Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • 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
  • 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
  • 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
  • H01M50/42—Acrylic 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
  • H01M50/411—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
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • 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
  • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic 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
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • 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
  • H01M50/494—Tensile strength
• • 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
• • 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 provides a binder composition for a non-aqueous secondary battery functional layer, a slurry composition for a non-aqueous secondary battery functional layer, a non-aqueous secondary battery functional layer, a non-aqueous secondary battery member, and a non-aqueous secondary battery. It is about.
• Non-aqueous secondary batteries such as lithium-ion secondary batteries (hereinafter sometimes simply referred to as “secondary batteries”) are characterized by their small size, light weight, high energy density, and the ability to be charged and discharged repeatedly. Yes, it is used for a wide range of purposes.
• a secondary battery generally comprises electrodes (a positive electrode and a negative electrode) and non-aqueous secondary battery members such as a separator that separates the positive electrode and the negative electrode (hereinafter sometimes simply referred to as “battery member”). It has
• the battery member of the secondary battery contains a binder, and optionally contains particles (hereinafter referred to as "functional particles") that are blended to allow the battery member to exhibit a desired function.
• a member provided with a functional layer for a non-aqueous secondary battery (hereinafter sometimes simply abbreviated as "functional layer”) is used.
• a separator for a secondary battery a separator having an adhesive layer containing a binder and a heat-resistant layer containing a binder and inorganic particles as functional particles on a separator base material is used. It is
• Patent Documents 1 to 4 propose compositions containing water-soluble polymers capable of exhibiting various favorable attributes.
• the functional layer provided in the secondary battery was required to have a low water content and excellent heat resistance.
• the functional layer formed using the conventional composition it was not possible to achieve both a reduction in water content and excellent heat resistance at a sufficiently high level.
• the present invention provides a binder composition for a non-aqueous secondary battery functional layer and a slurry composition for a non-aqueous secondary battery functional layer that can form a functional layer having a low water content and excellent heat resistance.
• Another object of the present invention is to provide a functional layer having a low water content and excellent heat resistance, and a non-aqueous secondary battery member including the functional layer.
• Another object of the present invention is to provide a non-aqueous secondary battery comprising a non-aqueous secondary battery member having a functional layer with a low water content and excellent heat resistance.
• the inventor of the present invention has made intensive studies with the aim of solving the above problems.
• the present inventors have found that the 10% molecular weight is 100,000 or less, and the storage elastic modulus E5 at a temperature of 50°C and a relative humidity of 5% and the storage elastic modulus E50 at a temperature of 50°C and a relative humidity of 50 %
• a binder composition for a non-aqueous secondary battery functional layer containing a water-soluble polymer that satisfies a predetermined relationship can form a functional layer with a low water content and excellent heat resistance, I completed the present invention.
• a binder composition for a secondary battery functional layer wherein the 10% molecular weight of the water-soluble polymer is 100,000 or less, and the storage elastic modulus of the water-soluble polymer at a temperature of 50°C and a relative humidity of 5% is defined as E5 , and the storage elastic modulus at a temperature of 50° C. and a relative humidity of 50% is defined as E50 , and the following formula (1) is satisfied. 0.300 ⁇ ( E5 - E50 ) /E5 ⁇ 0.990 (1) Thus, the 10% molecular weight is 100,000 or less, and the storage elastic modulus E5 at a temperature of 50° C.
• a binder composition containing a water-soluble polymer that satisfies the relationship of .300 ⁇ (E 5 ⁇ E 50 )/E 5 ⁇ 0.990 forms a functional layer with a low water content and excellent heat resistance. be able to.
• the 10% molecular weight and various storage elastic moduli of the water-soluble polymer can be measured according to the methods described in Examples of the present specification.
• the water-soluble polymer in the binder composition for a non-aqueous secondary battery functional layer of [1], preferably has a weight-average molecular weight of 700,000 or less. If the weight average molecular weight of the water-soluble polymer is 700,000 or less, the coatability of the obtained slurry composition for functional layer can be improved. Incidentally, the weight average molecular weight of the water-soluble polymer can be measured according to the method described in the Examples of the present specification.
• the water-soluble polymer preferably contains an amide group-containing monomer unit. If the water-soluble polymer contains amide group-containing monomer units, the heat resistance of the resulting functional layer can be enhanced.
• the "monomer unit" of the polymer means "a repeating unit derived from the monomer and contained in the polymer obtained using the monomer".
