generally used amount.
- the polymerization is started in the state of the polymerizable monomer, not in the state of the oligomer obtained by polymerizing the polymerizable monomer in the monomer composition to some extent. Thereby, the production
- the volume average particle diameter D of the particulate polymer can be adjusted by any known method. For example, by changing the reaction conditions of the polymerization reaction by changing the type and amount of the emulsifier, the amount of the polymerization initiator, the particulate polymer having a necessary particle size range from the polymer obtained by the polymerization reaction.
- the volume average particle diameter D of the particulate polymer can be adjusted by extracting or polymerizing by adding an appropriate amount of monomer in the presence of seed particles.
- the composition for a non-aqueous secondary battery functional layer of the present invention may contain an optional component in addition to the particulate polymer.
- the composition for a non-aqueous secondary battery functional layer of the present invention may contain a dispersion medium.
- the composition for a non-aqueous secondary battery functional layer of the present invention can have a slurry property.
- the composition for a non-aqueous secondary battery functional layer of the present invention having a slurry property may be referred to as a “functional layer slurry composition”.
- the dispersion medium is volatilized, whereby a functional layer made of the solid content of the functional layer slurry composition can be obtained.
- any medium that can be volatilized in the formation of the functional layer, has a low property of dissolving the particulate polymer, and can maintain the dispersed state of the particulate polymer can be used.
- an aqueous medium is preferable.
- the aqueous medium is water or a mixture of water and a medium other than water.
- Examples of media that can be used in combination with water in the aqueous medium include, for example, cycloaliphatic hydrocarbon compounds such as cyclopentane and cyclohexane; aromatic hydrocarbon compounds such as toluene and xylene; ketone compounds such as ethyl methyl ketone and cyclohexanone; Ester compounds such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone; nitrile compounds such as acetonitrile and propionitrile; ether compounds such as tetrahydrofuran and ethylene glycol diethyl ether: methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol And alcohol compounds such as monomethyl ether; amide compounds such as N-methylpyrrolidone (NMP) and N, N-dimethylformamide; and the like. One of these may be used alone, or two or more of these may be
- the amount of the dispersion medium in the functional layer slurry composition is preferably set so that the solid content concentration of the functional layer slurry composition falls within a desired range.
- the solid content concentration of the specific functional layer slurry composition is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more, preferably 80% by weight or less. Is 75% by weight or less, even more preferably 70% by weight or less, and particularly preferably 65% by weight or less.
- the slurry composition for functional layers can have the property suitable for the process of application
- the composition for a non-aqueous secondary battery functional layer of the present invention may contain inorganic particles as an optional component.
- the inorganic particles are inorganic compound particles.
- the inorganic particles do not dissolve in the dispersion medium that can be included in the functional layer composition or in the non-aqueous electrolyte solution of the non-aqueous secondary battery, and can maintain the shape thereof.
- the inorganic compound constituting the inorganic particles a material that is stably present in the environment in which the non-aqueous secondary battery is used and is electrochemically stable is preferable.
- preferable inorganic compounds from such a viewpoint include aluminum oxide (alumina), hydrated aluminum oxide (boehmite), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO 3 , ZrO.
- Oxide particles such as alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalently-bonded crystal particles such as silicon and diamond; sparingly soluble ions such as barium sulfate, calcium fluoride and barium fluoride Crystal particles; clay fine particles such as talc and montmorillonite;
- the inorganic particles may be obtained by subjecting particles made of these materials to element substitution, surface treatment, solid solution treatment, or the like.
- One kind of inorganic particles may be used alone, or two or more kinds may be used in combination.
- the volume average particle diameter of the inorganic particles is preferably 0.1 ⁇ m or more, more preferably 0.20 ⁇ m or more, even more preferably 0.30 ⁇ m or more, preferably 1.0 ⁇ m or less, more preferably 0.90 ⁇ m or less. Even more preferably, it is 0.80 ⁇ m or less.
- the binding force between particles can be expressed in the functional layer, and thus the cohesive failure when a peeling force is loaded on the functional layer can be suppressed, and the adhesive force of the functional layer can be improved. Furthermore, shrinkage when heat is applied to the functional layer can be reduced. By making the volume average particle diameter equal to or less than the above upper limit value, the thickness of the functional layer can be reduced, and as a result, the capacity of the non-aqueous secondary battery can be increased.
- thixotropy can be imparted to the functional layer composition, and as a result, the floating of the particulate polymer is suppressed and the functional layer is prevented from being blocked. be able to.
- the inorganic particles commercially available products having a desired volume average particle diameter can be used as they are or after being treated as necessary. Moreover, you may use, after adjusting the volume average particle diameter of an inorganic particle to the desired range by operations, such as classification and crushing.
- the content ratio of the inorganic particles in the solid content of 100% by weight of the functional layer composition is preferably 40% by weight or more, more preferably 50% by weight or more, particularly preferably 60% by weight or more, preferably 99% by weight. Hereinafter, it is more preferably 98% by weight or less, particularly preferably 97% by weight or less.
- the obtained functional layer can be provided with a porous property, and the functional layer can be used as a porous film.
- the composition for functional layers prepared in the slurry form can have a property suitable for application
- the weight ratio of the inorganic particles to the particulate polymer can be appropriately adjusted so as to obtain a functional layer composition and a functional layer having desired properties.
- the proportion of inorganic particles in the total 100% by weight of the inorganic particles and the particulate polymer is preferably 50% by weight or more, more preferably 55% by weight or more, still more preferably 60% by weight or more, while preferably 95% by weight. % Or less, more preferably 90% by weight or less, and still more preferably 85% by weight or less.
- the ratio of the inorganic particles in the total of the inorganic particles and the particulate polymer By setting the ratio of the inorganic particles in the total of the inorganic particles and the particulate polymer to the lower limit value or more, blocking of the functional layer can be suppressed, and the heat shrinkage resistance in the dry state is also improved in the electrolytic solution. Heat shrinkage resistance (less shrinkage due to heating in the electrolyte when the functional layer is bonded to other components depending on the conditions for pressing the components such as electrodes and separators when manufacturing secondary batteries. A good functional layer can be obtained. By making the ratio of the inorganic particles in the total of the inorganic particles and the particulate polymer not more than the above upper limit value, the ratio of the relative particulate polymer can be increased, and as a result, the functional layer can be reliably applied to the electrode. Adhesion can be achieved.
- the composition for a non-aqueous secondary battery functional layer of the present invention may contain a functional layer binder as an optional component.
- the binder for the functional layer has the ability to bind the components constituting the functional layer for the non-aqueous secondary battery to each other, in particular, the ability to bind the inorganic particles to each other, and the inorganic particles and the particulate polymer. Can have the ability to bind to each other.
- the functional layer binder preferably has a glass transition temperature lower than a certain level.
- the glass transition temperature of the functional layer binder is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, and further preferably ⁇ 5 ° C. or lower.
- the lower limit of the glass transition temperature of the binder for functional layers is not particularly limited, but can usually be ⁇ 80 ° C. or higher. Since the functional layer binder has such a low glass transition temperature, the functional layer binder melts in the process of producing the functional layer using the functional layer composition, and the binding function is good. Can be expressed.
- a polymer having desired properties can be used as the functional layer binder.
- a polymer may be a homopolymer composed of one kind of polymer unit or a copolymer containing two or more kinds of polymer units. From the viewpoint of adjusting the physical properties such as the particle size, glass transition temperature and ability as a binder to a desired range, a copolymer is preferable.
- the functional layer binder may include a (meth) acrylic acid alkyl ester monomer unit.
- the (meth) acrylic acid alkyl ester monomer corresponding to the (meth) acrylic acid alkyl ester monomer unit include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t- Acrylic acid alkyl esters such as butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; and methyl methacrylate, ethyl methacrylate , N-propyl methacrylate, is
- the proportion of the (meth) acrylic acid alkyl ester monomer unit in the functional layer binder is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more, preferably 99%. % By weight or less, more preferably 98% by weight or less, particularly preferably 97% by weight or less.
- the binder for a functional layer may contain an acidic group-containing monomer unit.
- the acidic group-containing monomer unit for example, one selected from the same range as that described as being usable for the particulate polymer can be used.
- an acidic group containing monomer unit may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the ratio of the acidic group-containing monomer unit in the functional layer binder is preferably 0.2% by weight or more, more preferably 0.4% by weight or more, and particularly preferably 0.6% by weight or more. Is 10.0% by weight or less, more preferably 6.0% by weight or less, and particularly preferably 4.0% by weight or less.
- the binder for the functional layer can contain a (meth) acrylonitrile monomer unit.
- acrylonitrile monomer corresponding to the (meth) acrylonitrile monomer unit acrylonitrile may be used, methacrylonitrile may be used, or acrylonitrile and methacrylonitrile are used in combination. May be.
- the ratio of the (meth) acrylonitrile monomer unit in the functional layer binder is preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and particularly preferably 1.0% by weight or more. Preferably it is 20.0 weight% or less, More preferably, it is 10.0 weight% or less, Most preferably, it is 5.0 weight% or less.
- the functional layer binder may contain a crosslinkable monomer unit.
- the crosslinkable monomer corresponding to the crosslinkable monomer unit include a polyethylenically unsaturated crosslinkable monomer and an epoxy / N-methylol crosslinkable monomer in the description of the particulate polymer. Examples similar to those exemplified above are given.
- a crosslinkable monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the proportion of the crosslinkable monomer unit in the functional layer binder is preferably 0.2% by weight or more, more preferably 0.6% by weight or more, particularly preferably 1.0% by weight or more, preferably It is 5.0% by weight or less, more preferably 4.0% by weight or less, and particularly preferably 3.0% by weight or less.
- the functional layer binder may further include any structural unit other than those described above.
- the arbitrary structural unit include a structural unit having a structure formed by polymerizing styrene (styrene unit) and a structural unit having a structure formed by polymerizing butadiene (butadiene unit).
- styrene unit a structural unit having a structure formed by polymerizing styrene
- butadiene unit butadiene unit
- these arbitrary structural units may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the functional layer binder may be present in a state of being dissolved in the dispersion medium in the functional layer composition, or may be present in a particulate shape.
- the volume average particle diameter of the particles of the functional layer binder is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 0. .15 ⁇ m or more, preferably 0.4 ⁇ m or less, more preferably 0.35 ⁇ m or less, and particularly preferably 0.3 ⁇ m or less.
- the binding property of a functional layer can be improved by making it below an upper limit.
- the composition for a non-aqueous secondary battery functional layer of the present invention contains a particulate polymer as a binder for the functional layer
- the polymer having a particle shape Of these the volume average particle diameter of those having a glass transition temperature of 20 ° C. or higher is adopted as the volume average particle diameter D.
- Examples of the method for producing the functional layer binder include a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
- the emulsion polymerization method and the suspension polymerization method are preferable because they can be polymerized in water and can be suitably used as the material for the functional layer slurry composition.
- the reaction system contains a dispersing agent.
- the functional layer binder is usually formed of a polymer substantially constituting the functional layer binder, but may be accompanied by optional components such as additives used in the polymerization.
- the amount of the functional layer binder is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 30 parts by weight with respect to 100 parts by weight of the total of the inorganic particles and the particulate polymer.
- the amount is not more than parts by weight, more preferably not more than 25 parts by weight.
- the composition for a non-aqueous secondary battery functional layer of the present invention may contain other optional components in addition to the components described above.
- the optional component is not particularly limited as long as it does not have an excessively unfavorable influence on the battery reaction in the secondary battery using the functional layer.
- the kind of the arbitrary component may be one kind or two or more kinds.
- the optional component include a wetting agent, a leveling agent, an electrolytic solution decomposition inhibitor, and a water-soluble polymer compound.
- the water-soluble polymer compound is not particularly limited, and for example, those described in JP-A-2014-063754 can be used.
- the method for preparing the functional layer composition is not particularly limited, but usually, the above-described particulate polymer and optional components (dispersion medium, inorganic particles, functional layer binder, And other optional components).