• the water-soluble polymer preferably has a glass transition temperature of 150° C. or higher. If the glass transition temperature of the water-soluble polymer is 150°C or higher, the heat resistance of the resulting functional layer can be enhanced. Incidentally, the glass transition temperature of the water-soluble polymer can be measured according to the method described in the examples of the present specification.
• the binder composition for a non-aqueous secondary battery functional layer has a storage elastic modulus E5 of 3 ⁇ 10 8 Pa or more. is preferred.
• the value of the storage elastic modulus E5 is 3 ⁇ 10 8 Pa or more, the heat resistance of the resulting functional layer can be enhanced.
• the water-soluble polymer contains a monomer unit having an ionic functional group. is preferred. If the water-soluble polymer contains a monomer unit having an ionic functional group, the dispersion stability of the resulting slurry composition can be enhanced.
• the ionic functional group is preferably a cationic group of a quaternary ammonium salt. If the water-soluble polymer contains a monomer unit containing a cationic group of a quaternary ammonium salt, the water content of the resulting functional layer can be further reduced.
• the slurry composition for a non-aqueous secondary battery functional layer of the present invention has a volume average particle size of 0.05 ⁇ m or more. It is characterized by comprising inorganic particles of 0.50 ⁇ m or less, a solvent, and the binder composition for non-aqueous secondary battery function according to any one of [1] to [7] above.
• the functional layer formed using a slurry composition containing inorganic particles having a volume average particle diameter of 0.05 ⁇ m or more and 0.50 ⁇ m or less, a solvent, and any of the binder compositions described above has a water content Small amount and excellent heat resistance.
• the volume average particle diameter of the inorganic particles can be measured by the method described in the Examples of the present specification.
• the inorganic particles preferably have a specific surface area of 3.5 m 2 /g or more and 20 m 2 /g or less.
• the specific surface area of the inorganic particles is 3.5 m 2 /g or more and 20 m 2 /g or less, the resulting functional layer can have a further reduced moisture content and a further improved heat resistance.
• the specific surface area of the inorganic particles means "BET (Brunauer Emmett Teller) specific surface area" and can be measured by the method described in the examples of the present specification.
• an object of the present invention is to advantageously solve the above problems, and the functional layer for a non-aqueous secondary battery of the present invention comprises the non-aqueous two It is characterized by being formed using a slurry composition for a secondary battery functional layer.
• a functional layer has a low moisture content and excellent heat resistance.
• an object of the present invention is to advantageously solve the above-mentioned problems, and a non-aqueous secondary battery member of the present invention comprises the functional layer for a non-aqueous secondary battery of [10] above. It is characterized by having A battery member having such a functional layer can improve the cycle characteristics of the secondary battery.
• an object of the present invention is to advantageously solve the above problems, and a non-aqueous secondary battery of the present invention comprises the non-aqueous secondary battery member of [11] above. Characterized by A secondary battery including the battery member described above has excellent cycle characteristics.
• the binder composition for non-aqueous secondary battery functional layers and the slurry composition for non-aqueous secondary battery functional layers which can form the functional layer which has little water content and is excellent in heat resistance are provided. be able to.
• the binder composition for non-aqueous secondary battery functional layers of the present invention can be used for preparing the slurry composition for non-aqueous secondary battery functional layers of the present invention.
• the slurry composition for non-aqueous secondary battery functional layer of the present invention is an arbitrary functional layer (for example, electrode mixture layer , a heat-resistant layer, and an adhesive layer), and can be particularly suitably used for forming a heat-resistant layer.
• the non-aqueous secondary battery member of the present invention includes a functional layer formed from the slurry composition for a non-aqueous secondary battery functional layer of the present invention.
• a non-aqueous secondary battery of the present invention includes the non-aqueous secondary battery member of the present invention.
• the binder composition of the present invention contains a water-soluble polymer as an essential ingredient and may optionally contain a solvent and other ingredients.
• the water-soluble polymer has a 10% molecular weight of 100,000 or less, and the storage elastic modulus of the water-soluble polymer at a temperature of 50 ° C. and a relative humidity of 5% is E5 , and storage at a temperature of 50 ° C. and a relative humidity of 50%
• E 50 is the modulus of elasticity. 0.300 ⁇ ( E5 - E50 ) /E5 ⁇ 0.990 (1)
• the binder composition of the present invention contains a water-soluble polymer that satisfies the above attributes, it is possible to form a functional layer with a low water content and excellent heat resistance. More specifically, the fact that the 10% molecular weight of the water-soluble polymer is 100,000 or less means that the molecular weight at the position corresponding to 10% from the low molecular weight side in the molecular weight distribution curve of the water-soluble polymer is 100,000 or less. is. This means that the water-soluble polymer contains 10% by volume of components having a molecular weight of 100,000 or less. Such low molecular weight components can function as dispersants when preparing slurry compositions.
• the density of the resulting functional layer can be increased and the mechanical strength thereof can be increased.
• the heat resistance of the obtained functional layer can be enhanced by containing the predetermined water-soluble polymer.
• the low molecular weight component of the water-soluble polymer protects the functional groups on the surface of the inorganic particles when the slurry composition is prepared, thereby suppressing the adsorption of moisture on the surface of the inorganic particles and obtaining a secondary It is possible to improve the cycle characteristics of the battery.
• the storage elastic modulus E5 at a temperature of 50°C and a relative humidity of 5% and the storage elastic modulus E50 at a temperature of 50°C and a relative humidity of 50 % of the water-soluble polymer were compared.
• the degree of decrease storage modulus change rate; (E 5 ⁇ E 50 )/E 5 value) is 0.300 or more, the movement of the inorganic particles is abruptly restricted in the drying process during the formation of the functional layer. It is considered that the heat resistance of the obtained functional layer can be improved by suppressing the heat resistance and increasing the density of the obtained functional layer.
• the degree of decrease in the storage elastic modulus E50 is 0.990 or less, it means that the water-soluble polymer does not excessively adsorb moisture, and the moisture content of the resulting functional layer increases. can be suppressed.
• the water-soluble polymer has a 10% molecular weight of 100,000 or less, a storage elastic modulus at a temperature of 50 ° C. and a relative humidity of 5% as E5 , and a storage elastic modulus at a temperature of 50 ° C. and a relative humidity of 50% as E50. , it is necessary to satisfy the following formula (1). 0.300 ⁇ ( E5 - E50 ) /E5 ⁇ 0.990 (1)
• the 10% molecular weight of the water-soluble polymer must be 100,000 or less, preferably 70,000 or less, more preferably 40,000 or less, and preferably 3,000 or more. , is more preferably 5,000 or more, and more preferably 10,000 or more. If the 10% molecular weight of the water-soluble polymer is equal to or less than the above upper limit, the heat resistance of the resulting functional layer can be enhanced. Further, when the 10% molecular weight of the water-soluble polymer is at least the above lower limit, the water content of the resulting functional layer can be further reduced.
• the 10% molecular weight of the water-soluble polymer can be adjusted based on the conditions (temperature, time, polymerization initiator addition amount and addition timing, etc.) in synthesizing the water-soluble polymer.
• the water-soluble polymer preferably has a storage modulus E 5 value of 3 ⁇ 10 8 Pa or more, more preferably 5 ⁇ 10 8 Pa or more at a temperature of 50° C. and a relative humidity of 5%.
• the upper limit of the storage modulus E 5 is preferably 1 ⁇ 10 10 Pa or less, more preferably 6 ⁇ 10 9 Pa or less.
• the value of the storage elastic modulus E5 is at least the above lower limit, the heat resistance of the resulting functional layer can be further enhanced.
• the value of the storage elastic modulus E5 is equal to or less than the upper upper limit, it is possible to effectively suppress the occurrence of cracks in the obtained functional layer.
• the value of the storage modulus of the water-soluble polymer can be comprehensively controlled according to the type, composition, molecular weight, and the like of the water-soluble polymer.
• the water-soluble polymer must satisfy the following formula (1), where E5 is the storage modulus at 50°C and 5% relative humidity, and E50 is the storage modulus at 50°C and 50% relative humidity. and 0.300 ⁇ ( E5 - E50 ) /E5 ⁇ 0.990 (1) Furthermore, the value of (E 5 -E 50 )/E 5 more preferably satisfies the following formula (2). 0.500 ⁇ ( E5 - E50 ) /E5 ⁇ 0.990 (2) Further, the value of (E 5 -E 50 )/E 5 more preferably satisfies the following formula (3).
• the weight average molecular weight of the water-soluble polymer is preferably 700,000 or less, more preferably 500,000 or less, even more preferably 400,000 or less, and 200,000 or more. Preferably, it is 250,000 or more.