- the mixing method is not particularly limited, but in order to disperse each component efficiently, mixing is performed using a disperser as a mixing device.
- the disperser is preferably an apparatus capable of uniformly dispersing and mixing the above components. Examples include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer.
- the non-aqueous secondary battery functional layer of the present invention is formed using the above-described non-aqueous secondary battery functional layer composition.
- the functional layer for a non-aqueous secondary battery of the present invention is, for example, by coating the functional layer composition described above on the surface of an appropriate substrate to form a coating film, and then drying the formed coating film, Can be formed. Since the functional layer for a non-aqueous secondary battery of the present invention is formed using the above-described composition for a functional layer of a non-aqueous secondary battery of the present invention, it can exhibit excellent adhesiveness.
- the nonaqueous secondary battery functional layer of the present invention is provided as a bonding layer for bonding other components or a porous film for separating the positive electrode and the negative electrode in the nonaqueous secondary battery, for example.
- effects such as improvement of low temperature output characteristics and life characteristics of the non-aqueous secondary battery can be exhibited.
- the substrate on which the functional layer composition is applied there is no limitation on the substrate on which the functional layer composition is applied.
- a functional layer composition coating film is formed on the surface of a release substrate, and the coating film is dried to form a functional layer.
- the release substrate may be peeled off from the functional layer.
- the functional layer peeled off from the release substrate can be used as a self-supporting film for forming a battery member of a secondary battery.
- the functional layer peeled off from the release substrate may be laminated on the separator substrate to form a separator having the functional layer, or the functional layer peeled off from the release substrate may be used as the electrode substrate.
- An electrode provided with a functional layer may be formed by stacking on the substrate.
- a separator substrate or an electrode substrate as the substrate.
- the functional layer provided on the separator substrate and the electrode substrate can suitably function as a protective layer (heat resistant layer) for improving the heat resistance and strength of the separator and the electrode.
- the separator substrate is not particularly limited and may be any separator substrate such as an organic separator substrate.
- the organic separator substrate is a porous member made of an organic material.
- Examples of the organic separator substrate include a micro functional layer and a nonwoven fabric containing a polyolefin resin such as polyethylene and polypropylene, an aromatic polyamide resin, and the like.
- a polyethylene functional layer and a nonwoven fabric are preferred because of their excellent strength.
- the thickness of the organic separator substrate can be any thickness, and is usually 0.5 ⁇ m or more, preferably 5 ⁇ m or more, and usually 40 ⁇ m or less, preferably 35 ⁇ m or less, more preferably 30 ⁇ m or less.
- the electrode substrate (positive electrode substrate and negative electrode substrate) is not particularly limited, and may include a current collector and an electrode mixture layer provided thereon.
- Current collector, electrode active material (positive electrode active material and negative electrode active material) in electrode mixture layer, and binder for electrode mixture layer (binder for positive electrode mixture layer and binder for negative electrode mixture layer) As well as the method for forming the electrode mixture layer on the current collector, known methods can be used. For example, those described in JP2013-145663A can be employed.
- Examples of methods for forming a functional layer on a substrate such as a separator substrate and an electrode substrate include the following methods. (1) A method in which the composition for a functional layer is applied to the surface of a separator substrate or an electrode substrate (in the case of an electrode substrate, the surface on the electrode mixture layer side, the same shall apply hereinafter) and then dried; (2) A method of drying a separator substrate or electrode substrate after immersing the separator layer or electrode substrate in the functional layer composition; (3) A method for producing a functional layer by applying and drying the functional layer composition on a release substrate, and transferring the obtained functional layer to the surface of a separator substrate or an electrode substrate; Among these, the method (1) is particularly preferable because the thickness of the functional layer can be easily controlled. Specifically, the method (1) includes a step of applying a functional layer composition on a substrate (application step), and drying the functional layer composition applied on the substrate to form a functional layer. Including a process (drying process).
- the method for coating the functional layer composition on the substrate is not particularly limited.
- the coating method include a doctor blade method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- the method for drying the functional layer composition on the substrate is not particularly limited, and a known method can be used.
- Examples of the drying method include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with infrared rays or electron beams.
- the drying conditions are not particularly limited, and the drying temperature is preferably 50 to 100 ° C. and the drying time is preferably 5 to 30 minutes.
- the thickness of the functional layer for a non-aqueous secondary battery of the present invention is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 1 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and further Preferably it is 5 micrometers or less.
- the thickness of the functional layer is 0.01 ⁇ m or more, the strength of the functional layer can be sufficiently ensured, and when it is 20 ⁇ m or less, the diffusibility of the electrolytic solution is secured, and the secondary using the functional layer The performance of the battery can be improved.
- the functional layer for a non-aqueous secondary battery of the present invention can be made into a functional layer having high adhesiveness by including a specific particulate polymer. Specifically, adhesion with other components can be easily achieved by pressing the components such as electrodes and separators when manufacturing the secondary battery. More specifically, when the functional layer for a non-aqueous secondary battery is provided as a layer on the surface of the separator, the electrode and the separator are overlapped and pressed under conditions such as a load of 10 kN / m and a temperature of 80 ° C. And a separator can be bonded and integrated to obtain a laminated body.
- the functional layer for a non-aqueous secondary battery of the present invention can also be a functional layer having a high blocking property as described above and having a suppressed blocking property by including a specific particulate polymer. . Specifically, in a state where the non-aqueous secondary battery functional layer is overlaid, after the non-aqueous secondary battery functional layer is put in close contact with the conditions when storing the secondary battery prior to the production of the secondary battery, The degree to which these are bonded can be reduced.
- the non-aqueous secondary battery of the present invention includes the above-described functional layer for a non-aqueous secondary battery of the present invention. More specifically, the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and at least one of the positive electrode, the negative electrode, and the separator functions as described above for the non-aqueous secondary battery of the present invention. Having a layer. Since the non-aqueous secondary battery of the present invention includes a functional layer formed using the composition for a functional layer of the present invention, high life characteristics (life in repeated use), high low temperature output characteristics (even at low temperatures, Excellent battery characteristics such as the ability to output a voltage close to room temperature).
- the separator When the non-aqueous secondary battery of the present invention includes the separator having the functional layer for a non-aqueous secondary battery of the present invention described above as a separator, the separator is on the separator substrate and one or both surfaces thereof. It may have a functional layer provided on the surface.
- the electrode When the non-aqueous secondary battery of the present invention includes the electrode having the functional layer for a non-aqueous secondary battery of the present invention described above as an electrode (positive electrode and / or negative electrode), the electrode includes a current collector and a current collector. It may have an electrode mixture layer provided thereon and a functional layer provided on the electrode mixture layer.
- the electrode mixture layer and the functional layer may be provided only on one surface of the current collector, or may be provided on both surfaces.
- the non-aqueous secondary battery of the present invention includes the above-described functional layer for a non-aqueous secondary battery of the present invention as one of a positive electrode, a negative electrode, or a separator
- the other is the non-aqueous secondary battery of the present invention. It may have a functional layer for a battery or may not have a functional layer for a non-aqueous secondary battery of the present invention.
- the electrode which does not have the functional layer for non-aqueous secondary batteries of this invention can consist of an electrical power collector and the electrode compound-material layer provided on the electrical power collector, for example.
- the separator which does not have the functional layer for non-aqueous secondary batteries of this invention can consist of a separator base material, for example.
- the secondary battery of the present invention is a non-aqueous secondary battery, and therefore a non-aqueous electrolyte is used as the electrolyte.
- a nonaqueous electrolytic solution an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
- a supporting electrolyte for example, a lithium salt is used in a lithium ion secondary battery.
- lithium salt examples 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 , and CF 3 SO 3 Li are preferable because they are easily dissolved in a solvent and exhibit a high degree of dissociation.
- One type of electrolyte may be used alone, or two or more types may be used in combination.
- the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
- an organic solvent capable of dissolving the supporting electrolyte can be appropriately selected.
- carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC);
- DMC dimethyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- PC propylene carbonate
- BC butylene carbonate
- MEC methyl ethyl carbonate
- esters such as ⁇ -butyrolactone and methyl formate
- ethers such as 1,2-dimethoxyethane and tetrahydrofuran
- sulfur-containing compounds such as sulfolane and dimethyl sulfoxide
- carbonates are preferable because they have a high dielectric constant and a wide stable potential region.
- the lower the viscosity of the solvent used the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted depending on the type of solvent.
- the concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate.
- Nonaqueous secondary battery shape and manufacturing method In the non-aqueous secondary battery of the present invention described above, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is placed in a battery container by winding or folding as necessary. It can be manufactured by pouring and sealing.
- the positive electrode, the negative electrode, and the separator at least one member is a member with a functional layer.
- an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like may be placed in the battery container to prevent an increase in pressure inside the battery or overcharge / discharge.
- the shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
- volume average particle diameter D The volume average particle diameter D of the particulate polymer was measured using a laser diffraction method. Specifically, an aqueous dispersion containing particles (solid content concentration 0.1% by weight) was prepared as a measurement sample, and a laser diffraction particle size distribution measuring device (manufactured by Beckman Coulter, product name “LS-230”) was prepared. )) was used to measure the volume average particle size of the particles. More specifically, in the particle size distribution (volume basis) obtained from the measurement result of the laser diffraction particle size distribution measuring device, the particle size at which the cumulative volume from the small diameter side becomes 50% is expressed as the volume average particle size ( ⁇ m).
- a nonaqueous electrolytic solution obtained by dissolving a supporting electrolyte at a concentration of 1 mol / L in a predetermined mixed solvent was used.
- ethylene carbonate (EC), diethyl carbonate (DEC), and vinylene carbonate (VC) mixed at a volume ratio: EC / DEC / VC 68.5 / 30 / 1.5 was used. LiPF 6 was used as the supporting electrolyte.
- Electrodes and separators obtained in the examples and comparative examples were cut out to form a slice having a width of 10 mm and a length of 50 mm.
- the positive electrode was cut out in Example 14, and the negative electrode was cut out in other Examples and Comparative Examples.
- the electrode piece and the separator piece were overlapped.
- the separator sections were superposed such that the separator base-side surface (the surface not having the porous film) was in contact with the positive electrode section.
- Example 15 the separator pieces were overlapped so that the surface of the separator base was in contact with the negative piece.
- the overlapped sections were pressed using a roll press under the conditions of a load of 10 kN / m and a temperature of 80 ° C. to obtain a test piece in which the electrode sections and the separator sections were integrated.
- a cellophane tape was fixed on a horizontal test bench with the adhesive surface facing upward.
- a cellophane tape defined in JIS Z1522 was used.
- the obtained test piece was attached to the cellophane tape with the electrode side surface facing down.
- one end on the separator side of the test piece was pulled off in the vertical direction at a speed of 50 mm / min, and the stress at that time was measured. The same measurement was performed three times, and the average value of the measurement results was obtained as the peel strength.
- the adhesiveness was determined according to the following criteria. It shows that the adhesiveness of the functional layer for non-aqueous secondary batteries is so high that the value of peel strength is large.
- the separators or electrodes obtained in the examples and comparative examples were cut into square sections having a width of 5 cm and a length of 5 cm.
- a separator or an electrode a positive electrode was cut out in Example 14, a negative electrode was cut out in Example 15, and a separator was cut out in other Examples and Comparative Examples.
- Two sections were superposed and placed under pressure conditions of 40 ° C. and 10 g / cm 2 for 5 minutes to prepare a measurement sample. The obtained measurement sample was allowed to stand for 24 hours, and then the blocking strength was measured.
- the blocking characteristics were determined according to the following criteria.
- Example 1 (1-1. Preparation of aqueous dispersion containing binder for functional layer)
- a reactor equipped with a stirrer 70 parts of ion-exchanged water, 0.15 part of sodium lauryl sulfate (product name “Emal 2F” manufactured by Kao Chemical Co., Ltd.) as an emulsifier, and ammonium persulfate as a polymerization initiator were added in an amount of 0. Five parts were supplied each. Subsequently, the gas phase in the reactor was replaced with nitrogen gas, and the temperature of the liquid phase in the reactor was raised to 60 ° C.
- sodium lauryl sulfate product name “Emal 2F” manufactured by Kao Chemical Co., Ltd.
- ammonium persulfate as a polymerization initiator
- a separate container 50 parts of ion exchange water, 0.5 part of sodium dodecylbenzenesulfonate as an emulsifier, 94 parts of n-butyl acrylate, 2 parts of acrylonitrile, 2 parts of methacrylic acid as a polymerizable monomer
- a monomer mixture was obtained by supplying and mixing 1 part of N-hydroxymethylacrylamide and 1 part of allyl glycidyl ether. The obtained monomer mixture was continuously supplied to the reactor over 4 hours to carry out polymerization. During the supply of the monomer mixture, the temperature in the reactor was maintained at 60 ° C.
- the temperature was raised to 70 ° C., and stirring was continued for another 3 hours, after which the polymerization reaction was terminated. Thereby, an aqueous dispersion containing an acrylic polymer as a binder for the functional layer was prepared.
- the glass transition temperature of the functional layer binder was measured and found to be -11 ° C.
- the reaction medium was cooled to stop the polymerization reaction.
- an aqueous dispersion containing the particulate polymer was prepared.
- the volume average particle diameter D, swelling degree S, and elution amount X of the obtained particulate polymer were measured. Moreover, it was 60 degreeC when the glass transition temperature of the particulate polymer was measured.
- Alumina product name “AKP3000” manufactured by Sumitomo Chemical Co., Ltd., volume average particle diameter: 0.5 ⁇ m; density 3.9 g / cm 3
- the aqueous dispersion of the particulate polymer obtained was 20 parts by weight corresponding to the solid content, and the aqueous dispersion of the functional layer binder obtained in (1-1) was increased to 5 parts by weight corresponding to the solid content.
- separator substrate As a separator substrate, a separator substrate composed of three layers of polypropylene / polyethylene / polypropylene (separator thickness: 25 ⁇ m, product name “Celguard 2325”) was prepared. On one surface of this separator substrate, the functional layer slurry composition obtained in (1-3) was applied so as to have a thickness of 2 ⁇ m, and then dried at 50 ° C. for 10 minutes. Thereby, the functional layer for non-aqueous secondary batteries was formed on one surface of the separator base material. Subsequently, by the same operation as this operation, a functional layer for a non-aqueous secondary battery was also formed on the other surface of the separator substrate.
- the separator which has a separator base material and the functional layer for non-aqueous secondary batteries provided in the both surfaces was obtained.
- the thickness of each functional layer was 2 ⁇ m.
- the blocking characteristic was evaluated.
- the slurry composition for negative electrode obtained in (1-6) is comma separated on one surface of a copper foil (thickness 20 ⁇ m) as a current collector for negative electrode so that the film thickness after drying becomes about 150 ⁇ m. It was applied using a coater.
- the negative electrode slurry composition was dried by conveying the copper foil coated with the negative electrode slurry composition through an oven at a temperature of 60 ° C. at a rate of 0.5 m / min for 2 minutes. . Thereafter, the copper foil coated with the negative electrode slurry composition was heat-treated at a temperature of 120 ° C. for 2 minutes. Thus, a negative electrode mixture layer was formed on one surface of the negative electrode current collector.
- the negative electrode current collector provided with the negative electrode current collector and the negative electrode mixture layer provided on both surfaces thereof is removed. Obtained.
- the negative electrode raw material was rolled by a roll press to obtain a negative electrode in which the thickness of the negative electrode mixture layer on each surface was 80 ⁇ m. With respect to the obtained negative electrode and the separator obtained in (1-4), the adhesion of the separator to the electrode was evaluated.
- the positive electrode slurry composition obtained in (1-8) is comma separated on one surface of an aluminum foil (thickness 20 ⁇ m) as a positive electrode current collector so that the film thickness after drying is about 150 ⁇ m. It was applied using a coater. Next, the positive electrode slurry composition was dried by conveying the aluminum foil coated with the positive electrode slurry composition through an oven at a temperature of 60 ° C. at a rate of 0.5 m / min for 2 minutes. . Thereafter, the aluminum foil coated with the positive electrode slurry composition was heat-treated at a temperature of 120 ° C. for 2 minutes. Thus, a positive electrode mixture layer was formed on one surface of the positive electrode current collector.
- the positive electrode current collector including the positive electrode current collector and the positive electrode mixture layer provided on both surfaces thereof is removed. Obtained.
- the positive electrode raw material was rolled with a roll press to obtain a positive electrode in which the thickness of the positive electrode mixture layer on each surface was 60 ⁇ m.
- the positive electrode obtained in (1-9) was cut out to obtain a rectangular positive electrode of 49 cm ⁇ 5.0 cm.
- the separator obtained in (1-4) was cut out to obtain two rectangular separators of 55 cm ⁇ 5.5 cm.
- the negative electrode obtained in (1-7) was cut out to obtain a rectangular negative electrode of 50 cm ⁇ 5.2 cm.
- These were stacked to obtain a laminate having a layer configuration of (rectangular positive electrode) / (rectangular separator) / (rectangular negative electrode) / (rectangular separator).
- the obtained laminate was wound from the end in the longitudinal direction by a winding machine to obtain a wound body.
- the wound body was pressed for 8 seconds under the pressing conditions of a temperature of 70 ° C. and a pressure of 1.0 MPa to obtain a flat body.
- the said flat body was wrapped with the aluminum packaging material as an exterior material for non-aqueous secondary batteries.
- the aluminum exterior was hermetically closed by heat-sealing the opening of the aluminum packaging material at 150 ° C.
- a wound lithium ion secondary battery (I) was produced as a non-aqueous secondary battery.
- the capacity of this non-aqueous secondary battery was 800 mAh.
- the obtained wound-type non-aqueous secondary battery was evaluated for low-temperature output characteristics and life characteristics.
- Example 2 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition is composed of 80 parts of styrene (St), 15 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and 1 part of ethylene dimethacrylate (EDMA). The composition was changed to
- Example 3 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition is composed of 55 parts of styrene (St), 40 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and 1 part of ethylene dimethacrylate (EDMA). The composition was changed to
- Example 4 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition is composed of 20 parts of styrene (St), 75 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and 1 part of ethylene dimethacrylate (EDMA). The composition was changed to
- Example 5 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition is composed of 75.9 parts of styrene (St), 20 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and ethylene dimethacrylate (EDMA) 0
- the composition was changed to 0.01 parts.
- Example 6 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition is composed of 75 parts of styrene (St), 20 parts of n-butyl acrylate (BA), 3 parts of methacrylic acid (MAA), and 2 parts of ethylene dimethacrylate (EDMA). The composition was changed to
- Example 7 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition was prepared by adding 75 parts of styrene (St), 20 parts of n-butyl acrylate (BA), 4.6 parts of methacrylic acid (MAA), and 0. The composition was changed to 4 parts.
- Example 8> A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the volume average particle diameter D of the particulate polymer obtained was changed to 0.5 ⁇ m by changing the amount of the emulsifier to 1.2 parts.
- Example 9> (9-1. Preparation of particulate polymer for functional layer)
- a monomer composition 1.2 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator were added, After sufficiently stirring, the mixture was heated to 60 ° C.
- the monomer composition was a composition comprising 75 parts of styrene (St), 20 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and 1 part of ethylene glycol dimethacrylate (EDMA).
- the reaction medium was cooled to stop the polymerization reaction.
- an aqueous dispersion containing seed particles was prepared.
- an additional monomer composition was added to the aqueous dispersion of seed particles.
- the additional monomer composition was a composition consisting of 75,000 parts of styrene (St), 20000 parts of n-butyl acrylate (BA), 4000 parts of methacrylic acid (MAA), and 1000 of ethylene glycol dimethacrylate (EDMA). The mixture was stirred well and then warmed to 60 ° C. Thereby, polymerization of the polymerizable monomer was started.
- the reaction medium was cooled to stop the polymerization reaction.
- an aqueous dispersion containing a particulate polymer having a volume average particle diameter of 5.0 ⁇ m was prepared.
- the volume average particle diameter D, swelling degree S, elution amount X, and glass transition temperature of the obtained particulate polymer were measured.
- Example 10 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed. In (1-3), inorganic particles were not used. In (1-3), the amount of particulate polymer used was changed to 100 parts by weight.
- Example 11 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- boehmite (trade name) BMM” manufactured by Kawai Lime Industry Co., Ltd.); number average particle diameter 0.9 ⁇ m; density 3.5 g / cm 3 ; (Aluminum oxide hydrate: AlOOH)) was used in an amount of 76 parts by weight.
- the amount of particulate polymer used was changed to 24 parts by weight.
- Example 12 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the amount of inorganic particles used was changed to 49 parts by weight.
- the amount of particulate polymer used was changed to 51 parts by weight.
- Example 13 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the amount of inorganic particles used was changed to 94 parts by weight.
- the amount of particulate polymer used was changed to 6 parts by weight.
- Example 14> (14-1. Fabrication of positive electrode with functional layer) On one surface of the positive electrode obtained in (1-9) of Example 1, the functional layer slurry composition obtained in (1-3) was applied so that its thickness was 2 ⁇ m, and then Dry at 50 ° C. for 10 minutes. Thereby, the functional layer for non-aqueous secondary batteries was formed on one surface of the positive electrode. Subsequently, a functional layer for a non-aqueous secondary battery was also formed on the other surface of the positive electrode by the same operation as this operation. Thus, a functional layer-attached electrode having a current collector, a positive electrode mixture layer provided on both surfaces of the current collector, and a non-aqueous secondary battery functional layer provided on each positive electrode mixture layer is provided. Obtained. In the obtained positive electrode with a functional layer, the thickness of each functional layer was 2.0 ⁇ m. About the obtained positive electrode with a functional layer, the blocking characteristic was evaluated.
- a non-aqueous secondary battery function is the same as that in Example 1-4 (1-4) except that the non-aqueous secondary battery functional layer is formed only on one side of the separator substrate.
- a separator having a layer was obtained.
- the obtained separator had a separator substrate and a functional layer for a non-aqueous secondary battery provided only on one side thereof.
- the resulting separator and the positive electrode obtained in (14-1) were evaluated for adhesion.
- a non-aqueous secondary battery was manufactured and evaluated by the same operation as (1-10) of Example 1 except that the following matters were changed.
- the positive electrode obtained in (1-9) the positive electrode with a functional layer obtained in (14-1) was used.
- the separator obtained in (1-4) the separator obtained in (14-2) was used.
- the direction of the rectangular separator is the negative electrode whose surface on the functional layer side is rectangular The direction was opposite.
- Example 15> (15-1. Production of negative electrode with functional layer) On one surface of the negative electrode obtained in (1-7) of Example 1, the functional layer slurry composition obtained in (1-3) of Example 1 was applied so that the thickness thereof was 2 ⁇ m. And then dried at 50 ° C. for 10 minutes. Thereby, the functional layer for non-aqueous secondary batteries was formed on one surface of the negative electrode. Subsequently, a functional layer for a non-aqueous secondary battery was also formed on the other surface of the negative electrode by the same operation as this operation.
- a negative electrode with a functional layer having a current collector, a negative electrode composite material layer provided on both surfaces of the current collector, and a functional layer for a nonaqueous secondary battery provided on each negative electrode composite material layer is obtained. It was. In the obtained negative electrode with a functional layer, the thickness of each functional layer was 2.0 ⁇ m. About the obtained negative electrode with a functional layer, the blocking characteristic was evaluated.
- the orientation of the rectangular separator is set so that the surface on the separator substrate side is rectangular The direction was opposite to the negative electrode.
- Example 1 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition is composed of 75 parts of styrene (St), 20 parts of n-butyl acrylate (BA), and 4 parts of methacrylic acid (MAA) (ethylene dimethacrylate is not Used).
- ⁇ Comparative example 2> A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition was prepared by adding 85.9 parts of styrene (St), 10 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and 0. The composition was changed to 1 part.
- Example 3 A nonaqueous secondary battery and its components were manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed.
- the monomer composition was mixed with 15.9 parts of styrene (St), 80 parts of n-butyl acrylate (BA), 4 parts of methacrylic acid (MAA), and 0. The composition was changed to 1 part.
- Particulate polymer The amount (parts) of particulate polymer used in the preparation of the slurry composition for functional layers.
- Swelling degree S The measured value of the swelling degree for the solid content of the slurry composition for functional layers.
- Elution amount X Measured value of the elution amount for the solid content of the slurry composition for functional layers.
- D50 D50 value obtained from the measurement result of the volume average particle diameter D of the inorganic particles.
- Adhesiveness Evaluation results of adhesiveness of the functional layer for non-aqueous secondary batteries.
- Blocking characteristics Evaluation results of the blocking characteristics of the separator or electrode.
- Example 14 it is an evaluation result of a positive electrode
- Example 15 it is an evaluation result of a negative electrode
- others are evaluation results of a separator.
- Low temperature output characteristics Evaluation results of low temperature output characteristics of non-aqueous secondary batteries.
- Life characteristics Evaluation results of life characteristics of non-aqueous secondary batteries.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
すなわち、本発明は以下の通りである。
前記粒子状重合体が、
20重量%以上80重量%以下の芳香族モノビニル単量体単位;及び
0.01重量%以上2重量%以下の多価エチレン性不飽和系架橋性単量体単位
を含む共重合体であり、
前記粒子状重合体の体積平均粒子径Dが、0.5μm以上5μm以下であり、かつ、
前記粒子状重合体の電解液に対する膨潤度が、1倍超3倍以下である、非水系二次電池機能層用組成物。
〔2〕 前記粒子状重合体の前記電解液への溶出量が、0.01重量%以上10重量%以下である、〔1〕に記載の非水系二次電池機能層用組成物。
〔3〕 さらに無機粒子を含む、〔1〕又は〔2〕に記載の非水系二次電池機能層用組成物。
〔4〕 〔1〕~〔3〕のいずれか一項に記載の非水系二次電池機能層用組成物を用いて形成した、非水系二次電池用機能層。
〔5〕 正極と、負極と、セパレータと、電解液とを備える非水系二次電池であって、
前記正極、前記負極及び前記セパレータの1以上が、〔4〕に記載の非水系二次電池用機能層を有する、非水系二次電池。
〔6〕 粒子状重合体を含む非水系二次電池用機能層であって、
前記粒子状重合体が、
20重量%以上80重量%以下の芳香族モノビニル単量体単位;及び
0.01重量%以上2重量%以下の多価エチレン性不飽和系架橋性単量体
を含む共重合体であり、
前記粒子状重合体の体積平均粒子径が、0.5μm以上5μm以下であり、かつ、
前記粒子状重合体の所定の電解液に対する膨潤度が、1倍超3倍以下である、非水系二次電池用機能層。
本発明の非水系二次電池機能層用組成物は、特定の粒子状重合体を含む。
粒子状重合体は、粒子状の形状を有する重合体である。粒子状重合体は、機能層用組成物及びそれを用いて形成した機能層において、粒子状の形状を維持しうる。
芳香族モノビニル単量体単位を形成しうる芳香族モノビニル単量体としては、スチレン、スチレンスルホン酸及びその塩(例えば、スチレンスルホン酸ナトリウムなど)、α-メチルスチレン、ビニルトルエン、4-(tert-ブトキシ)スチレンなどが挙げられる。これらの中でも、スチレン、スチレンスルホン酸ナトリウムが好ましく、スチレンがより好ましい。これらは1種単独で、又は、2種以上を組み合わせて用いることができる。
多価エチレン性不飽和系架橋性単量体単位を形成しうる多価エチレン性不飽和系架橋性単量体は、2つ以上のエチレン性不飽和結合を有する化合物である。多価エチレン性不飽和系架橋性単量体の例としては、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、トリメチロールプロパン-トリ(メタ)アクリレートなどの多官能(メタ)アクリレート類;ジプロピレングリコールジアリルエーテル、ポリグリコールジアリルエーテル、トリエチレングリコールジビニルエーテル、ヒドロキノンジアリルエーテル、テトラアリルオキシエタンなどの多官能アリル/ビニルエーテル類;ジビニルベンゼンなどが挙げられる。これらの中でも、エチレングリコールジ(メタ)アクリレート及びアリル(メタ)アクリレートが好ましく、エチレングリコールジ(メタ)アクリレートがより好ましい。これらは1種単独で、又は、2種以上を組み合わせて用いることができる。
粒子状重合体は、芳香族モノビニル単量体単位及び多価エチレン性不飽和系架橋性単量体単位に加えて、任意の単位を含みうる。任意の単位の例としては、(メタ)アクリル酸アルキルエステル単量体単位及び酸性基含有単量体単位が挙げられる。
粒子状重合体の体積平均粒子径Dは、好ましくは0.5μm以上であり、好ましくは5μm以下、より好ましくは2μm以下、さらに好ましくは1.5μm以下である。体積平均粒子径Dを前記下限値以上にすることにより、表面に露出した粒子状重合体による、機能層と、機能層に接する層との良好な接着力を得ることができる。体積平均粒子径Dを前記上限値以下にすることにより、機能層の厚みを薄くすることが可能となり、ひいては、非水系二次電池の高容量化を実現することができる。
粒子状重合体は、機能層組成物の調製、機能層組成物を用いた機能層の形成、及び二次電池における機能層の使用に際して、その粒子状の形状の少なくとも一部が維持されることが好ましい。そのため、粒子状重合体のガラス転移温度は、ある程度以上高いことが好ましい。具体的には、粒子状重合体のガラス転移温度は、好ましくは20℃以上、より好ましくは30℃以上、更に好ましくは35℃以上である。粒子状重合体のガラス転移温度の上限は特に限定されないが、通常65℃以下としうる。本願において、ガラス転移温度は、JIS K7121に準じて、市販の示差走査熱量分析計等を用いて測定しうる。具体的には、以下の手順で測定しうる。まず、測定対象を、厚み1±0.3mmのフィルムに成形する。このフィルムを、120℃の熱風オーブンで1時間乾燥させる。その後、乾燥させたフィルムをサンプルとして、JIS K7121に準じて、測定温度-100℃~180℃、昇温速度5℃/分にて、示差走査熱量分析計(DSC6220SII、ナノテクノロジー社製)を用いてガラス転移温度(℃)を測定する。
粒子状重合体は、電解液に対する膨潤度が、特定の範囲内である。電解液に対する膨潤度とは、粒子状重合体を成形しフィルムとし、これを所定の電解液に60℃で72時間浸漬することによる重量の変化の割合である。膨潤度の具体的な測定方法は、以下の通りである。即ち、乾燥させた粒子状重合体0.2g程度を、200℃、5MPaのプレス条件で、2分間プレスすることにより、フィルムとする。得られたフィルムを1cm角に裁断し、試験片とし、この試験片の重量W0を測定する。その後、試験片を、所定の電解液に60℃で72時間浸漬する。その後、試験片を電解液から取り出し、表面の電解液を拭き取り、試験片の重量W1を測定する。得られた重量W0及びW1の値から、粒子状重合体の膨潤度S(倍)を、式S=W1/W0により求める。上記所定の電解液としては、所定の混合溶媒に、支持電解質を1mol/Lの濃度で溶解して得られる非水電解液を用いる。所定の混合溶媒としては、エチレンカーボネート(EC)と、ジエチルカーボネート(DEC)と、ビニレンカーボネート(VC)を、体積比:EC/DEC/VC=68.5/30/1.5で混合したものを用いる。支持電解質としては、LiPF6を用いる。
機能層用組成物の固形分100重量%中の粒子状重合体の含有割合は、好ましくは3重量%以上、より好ましくは4重量%以上、特に好ましくは5重量%以上であり、好ましくは95重量%以下、より好ましくは90重量%以下、特に好ましくは85重量%以下である。本願において、機能層用組成物の固形分とは、機能層用組成物を用いた、乾燥の工程を含む機能層の形成の後に、当該機能層に残留する成分をいい、通常は、溶媒以外の全成分の合計となる。粒子状重合体の含有割合を前記範囲内とすることにより、スラリー状に調製した機能層用組成物を、塗布に適した性状を有するものとすることができる。
粒子状重合体は、上に述べた複数の単量体を共重合することにより調製しうる。共重合体の調製において、単量体の割合は、通常、粒子状重合体における単量体単位の割合と同じ割合としうる。
本発明の非水系二次電池機能層用組成物は、粒子状重合体に加えて、任意の成分を含みうる。例えば、本発明の非水系二次電池機能層用組成物は、分散媒を含みうる。分散媒を含むことにより、本発明の非水系二次電池機能層用組成物を、スラリーの性状を有するものとしうる。以下において、本発明の非水系二次電池機能層用組成物であってスラリーの性状を有するものを、「機能層用スラリー組成物」ということがある。機能層用スラリー組成物を用いた、乾燥の工程を含む機能層の形成においては、分散媒は揮発し、それにより、機能層用スラリー組成物の固形分からなる機能層を得ることができる。
本発明の非水系二次電池機能層用組成物は、任意の成分として無機粒子を含みうる。無機粒子は、無機化合物の粒子である。無機粒子は、機能層用組成物に含まれうる分散媒にも、非水系二次電池の非水電解液にも溶解せず、それらの中においても、その形状を維持しうる。
無機粒子は、1種類を単独で使用してもよいし、2種類以上を組み合わせて用いてもよい。
無機粒子の体積平均粒子径は、好ましくは0.1μm以上、より好ましくは、0.20μm以上、さらにより好ましくは0.30μm以上であり、好ましくは1.0μm以下、より好ましくは0.90μm以下、さらにより好ましくは0.80μm以下である。体積平均粒子径を前記下限値以上にすることにより、非水系二次電池機能層用組成物において無機粒子をスラリー状に分散させることが可能となる。また、機能層において粒子間の結着力を発現させることができ、ひいては機能層に剥離力が負荷された際の凝集破壊を抑制することができ、機能層の接着力を向上させることができる。さらに、機能層に熱が負荷されたときの収縮を低減することができる。体積平均粒子径を前記上限値以下にすることにより、機能層の膜厚を薄くすることができ、ひいては、非水系二次電池の高容量化を実現することができる。また、機能層用組成物をスラリー状に調製した場合において、機能層用組成物にチキソトロピーを付与することができ、その結果、粒子状重合体の浮きを抑制し、機能層のブロッキングを抑制させることができる。
機能層用組成物の固形分100重量%中の無機粒子の含有割合は、好ましくは40重量%以上、より好ましくは50重量%以上、特に好ましくは60重量%以上であり、好ましくは99重量%以下、より好ましくは98重量%以下、特に好ましくは97重量%以下である。無機粒子の含有割合を前記範囲内とすることにより、得られる機能層に多孔性の性状を付与し、機能層を多孔膜として用いうる層としうる。また、無機粒子の含有割合を前記範囲内とすることにより、スラリー状に調製した機能層用組成物を、塗布に適した性状を有するものとすることができる。
本発明の非水系二次電池機能層用組成物においては、無機粒子対粒子状重合体の重量比は、所望の性状の機能層用組成物及び機能層が得られるよう適宜調整しうる。無機粒子及び粒子状重合体の合計100重量%における無機粒子の割合は、好ましくは50重量%以上、より好ましくは55重量%以上、さらにより好ましくは60重量%以上であり、一方好ましくは95重量%以下、より好ましくは90重量%以下、さらにより好ましくは85重量%以下である。無機粒子及び粒子状重合体の合計における無機粒子の割合を前記下限値以上とすることにより、機能層のブロッキングを抑制することができ、また、乾燥状態での耐熱収縮性も、電解液中での耐熱収縮性(二次電池を製造する際の電極及びセパレータ等の構成要素をプレスする条件により、機能層を他の構成要素と接着させた状態における、電解液中での加熱による収縮の少なさ)も良好な機能層を得ることができる。無機粒子及び粒子状重合体の合計における無機粒子の割合を前記上限値以下とすることにより、相対的な粒子状重合体の割合を多くすることができ、その結果、機能層の電極への確実な接着を達成することができる。
本発明の非水系二次電池機能層用組成物は、任意の成分として機能層用結着材を含みうる。機能層用結着材は、非水系二次電池用機能層を構成する成分同士を互いに結着する能力、特には、上述した無機粒子同士を互いに結着する能力及び無機粒子と粒子状重合体を互いに結着する能力を有するものとしうる。
本発明の非水系二次電池機能層用組成物は、上に述べた成分以外に、他の任意の成分を含みうる。前記任意の成分は、機能層を用いた二次電池における電池反応に過度に好ましくない影響を及ぼさないものであれば、特に制限は無い。また、前記任意の成分の種類は、1種類でもよく、2種類以上でもよい。
前記任意の成分としては、例えば、濡れ剤、レベリング剤、電解液分解抑制剤、水溶性高分子化合物などが挙げられる。なお、水溶性高分子化合物としては特に限定されず、例えば特開2014-063754号公報の記載のものを使用することができる。
機能層用組成物の調製方法は、特に限定はされないが、通常は、上述した粒子状重合体と、必要に応じて用いられる任意の成分(分散媒、無機粒子、機能層用結着材、及びその他の任意の成分)とを混合して得られる。混合方法は特に制限されないが、各成分を効率よく分散させるべく、混合装置として分散機を用いて混合を行う。
分散機は、上記成分を均一に分散および混合できる装置が好ましい。例を挙げると、ボールミル、サンドミル、顔料分散機、擂潰機、超音波分散機、ホモジナイザー、プラネタリーミキサーなどが挙げられる。
本発明の非水系二次電池用機能層は、上述した非水系二次電池機能層用組成物を用いて形成したものである。
本発明の非水系二次電池用機能層は、例えば、上述した機能層用組成物を適切な基材の表面に塗布して塗膜を形成した後、形成した塗膜を乾燥することにより、形成することができる。
本発明の非水系二次電池用機能層は、上述した本発明の非水系二次電池機能層用組成物を用いて形成しているので、優れた接着性を発現することができる。したがって、非水系二次電池において本発明の非水系二次電池用機能層を、例えば他の構成要素を接着するための接着層、又は正極と負極とを離隔するための多孔膜として設けた場合、非水系二次電池の低温出力特性及び寿命特性の向上等の効果を発現することができる。
ここで、機能層用組成物を塗布する基材に制限は無く、例えば離型基材の表面に機能層用組成物の塗膜を形成し、その塗膜を乾燥して機能層を形成し、機能層から離型基材を剥がしてもよい。このように、離型基材から剥がされた機能層を自立膜として二次電池の電池部材の形成に用いることもできる。具体的には、離型基材から剥がした機能層をセパレータ基材の上に積層して機能層を備えるセパレータを形成してもよいし、離型基材から剥がした機能層を電極基材の上に積層して機能層を備える電極を形成してもよい。
しかし、機能層を剥がす工程を省略して電池部材の製造効率を高める観点からは、基材としてセパレータ基材または電極基材を用いることが好ましい。セパレータ基材および電極基材上に設けられた機能層は、セパレータおよび電極の耐熱性や強度などを向上させる保護層(耐熱層)として好適に機能しうる。
セパレータ基材は、特に限定されず、有機セパレータ基材などの任意のセパレータ基材としうる。有機セパレータ基材は、有機材料からなる多孔性部材である。有機セパレータ基材の例としては、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、芳香族ポリアミド樹脂などを含む微機能層及び不織布が挙げられる。強度に優れることからポリエチレン製の微機能層及び不織布が好ましい。有機セパレータ基材の厚さは、任意の厚さとすることができ、通常0.5μm以上、好ましくは5μm以上であり、通常40μm以下、好ましくは35μm以下、より好ましくは30μm以下である。
電極基材(正極基材および負極基材)は、特に限定されず、集電体及びその上に設けられた電極合材層を備えるものとしうる。
集電体、電極合材層中の電極活物質(正極活物質及び負極活物質)及び電極合材層用結着材(正極合材層用結着材及び負極合材層用結着材)、並びに、集電体上への電極合材層の形成方法は、既知のものを用いることができる。例えば特開2013-145763号公報に記載のものを採用しうる。
セパレータ基材及び電極基材などの基材上に機能層を形成する方法としては、以下の方法が挙げられる。
(1)機能層用組成物をセパレータ基材または電極基材の表面(電極基材の場合は電極合材層側の表面、以下同じ)に塗布し、次いで乾燥する方法;
(2)機能層用組成物にセパレータ基材または電極基材を浸漬後、これを乾燥する方法;
(3)機能層用組成物を離型基材上に塗布、乾燥して機能層を製造し、得られた機能層をセパレータ基材または電極基材の表面に転写する方法;
これらの中でも、前記(1)の方法が、機能層の膜厚制御をしやすいことから特に好ましい。前記(1)の方法は、詳細には、機能層用組成物を基材上に塗布する工程(塗布工程)、基材上に塗布された機能層用組成物を乾燥させて機能層を形成する工程(乾燥工程)を含む。
塗布工程において、機能層用組成物を基材上に塗布する方法は、特に制限は無い。塗布方法の例としては、ドクターブレード法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、及びハケ塗り法が挙げられる。
基材上の機能層用組成物を乾燥する方法は、特に限定されず、既知の方法を用いることができる。乾燥方法の例としては、温風、熱風、低湿風による乾燥、真空乾燥、赤外線や電子線などの照射による乾燥方法が挙げられる。乾燥条件は特に限定されず、乾燥温度は好ましくは50~100℃で、乾燥時間は好ましくは5~30分である。
本発明の非水系二次電池用機能層の厚みは、好ましくは0.01μm以上、より好ましくは0.1μm以上、更に好ましくは1μm以上であり、好ましくは20μm以下、より好ましくは10μm以下、更に好ましくは5μm以下である。機能層の厚みが0.01μm以上であることで、機能層の強度を十分に確保することができ、20μm以下であることで、電解液の拡散性を確保し、機能層を用いた二次電池の性能を向上させることができる。
本発明の非水系二次電池用機能層は、特定の粒子状重合体を含むことにより、接着性の高い機能層とすることができる。具体的には、二次電池を製造する際の電極及びセパレータ等の構成要素をプレスする条件により、容易に他の構成要素との接着を達成することができる。より具体的には、非水系二次電池用機能層をセパレータの表面の層として設けた場合、電極とセパレータとを重ね合わせ、荷重10kN/m、温度80℃といった条件でプレスすることにより、電極とセパレータとが接着し一体化した積層体を得ることができる。
本発明の非水系二次電池は、上述した本発明の非水系二次電池用機能層を備える。より具体的には、本発明の非水系二次電池は、正極、負極、セパレータ、および電解液を備え、正極、負極及びセパレータの1以上が、上述した本発明の非水系二次電池用機能層を有する。本発明の非水系二次電池は、本発明の機能層用組成物を用いて形成した機能層を備えているので、高い寿命特性(繰り返し使用における寿命)、高い低温出力特性(低温においても、常温に近い電圧を出力しうる特性)等の優れた電池特性を発揮する。
本発明の非水系二次電池が、セパレータとして上述した本発明の非水系二次電池用機能層を有するセパレータを備える場合、当該セパレータは、セパレータ基材、及びその一方の面又は両方の面上に設けられた機能層を有するものとしうる。
本発明の非水系二次電池が、電極(正極及び/又は負極)として上述した本発明の非水系二次電池用機能層を有する電極を備える場合、当該電極は、集電体、集電体上に設けられた電極合材層、及び電極合材層上に設けられた機能層を有するものとしうる。電極合材層及び機能層は、集電体の一方の面上のみに設けられてもよく、両方の面上に設けられてもよい。
本発明の非水系二次電池が、正極、負極、又はセパレータの一つとして上述した本発明の非水系二次電池用機能層を有するものを備える場合、その他は、本発明の非水系二次電池用機能層を有するものであっても良く、本発明の非水系二次電池用機能層を有しないものであっても良い。本発明の非水系二次電池用機能層を有しない電極は、例えば、集電体、及び集電体上に設けられた電極合材層からなるものとしうる。本発明の非水系二次電池用機能層を有しないセパレータは、例えば、セパレータ基材からなるものとしうる。
本発明の二次電池は非水系二次電池であり、従って、電解液としては非水系の電解液を用いる。
非水系の電解液としては、通常、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、例えば、リチウムイオン二次電池においてはリチウム塩が用いられる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどが挙げられる。なかでも、溶媒に溶けやすく高い解離度を示すので、LiPF6、LiClO4、CF3SO3Liが好ましい。電解質は1種類を単独で用いてもよく、2種類以上を組み合わせて用いてもよい。通常は、解離度の高い支持電解質を用いるほどリチウムイオン伝導度が高くなる傾向があるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。
電解液中の電解質の濃度は適宜調整しうる。また、電解液には、既知の添加剤を添加してもよい。
上述した本発明の非水系二次電池は、例えば、正極と負極とをセパレータを介して重ね合わせ、これを必要に応じて、巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口することで製造することができる。正極、負極、セパレータのうち、少なくとも一つの部材を機能層付きの部材とする。また、電池容器には、必要に応じてエキスパンドメタルや、ヒューズ、PTC素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をしてもよい。電池の形状は、例えば、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、何れであってもよい。
以下の説明において、量を表す「%」及び「部」は、別に断らない限り重量基準である。また、以下に説明する操作は、別に断らない限り、常温及び常圧の条件において行った。
(体積平均粒子径D)
粒子状重合体の体積平均粒子径Dは、レーザー回折法を用いて測定した。具体的には、粒子を含む水分散液(固形分濃度0.1重量%)を測定試料として調製して、レーザー回折式粒子径分布測定装置(ベックマン・コールター社製、製品名「LS-230」)を用いて粒子の体積平均粒子径を測定した。より具体的には、該レーザー回折式粒子径分布測定装置の測定結果から得られた粒度分布(体積基準)において、小径側からの累積体積が50%となる粒子径を、体積平均粒子径(μm)とした。
粒子状重合体を含む水分散液をポリテトラフルオロエチレン製のシャーレに入れ、25℃、48時間の条件で乾燥して粉末を作成した。その粉末0.2g程度を、200℃、5MPaのプレス条件で、2分間プレスすることにより、フィルムを得た。得られたフィルムを1cm角に裁断し、試験片を得た。この試験片の重量W0を測定した。
その後、試験片を、所定の電解液に60℃で72時間浸漬した。その後、試験片を電解液から取り出し、表面の電解液を拭き取り、試験片の重量W1を測定した。
得られた重量W0及びW1の値から、粒子状重合体の膨潤度S(倍)を、式S=W1/W0により求めた。
上記所定の電解液としては、所定の混合溶媒に、支持電解質を1mol/Lの濃度で溶解して得られる非水電解液を用いた。所定の混合溶媒としては、エチレンカーボネート(EC)と、ジエチルカーボネート(DEC)と、ビニレンカーボネート(VC)を、体積比:EC/DEC/VC=68.5/30/1.5で混合したものを用いた。支持電解質としては、LiPF6を用いた。
膨潤度測定後の試験片をメタノールで5回洗浄後、乾燥させた。乾燥後の試験片の重量W2を測定した。
得られた重量W0及びW2の値から、溶出量X(%)を、式X=(W2/W0)×100により求めた。
機能層用結着材を含む水分散液又は粒子状重合体を含む水分散液を、50%湿度、23~25℃の環境下で3日間乾燥させて、厚み1±0.3mmのフィルムを得た。このフィルムを、120℃の熱風オーブンで1時間乾燥させた。この乾燥させたフィルムをサンプルとして、JIS K7121に準じて、測定温度-100℃~180℃、昇温速度5℃/分にて、示差走査熱量分析計(DSC6220SII、ナノテクノロジー社製)を用いてガラス転移温度(℃)を測定した。
実施例及び比較例で得た電極及びセパレータのそれぞれを切り出し、幅10mm×長さ50mmの切片とした。電極としては、実施例14では正極を切り出し、他の実施例及び比較例では負極を切り出した。
電極の切片とセパレータの切片とを重ね合わせた。実施例14では、セパレータ切片は、そのセパレータ基材側の面(多孔膜を有しない側の面)が正極の切片に接触させるよう重ね合わせた。実施例15では、セパレータ切片は、そのセパレータ基材側の面が負極の切片に接触させるよう重ね合わせた。
重ね合わせた切片を、ロールプレスを用いて、荷重10kN/m、温度80℃の条件でプレスすることにより、電極の切片及びセパレータの切片が一体化した試験片を得た。
水平な試験台の上に、セロハンテープを、粘着面を上向きにして固定した。この際、セロハンテープとしてはJIS Z1522に規定されるものを用いた。得られた試験片の電極側の面を下にして、セロハンテープに貼り付けた。そして、試験片のうちセパレータ側の一端を、50mm/分の速度で鉛直方向に引張って剥がし、そのときの応力を測定した。同じ測定を3回行い、測定結果の平均値をピール強度として求めた。得られたピール強度の値に基づき、以下の基準にて接着性を判定した。ピール強度の値が大きいほど、非水系二次電池用機能層の接着性が高いことを示す。
A:ピール強度が20N/m以上
B:ピール強度が15N/m以上20N/m未満
C:ピール強度が15N/m未満
実施例及び比較例で得たセパレータ又は電極を裁断して、幅5cm×長さ5cmの正方形の切片とした。セパレータ又は電極としては、実施例14では正極を切り出し、実施例15では負極を切り出し、その他の実施例及び比較例ではセパレータを切り出した。
2枚の切片を重ね合わせ、40℃、10g/cm2の加圧条件下に5分間置いて、測定試料を作製した。
得られた測定試料を24時間放置した後、ブロッキング強度を測定した。具体的には、測定試料を2cm×5cmの短冊状に裁断した後に、2枚の切片の一方を水平に固定し、もう一方を50mm/分の速度で鉛直方向に引張って剥がし、そのときの応力を測定した。同様の測定を3回行い、測定結果の平均値をブロッキング強度として求めた。得られたブロッキング強度の値に基づき、以下の基準にてブロッキング特性を判定した。
A:24時間放置後に接着していない。
B:ブロッキング強度が0N/m超0.25N/m未満
C:ブロッキング強度が0.25N/m以上
実施例及び比較例で製造した800mAh捲回型リチウムイオン二次電池を、25℃の環境下で24時間静置した。その後、25℃の環境下で、0.1Cの充電レートで5時間の充電を行い、充電完了後の電圧V0を測定した。
次に、-10℃環境下で、1Cの放電レートにて放電を行い、放電開始から15秒後の電圧V1を測定した。そして、電圧変化ΔVを、ΔV=V0-V1の式にて計算した。
計算で得られた電圧変化ΔVの値に基づき、以下の基準にて非水系二次電池の低温出力特性を判定した。当該電圧変化ΔVの値が小さいほど、非水系二次電池の低温出力特性が優れていることを示す。
A:電圧変化ΔVが100mV未満
B:電圧変化ΔVが100mV以上200mV未満
C:電圧変化ΔVが200mV以上
実施例および比較例で製造した800mAhの非水系二次電池を、25℃環境下、一定電流800mAで4.2Vまで充電後、4.2V一定電圧で電流値が20mAとなるまで充電した。その後、25℃環境下、一定電流800mAで3.0Vまで放電を行なった。この充放電を繰り返し、放電容量が640mAhとなった時点を電池の寿命とした。評価はA~Eの5段階で行い、充放電回数が多いほど、寿命特性に優れることを示す。
A:500回以上
B:450回以上500回未満
C:400回以上450回未満
D:300回以上400回未満
E:300回未満
(1-1.機能層用結着材を含む水分散液の調製)
撹拌機を備えた反応器に、イオン交換水70部、乳化剤としてのラウリル硫酸ナトリウム(花王ケミカル社製、製品名「エマール2F」)0.15部、及び、重合開始剤としての過硫酸アンモニウム0.5部をそれぞれ供給した。続いて、反応器内の気相を窒素ガスで置換し、反応器内の液相の温度を60℃に昇温した。
一方、別の容器に、イオン交換水50部、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム0.5部、並びに、重合性単量体としての、n-ブチルアクリレート94部、アクリロニトリル2部、メタクリル酸2部、N-ヒドロキシメチルアクリルアミド1部、及びアリルグリシジルエーテル1部を供給し、混合することにより、単量体混合物を得た。
得られた単量体混合物を、4時間かけて前記反応器に連続的に供給し、重合を行った。単量体混合物の供給中は、反応器内の温度を60℃に保持した。単量体混合物の供給を終了した後、温度を70℃に昇温し、さらに3時間にわたって撹拌を継続し、その後、重合反応を終了した。これにより、機能層用結着材としてのアクリル系重合体を含む水分散液を調製した。機能層用結着材のガラス転移温度を測定したところ-11℃であった。
撹拌機付き5MPa耐圧容器に、単量体組成物、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム1部、イオン交換水150部、並びに、重合開始剤としての過硫酸カリウム0.5部を入れ、十分に攪拌した後、60℃に加温した。単量体組成物は、スチレン(St)75部、n-ブチルアクリレート(BA)20部、メタクリル酸(MAA)4部、及びエチレングリコールジメタクリレート(EDMA)1部からなる組成物とした。これにより、重合性単量体の重合を開始した。重合転化率が96%になった時点で、反応媒体を冷却して、重合反応を停止させた。これにより、粒子状重合体を含む水分散液を調製した。
得られた粒子状重合体の体積平均粒子径D、膨潤度S、及び溶出量Xを測定した。また、粒子状重合体のガラス転移温度を測定したところ60℃であった。
無機粒子としてのアルミナ(住友化学社製、製品名「AKP3000」、体積平均粒子径:0.5μm;密度3.9g/cm3)を固形分相当で80重量部と、(1-2)で得た粒子状重合体の水分散液を固形分相当で20重量部と、(1-1)で得た機能層用結着材の水分散液を固形分相当で5重量部と、増粘剤としてのポリアクリルアミド(PAAm)を1.5重量部と、分散剤としてのポリアクリル酸ナトリウム(製品名:アクアリックGL366、日本触媒社製)を0.8重量部と、反応媒体中の固形分濃度が40%となる量のイオン交換水を、ボールミルを用いて混合した。これにより、機能層用スラリー組成物を調製した。
セパレータ基材として、ポリプロピレン/ポリエチレン/ポリプロピレンの3層で構成されたセパレータ基材(セパレータの厚さ:25μm、製品名「セルガード2325」)を用意した。このセパレータ基材の一方の表面の上に、(1-3)で得た機能層用スラリー組成物を、その厚みが2μmとなるように塗布し、その後、50℃で10分間乾燥させた。これにより、セパレータ基材の一方の面の上に非水系二次電池用機能層を形成した。続いて、この操作と同じ操作により、セパレータ基材のもう一方の表面の上にも非水系二次電池用機能層を形成した。これにより、セパレータ基材及びその両面に設けられた非水系二次電池用機能層を有するセパレータを得た。得られたセパレータにおいて、各層の機能層の厚さは、2μmであった。得られたセパレータについて、ブロッキング特性を評価した。
重合性単量体としての、スチレン61.5部、1,3-ブタジエン35部、及びイタコン酸3.5部、連鎖移動剤としてのt-ドデシルメルカプタン0.25部、並びに、乳化剤としてのラウリル硫酸ナトリウム0.35部の混合液を用意した。混合液を、当該混合液の入った容器から耐圧容器へ供給した。当該供給と同時に、重合開始剤としての過硫酸カリウム1部を耐圧容器へ添加した。これにより、重合性単量体の重合反応を開始した。重合反応の温度は、75℃に維持した。
負極活物質としての人造黒鉛(体積平均粒子径:15.6μm)97部、及び、増粘剤としてのカルボキシメチルセルロースナトリウム塩(日本製紙社製、製品名「MAC350HC」)の2%水溶液を固形分相当で1部混合し、イオン交換水を加えて固形分濃度を68%に調整し、その後に、温度25℃下で60分間撹拌し、混合液を得た。得られた混合液に、イオン交換水を更に加えて固形分濃度を62%に調整し、その後、温度25℃下で15分間撹拌を行った。
当該混合液に、(1-5)で得た負極用結着材の水分散液を固形分相当で2部加え、イオン交換水を加えて、最終固形分濃度を52%にし、10分間撹拌を続けて、重合体混合液を得た。当該重合体混合液を減圧下で脱泡処理し、負極用スラリー組成物を得た。
(1-6)で得た負極用スラリー組成物を、負極用集電体としての銅箔(厚さ20μm)の一方の面の上に、乾燥後の膜厚が150μm程度になるようにコンマコーターを用いて塗布した。次に、負極用スラリー組成物が塗布された銅箔を、0.5m/分の速度で温度60℃のオーブン内を2分間かけて搬送することにより、当該負極用スラリー組成物を乾燥させた。その後、負極用スラリー組成物が塗布された銅箔に対し、温度120℃下にて2分間加熱処理を行った。これにより、負極用集電体の一方の面に負極用合材層を形成した。引き続いて、同じ操作を、負極用集電体のもう一方の面に対しても行うことにより、負極用集電体、及びその両面の上に設けられた負極合材層を備える負極原反を得た。当該負極原反をロールプレスで圧延することにより、各面の負極合材層の厚みが80μmである、負極を得た。得られた負極及び(1-4)で得たセパレータについて、セパレータの電極に対する接着性を評価した。
正極活物質としてのNMC(LiNi0.8Co0.1Mn0.1O2、体積平均粒子径:10μm)を94部、導電材としてのアセチレンブラック(電気化学工業社製、製品名「HS-100」)を3部、及び、正極用結着材としてポリフッ化ビニリデン(クレハ社製、製品名「#7208」)を固形分相当で3部混合し、当該混合物に溶媒としてN-メチルピロリドンを加え、全固形分濃度を70%に調整した混合液を得た。そして、当該混合液をプラネタリーミキサーにより混合した。これにより、正極用スラリー組成物を得た。
(1-8)で得た正極用スラリー組成物を、正極用集電体としてのアルミニウム箔(厚さ20μm)の一方の面の上に、乾燥後の膜厚が150μm程度になるようにコンマコーターを用いて塗布した。次に、正極用スラリー組成物が塗布されたアルミニウム箔を、0.5m/分の速度で温度60℃のオーブン内を2分間かけて搬送することにより、当該正極用スラリー組成物を乾燥させた。その後、正極用スラリー組成物が塗布されたアルミニウム箔に対し、温度120℃下にて2分間加熱処理を行った。これにより、正極用集電体の一方の面に正極用合材層を形成した。引き続いて、同じ操作を、正極用集電体のもう一方の面に対しても行うことにより、正極用集電体、及びその両面の上に設けられた正極合材層を備える正極原反を得た。当該正極原反をロールプレスで圧延することにより、各面の正極合材層の厚みが60μmである、正極を得た。
(1-9)で得た正極を切り出し、49cm×5.0cmの矩形の正極を得た。(1-4)で得たセパレータを切り出し、55cm×5.5cmの矩形のセパレータを2枚得た。また、(1-7)で得た負極を切り出し、50cm×5.2cmの矩形の負極を得た。
これらを重ねて、(矩形の正極)/(矩形のセパレータ)/(矩形の負極)/(矩形のセパレータ)の層構成を有する積層体を得た。
得られた積層体を捲回機によって長手方向端部から捲回して、捲回体を得た。更に、当該捲回体を温度70℃及び圧力1.0MPaのプレス条件で8秒間プレスすることにより、扁平体とした。
そして、当該扁平体を、非水系二次電池用の外装材としてのアルミニウム包材で包んだ。続いて、アルミニウム包材が形成する空間に、電解液(電解質:濃度1MのLiPF6、溶媒:エチレンカーボネート(EC)/ジエチルカーボネート(DEC)/ビニレンカーボネート(VC)=68.5/30/1.5(体積比))を空気が残らないように注入した。さらに、アルミニウム包材の開口を150℃でヒートシールすることにより、アルミニウム外装を密封閉口した。これにより、非水系二次電池として、捲回型リチウムイオン二次電池(I)を製造した。この非水系二次電池の容量は800mAhであった。
得られた捲回型の非水系二次電池について、低温出力特性及び寿命特性を評価した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)80部、n-ブチルアクリレート(BA)15部、メタクリル酸(MAA)4部、及びエチレンジメタクリレート(EDMA)1部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)55部、n-ブチルアクリレート(BA)40部、メタクリル酸(MAA)4部、及びエチレンジメタクリレート(EDMA)1部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)20部、n-ブチルアクリレート(BA)75部、メタクリル酸(MAA)4部、及びエチレンジメタクリレート(EDMA)1部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)75.99部、n-ブチルアクリレート(BA)20部、メタクリル酸(MAA)4部、及びエチレンジメタクリレート(EDMA)0.01部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)75部、n-ブチルアクリレート(BA)20部、メタクリル酸(MAA)3部、及びエチレンジメタクリレート(EDMA)2部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)75部、n-ブチルアクリレート(BA)20部、メタクリル酸(MAA)4.6部、及びアリルメタクリレート(AMA)0.4部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、乳化剤の量を1.2部に変更することにより、得られる粒子状重合体の体積平均粒子径Dを0.5μmとした。
(9-1.機能層用の粒子状重合体の調製)
撹拌機付き5MPa耐圧容器に、単量体組成物、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム1.2部、イオン交換水150部、並びに、重合開始剤としての過硫酸カリウム0.5部を入れ、十分に攪拌した後、60℃に加温した。単量体組成物は、スチレン(St)75部、n-ブチルアクリレート(BA)20部、メタクリル酸(MAA)4部、及びエチレングリコールジメタクリレート(EDMA)1部からなる組成物とした。これにより、重合性単量体の重合を開始した。重合転化率が96%になった時点で、反応媒体を冷却して、重合反応を停止させた。これにより、シード粒子を含む水分散液を調製した。
さらに、追加の単量体組成物を、シード粒子の水分散液に加えた。追加の単量体組成物は、スチレン(St)75000部、n-ブチルアクリレート(BA)20000部、メタクリル酸(MAA)4000部、及びエチレングリコールジメタクリレート(EDMA)1000からなる組成物とした。混合物を十分に攪拌した後、60℃に加温した。これにより、重合性単量体の重合を開始した。重合転化率が96%になった時点で、反応媒体を冷却して、重合反応を停止させた。これにより、体積平均粒子径5.0μmの粒子状重合体を含む水分散液を調製した。
得られた粒子状重合体の体積平均粒子径D、膨潤度S、溶出量X、及びガラス転移温度を測定した。
以下の事項を変更した他は、実施例1の(1-1)及び(1-3)~(1-10)と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・粒子状重合体の水分散液として、(1-2)で得たものに代えて、(9-1)で得たものを用いた。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-3)において、無機粒子を用いなかった。
・(1-3)において、粒子状重合体の使用量を100重量部に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-3)において、無機粒子として、アルミナ80重量部に代えて、ベーマイト(河合石灰工業社製「(商品名)BMM」;個数平均粒子径0.9μm;密度3.5g/cm3;(酸化アルミニウムの水和物:AlOOH))を76重量部用いた。
・(1-3)において、粒子状重合体の使用量を24重量部に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-3)において、無機粒子の使用量を49重量部に変更した。
・(1-3)において、粒子状重合体の使用量を51重量部に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-3)において、無機粒子の使用量を94重量部に変更した。
・(1-3)において、粒子状重合体の使用量を6重量部に変更した。
(14-1.機能層付き正極の作製)
実施例1の(1-9)で得た正極の一方の表面の上に、(1-3)で得た機能層用スラリー組成物を、その厚みが2μmとなるように塗布し、その後、50℃で10分間乾燥させた。これにより、正極の一方の面の上に非水系二次電池用機能層を形成した。続いて、この操作と同じ操作により、正極のもう一方の表面の上にも非水系二次電池用機能層を形成した。これにより、集電体、集電体の両面に設けられた正極合材層、及び各正極合材層の上に設けられた非水系二次電池用機能層を有する、機能層付き性極を得た。得られた機能層付き正極において、各々の機能層の厚さは、2.0μmであった。得られた機能層付き正極について、ブロッキング特性を評価した。
セパレータ基材の両方の面ではなく、一方の面のみに非水系二次電池用機能層を形成した他は、実施例1の(1-4)と同じ操作により、非水系二次電池用機能層を有するセパレータを得た。得られたセパレータは、セパレータ基材及びその片面のみに設けられた非水系二次電池用機能層を有していた。得られたセパレータ及び(14-1)で得た正極について、接着性を評価した。
以下の事項を変更した他は、実施例1の(1-10)と同じ操作により、非水系二次電池を製造し評価した。
・(1-9)で得た正極に代えて、(14-1)で得た機能層付き正極を用いた。
・(1-4)で得たセパレータに代えて、(14-2)で得たセパレータを用いた。
・(矩形の正極)/(矩形のセパレータ)/(矩形の負極)/(矩形のセパレータ)の層構成を有する積層体において、矩形のセパレータの向きを、その機能層側の面が矩形の負極に対向する向きとした。
(15-1.機能層付き負極の作製)
実施例1の(1-7)で得た負極の一方の表面の上に、実施例1の(1-3)で得た機能層用スラリー組成物を、その厚みが2μmとなるように塗布し、その後、50℃で10分間乾燥させた。これにより、負極の一方の面の上に非水系二次電池用機能層を形成した。続いて、この操作と同じ操作により、負極のもう一方の表面の上にも非水系二次電池用機能層を形成した。これにより、集電体、集電体の両面に設けられた負極合材層、及び各負極合材層の上に設けられた非水系二次電池用機能層を有する、機能層付き負極を得た。得られた機能層付き負極において、各々の機能層の厚さは、2.0μmであった。得られた機能層付き負極について、ブロッキング特性を評価した。
以下の事項を変更した他は、実施例1の(1-10)と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-7)で得た負極に代えて、(15-1)で得た機能層付き負極を用いた。
・(1-4)で得たセパレータに代えて、実施例14の(14-2)で得たセパレータを用いた。接着性の評価は、得られたセパレータ及び(15-1)で得た正極について行った。
・(矩形の正極)/(矩形のセパレータ)/(矩形の負極)/(矩形のセパレータ)の層構成を有する積層体において、矩形のセパレータの向きを、そのセパレータ基材側の面が矩形の負極に対向する向きとした。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)75部、n-ブチルアクリレート(BA)20部、及びメタクリル酸(MAA)4部からなる組成物(エチレンジメタクリレートは不使用)に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)85.9部、n-ブチルアクリレート(BA)10部、メタクリル酸(MAA)4部、及びアリルメタクリレート(AMA)0.1部からなる組成物に変更した。
以下の事項を変更した他は、実施例1と同じ操作により、非水系二次電池及びその構成要素を製造し評価した。
・(1-2)において、単量体組成物を、スチレン(St)15.9部、n-ブチルアクリレート(BA)80部、メタクリル酸(MAA)4部、及びアリルメタクリレート(AMA)0.1部からなる組成物に変更した。
St:スチレン使用量(部)。
BA:n-ブチルアクリレー使用量(部)。
MMA:メチルメタクリレート使用量(部)。
EDMA:エチレンジメタクリレート使用量(部)。
AMA:アリルメタクリレート使用量(部)。
粒子Tg:粒子状重合体のガラス転移温度(℃)。
無機粒子:機能層用スラリー組成物調製における無機粒子使用量(部)。実施例1においてはベーマイトの使用量。その他においてはアルミナの使用量。
粒子状重合体:機能層用スラリー組成物調製における粒子状重合体使用量(部)。
膨潤度S:機能層用スラリー組成物の固形分についての膨潤度の測定値。
溶出量X:機能層用スラリー組成物の固形分についての溶出量の測定値。
D50:無機粒子の体積平均粒子径Dの測定結果から得られたD50値。
接着性:非水系二次電池用機能層の接着性の評価結果。
ブロッキング特性:セパレータ又は電極のブロッキング特性の評価結果。実施例14においては正極の評価結果であり、実施例15においては負極の評価結果であり、その他においてはセパレータの評価結果である。
低温出力特性:非水系二次電池の低温出力特性の評価結果。
寿命特性:非水系二次電池の寿命特性の評価結果。
表1~表3の結果から、粒子状重合体が本発明の要件を満たす実施例においては、接着性、ブロッキング特性、低温出力特性及び寿命特性においてバランス良く優れた結果が得られることが分かる。これに対して、膨潤度が本発明の規定の範囲外である比較例1、並びに単量体単位の組成が本発明の規定の範囲外である比較例2及び3では、実施例に比べて劣る評価結果が得られた。
Claims (6)
- 粒子状重合体を含む非水系二次電池機能層用組成物であって、
前記粒子状重合体が、
20重量%以上80重量%以下の芳香族モノビニル単量体単位;及び
0.01重量%以上2重量%以下の多価エチレン性不飽和系架橋性単量体単位
を含む共重合体であり、
前記粒子状重合体の体積平均粒子径Dが、0.5μm以上5μm以下であり、かつ、
前記粒子状重合体の電解液に対する膨潤度が、1倍超3倍以下である、非水系二次電池機能層用組成物。 - 前記粒子状重合体の前記電解液への溶出量が、0.01重量%以上10重量%以下である、請求項1に記載の非水系二次電池機能層用組成物。
- さらに無機粒子を含む、請求項1又は2に記載の非水系二次電池機能層用組成物。
- 請求項1~3のいずれか一項に記載の非水系二次電池機能層用組成物を用いて形成した、非水系二次電池用機能層。
- 正極と、負極と、セパレータと、電解液とを備える非水系二次電池であって、
前記正極、前記負極及び前記セパレータの1以上が、請求項4に記載の非水系二次電池用機能層を有する、非水系二次電池。 - 粒子状重合体を含む非水系二次電池用機能層であって、
前記粒子状重合体が、
20重量%以上80重量%以下の芳香族モノビニル単量体単位;及び
0.01重量%以上2重量%以下の多価エチレン性不飽和系架橋性単量体
を含む共重合体であり、
前記粒子状重合体の体積平均粒子径が、0.5μm以上5μm以下であり、かつ、
前記粒子状重合体の所定の電解液に対する膨潤度が、1倍超3倍以下である、非水系二次電池用機能層。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL17841321.7T PL3503253T3 (pl) | 2016-08-17 | 2017-07-14 | Kompozycja warsty funkcyjnej dla niewodnego akumulatora, warstwa funkcyjna dla niewodnego akumulatora i niewodny akumulator |
CN201780047435.3A CN109565017B (zh) | 2016-08-17 | 2017-07-14 | 非水系二次电池功能层用组合物、非水系二次电池用功能层及非水系二次电池 |
EP17841321.7A EP3503253B1 (en) | 2016-08-17 | 2017-07-14 | Nonaqueous secondary battery functional layer composition, nonaqueous secondary battery functional layer, and nonaqueous secondary battery |
US16/323,324 US11417933B2 (en) | 2016-08-17 | 2017-07-14 | Nonaqueous secondary battery functional layer composition, nonaqueous secondary battery functional layer, and nonaqueous secondary battery |
JP2018534304A JP6988808B2 (ja) | 2016-08-17 | 2017-07-14 | 非水系二次電池機能層用組成物、非水系二次電池用機能層及び非水系二次電池 |
KR1020197002513A KR102422558B1 (ko) | 2016-08-17 | 2017-07-14 | 비수계 이차 전지 기능층용 조성물, 비수계 이차 전지용 기능층 및 비수계 이차 전지 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-159810 | 2016-08-17 | ||
JP2016159810 | 2016-08-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018034093A1 true WO2018034093A1 (ja) | 2018-02-22 |
Family
ID=61197358
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/025765 WO2018034093A1 (ja) | 2016-08-17 | 2017-07-14 | 非水系二次電池機能層用組成物、非水系二次電池用機能層及び非水系二次電池 |
Country Status (8)
Country | Link |
---|---|
US (1) | US11417933B2 (ja) |
EP (1) | EP3503253B1 (ja) |
JP (1) | JP6988808B2 (ja) |
KR (1) | KR102422558B1 (ja) |
CN (1) | CN109565017B (ja) |
HU (1) | HUE065401T2 (ja) |
PL (1) | PL3503253T3 (ja) |
WO (1) | WO2018034093A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020077618A (ja) * | 2018-09-26 | 2020-05-21 | 東レ株式会社 | 多孔性フィルム、二次電池用セパレータおよび二次電池 |
JP2021501453A (ja) * | 2017-10-30 | 2021-01-14 | アーケマ・インコーポレイテッド | リチウムイオンバッテリーセパレーター |
KR20220140491A (ko) | 2020-02-12 | 2022-10-18 | 니폰 제온 가부시키가이샤 | 전기 화학 소자용 적층체 및 전기 화학 소자 |
WO2022249933A1 (ja) * | 2021-05-27 | 2022-12-01 | 日本ゼオン株式会社 | 全固体二次電池用バインダー組成物、全固体二次電池用スラリー組成物、全固体二次電池用機能層、および全固体二次電池 |
KR20220161300A (ko) | 2020-03-31 | 2022-12-06 | 니폰 제온 가부시키가이샤 | 전기 화학 소자 기능층용 조성물, 전기 화학 소자용 적층체, 및 전기 화학 소자 |
KR20220161301A (ko) | 2020-03-31 | 2022-12-06 | 니폰 제온 가부시키가이샤 | 전기 화학 소자 기능층용 조성물, 전기 화학 소자용 기능층, 전기 화학 소자용 적층체, 및 전기 화학 소자 |
WO2024048378A1 (ja) * | 2022-08-31 | 2024-03-07 | 日本ゼオン株式会社 | 電気化学素子機能層用組成物、電気化学素子用機能層、電気化学素子用積層体、および電気化学素子 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015145967A1 (ja) * | 2014-03-24 | 2015-10-01 | 日本ゼオン株式会社 | 非水系二次電池多孔膜用バインダー、非水系二次電池多孔膜用組成物、非水系二次電池用多孔膜および非水系二次電池 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008210686A (ja) | 2007-02-27 | 2008-09-11 | Sanyo Electric Co Ltd | 非水電解質二次電池及びその製造方法 |
WO2009096528A1 (ja) | 2008-01-30 | 2009-08-06 | Zeon Corporation | 多孔膜および二次電池電極 |
KR101801049B1 (ko) * | 2010-08-31 | 2017-11-24 | 제온 코포레이션 | 전지 다공막용 슬러리 조성물, 이차 전지용 다공막의 제조 방법, 이차 전지용 다공막, 이차 전지용 전극, 이차 전지용 세퍼레이터 및 이차 전지 |
KR102165556B1 (ko) * | 2012-04-05 | 2020-10-14 | 제온 코포레이션 | 이차 전지용 세퍼레이터 |
WO2013161786A1 (ja) * | 2012-04-23 | 2013-10-31 | 日本ゼオン株式会社 | リチウムイオン二次電池 |
KR102129829B1 (ko) * | 2012-06-20 | 2020-07-03 | 제온 코포레이션 | 리튬 이온 이차 전지 부극용 슬러리, 리튬 이온 이차 전지용 전극 및 그 제조 방법, 그리고 리튬 이온 이차 전지 |
WO2014157715A1 (ja) | 2013-03-27 | 2014-10-02 | Jsr株式会社 | 蓄電デバイス用バインダー組成物 |
JP6186852B2 (ja) | 2013-04-30 | 2017-08-30 | 日本ゼオン株式会社 | 二次電池多孔膜用スラリー組成物、二次電池用電極、二次電池用セパレータおよび二次電池 |
EP3021380B1 (en) * | 2013-07-10 | 2018-04-18 | Zeon Corporation | Porous film composition for lithium ion secondary batteries, separator for lithium ion secondary batteries, electrode for lithium ion secondary batteries, and lithium ion secondary battery |
KR101783568B1 (ko) * | 2013-10-07 | 2017-09-29 | 닛산 지도우샤 가부시키가이샤 | 비수전해질 이차 전지용 전극 재료, 및 이것을 사용한 비수전해질 이차 전지용 전극 및 비수전해질 이차 전지 |
JP6409782B2 (ja) * | 2013-10-31 | 2018-10-24 | 日本ゼオン株式会社 | リチウムイオン二次電池のバインダー用の粒子状重合体、接着層及び多孔膜組成物 |
JP2015145967A (ja) | 2014-02-03 | 2015-08-13 | キヤノン株式会社 | 画像形成装置、エンジンおよびこれらの制御方法 |
KR102422232B1 (ko) | 2014-06-27 | 2022-07-15 | 니폰 제온 가부시키가이샤 | 비수계 이차전지 기능층용 조성물, 비수계 이차전지용 기능층 및 비수계 이차전지 |
KR102493659B1 (ko) * | 2014-11-28 | 2023-01-30 | 니폰 제온 가부시키가이샤 | 비수계 2차 전지 기능층용 조성물, 비수계 2차 전지용 기능층 및 비수계 2차 전지 |
EP3474348B1 (en) * | 2016-06-21 | 2023-10-11 | Zeon Corporation | Composition for non-aqueous secondary battery function layer, functional layer for non-aqueous secondary battery, and non-aqueous secondary battery |
-
2017
- 2017-07-14 EP EP17841321.7A patent/EP3503253B1/en active Active
- 2017-07-14 HU HUE17841321A patent/HUE065401T2/hu unknown
- 2017-07-14 PL PL17841321.7T patent/PL3503253T3/pl unknown
- 2017-07-14 US US16/323,324 patent/US11417933B2/en active Active
- 2017-07-14 WO PCT/JP2017/025765 patent/WO2018034093A1/ja active Application Filing
- 2017-07-14 JP JP2018534304A patent/JP6988808B2/ja active Active
- 2017-07-14 CN CN201780047435.3A patent/CN109565017B/zh active Active
- 2017-07-14 KR KR1020197002513A patent/KR102422558B1/ko active IP Right Grant
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015145967A1 (ja) * | 2014-03-24 | 2015-10-01 | 日本ゼオン株式会社 | 非水系二次電池多孔膜用バインダー、非水系二次電池多孔膜用組成物、非水系二次電池用多孔膜および非水系二次電池 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021501453A (ja) * | 2017-10-30 | 2021-01-14 | アーケマ・インコーポレイテッド | リチウムイオンバッテリーセパレーター |
JP7381459B2 (ja) | 2017-10-30 | 2023-11-15 | アーケマ・インコーポレイテッド | リチウムイオンバッテリーセパレーター |
JP2020077618A (ja) * | 2018-09-26 | 2020-05-21 | 東レ株式会社 | 多孔性フィルム、二次電池用セパレータおよび二次電池 |
JP7327044B2 (ja) | 2018-09-26 | 2023-08-16 | 東レ株式会社 | 多孔性フィルム、二次電池用セパレータおよび二次電池 |
KR20220140491A (ko) | 2020-02-12 | 2022-10-18 | 니폰 제온 가부시키가이샤 | 전기 화학 소자용 적층체 및 전기 화학 소자 |
KR20220161300A (ko) | 2020-03-31 | 2022-12-06 | 니폰 제온 가부시키가이샤 | 전기 화학 소자 기능층용 조성물, 전기 화학 소자용 적층체, 및 전기 화학 소자 |
KR20220161301A (ko) | 2020-03-31 | 2022-12-06 | 니폰 제온 가부시키가이샤 | 전기 화학 소자 기능층용 조성물, 전기 화학 소자용 기능층, 전기 화학 소자용 적층체, 및 전기 화학 소자 |
WO2022249933A1 (ja) * | 2021-05-27 | 2022-12-01 | 日本ゼオン株式会社 | 全固体二次電池用バインダー組成物、全固体二次電池用スラリー組成物、全固体二次電池用機能層、および全固体二次電池 |
WO2024048378A1 (ja) * | 2022-08-31 | 2024-03-07 | 日本ゼオン株式会社 | 電気化学素子機能層用組成物、電気化学素子用機能層、電気化学素子用積層体、および電気化学素子 |
Also Published As
Publication number | Publication date |
---|---|
EP3503253A1 (en) | 2019-06-26 |
JP6988808B2 (ja) | 2022-01-05 |
JPWO2018034093A1 (ja) | 2019-06-13 |
PL3503253T3 (pl) | 2024-04-29 |
US20200052270A1 (en) | 2020-02-13 |
US11417933B2 (en) | 2022-08-16 |
KR20190039932A (ko) | 2019-04-16 |
KR102422558B1 (ko) | 2022-07-18 |
CN109565017B (zh) | 2023-03-24 |
EP3503253A4 (en) | 2020-01-01 |
HUE065401T2 (hu) | 2024-05-28 |
CN109565017A (zh) | 2019-04-02 |
EP3503253B1 (en) | 2024-01-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6943247B2 (ja) | 非水系二次電池多孔膜用組成物、非水系二次電池用多孔膜及び非水系二次電池 | |
JP6988808B2 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層及び非水系二次電池 | |
WO2019131348A1 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用電池部材、非水系二次電池用積層体の製造方法、および非水系二次電池 | |
US20170309916A1 (en) | Binder for non-aqueous secondary battery, composition for non-aqueous secondary battery functional layer, functional layer for non-aqueous secondary battery, and non-aqueous secondary battery | |
US10714722B2 (en) | Composition for non-aqueous secondary battery functional layer, functional layer for non-aqueous secondary battery, and non-aqueous secondary battery | |
JPWO2016017066A1 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層付き基材、非水系二次電池用積層体の製造方法および非水系二次電池 | |
JP6737182B2 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池 | |
WO2016031163A1 (ja) | 非水系二次電池用積層体および非水系二次電池部材の製造方法 | |
JP6515574B2 (ja) | 非水系二次電池機能層用バインダー、非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池 | |
JP6702327B2 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池 | |
WO2020090395A1 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層、非水系二次電池用セパレータ、および非水系二次電池 | |
WO2019065130A1 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池 | |
JP6891392B2 (ja) | 非水系二次電池用積層体 | |
WO2019131347A1 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用電池部材、非水系二次電池用積層体の製造方法、および、非水系二次電池 | |
JP2016154108A (ja) | 非水系二次電池機能層用バインダー組成物、非水系二次電池機能層用スラリー組成物、非水系二次電池用機能層、非水系二次電池およびその製造方法 | |
JP7020475B2 (ja) | 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池 | |
JP2017103056A (ja) | 非水系二次電池機能層用組成物、非水系二次電池機能層用組成物の製造方法、非水系二次電池用機能層及び非水系二次電池 | |
WO2023162605A1 (ja) | 非水系二次電池接着層用組成物、非水系二次電池用接着層、非水系二次電池用電池部材及びその製造方法、非水系二次電池用積層体及びその製造方法、並びに、非水系二次電池 | |
WO2023008319A1 (ja) | 電気化学素子機能層用組成物及びその製造方法、電気化学素子用機能層及び電気化学素子 | |
WO2022124126A1 (ja) | 電気化学素子機能層用組成物、電気化学素子用積層体及び電気化学素子 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2018534304 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17841321 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20197002513 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2017841321 Country of ref document: EP Effective date: 20190318 |