• the weight-average molecular weight is equal to or less than the above upper limit, it is possible to suppress an increase in viscosity when preparing a slurry composition, and to improve coatability. Further, when the weight-average molecular weight is at least the above lower limit, the heat resistance of the resulting functional layer can be further enhanced, and the relatively high-molecular-weight component exerts a thickening effect on the binder composition and the slurry composition.
• the weight average molecular weight of the water-soluble polymer depends on the conditions for synthesizing the water-soluble polymer (in particular, the amount of the polymerization initiator, the amount of the molecular weight modifier, the monomer composition, temperature, time, etc.). can be adjusted accordingly.
• composition of the water-soluble polymer is not particularly limited as long as the 10% molecular weight and (E 5 -E 50 )/E 5 values satisfy the essential conditions mentioned above.
• the water-soluble polymer may contain amide group-containing monomeric units, monomeric units having ionic functional groups, and other monomeric units copolymerizable with these monomeric units. Above all, it preferably contains at least one of an amide group-containing monomer unit and a monomer unit having an ionic functional group, and more preferably contains both of them.
• the glass transition temperature of the water-soluble polymer is increased, and the heat resistance of the resulting functional layer can be further enhanced.
• the water-soluble polymer contains a monomer unit having an ionic functional group, in the slurry composition, an electrostatic interaction occurs with the functional group on the surface of the inorganic particles, and the surface of the inorganic particles Adsorption of water-soluble polymers becomes easier. As a result, the moisture content of the resulting functional layer can be further reduced.
• amide group-containing monomers capable of forming amide group-containing monomer units include methacrylamide, acrylamide, dimethylacrylamide, diethylacrylamide, diacetone acrylamide, hydroxyethylacrylamide, hydroxymethylacrylamide, hydroxypropylacrylamide and hydroxybutylacrylamide. , and so on. One of these may be used alone, or two or more of them may be used in combination at any ratio. Among these, acrylamide is preferable from the viewpoint of heat resistance.
• the content of the amide group-containing monomer units in the water-soluble polymer is preferably 75% by mass or more, preferably 80% by mass or more, based on 100% by mass of all repeating units constituting the water-soluble polymer. is more preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90.0% by mass or less. If the content of the amide group-containing monomer units in the water-soluble polymer is at least the above lower limit, the heat resistance of the resulting functional layer can be further enhanced. Further, when the content of the amide group-containing monomer unit in the water-soluble polymer is equal to or less than the above upper limit, the dispersibility of the inorganic particles can be further enhanced when preparing the slurry composition.
• the content of the amide group-containing monomer unit in the water-soluble polymer is equal to or less than the above upper limit, the water content of the functional layer may be further reduced.
• the content of amide group-containing monomeric units in the water-soluble polymer can be measured using a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
• the monomer having an ionic functional group capable of forming a monomer unit having an ionic functional group includes a monomer having a cationic functional group and a monomer having an anionic functional group.
• Examples of monomers having a cationic functional group include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium methylsulfate, (meth)acryloylamino Examples include cationic groups of quaternary ammonium salts such as propyltrimethylammonium methylsulfate and diallyldimethylammonium chloride. One of these may be used alone, or two or more of them may be used in combination at any ratio. Among these, diallyldimethylammonium chloride is preferable from the viewpoint of further reducing the moisture content of the resulting functional layer.
• monomers having an anionic functional group examples include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid and itaconic acid, t-butylacrylamidosulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid. , and sulfonic acid group-containing monomers such as sodium p-styrenesulfonate, phosphoric acid group-containing monomers such as 2-(meth)acryloyloxyethyl phosphate and methyl-2-(meth)acryloyloxyethyl phosphate body. One of these may be used alone, or two or more of them may be used in combination at any ratio. Among these, acrylic acid is preferable from the viewpoint of further reducing the moisture content of the resulting functional layer.
• the content of the monomer unit having an ionic functional group in the water-soluble polymer is preferably 1% by mass or more, preferably 2% by mass or more, based on 100% by mass of all repeating units constituting the water-soluble polymer. is more preferable, 10% by mass or more is still more preferable, 25% by mass or less is preferable, and 20% by mass or less is more preferable. If the proportion of monomer units having an ionic functional group in the water-soluble polymer is at least the above lower limit, the dispersion stability in preparing the slurry composition can be further enhanced. Moreover, if the content of monomer units having an ionic functional group in the water-soluble polymer is equal to or less than the above upper limit, the water content of the resulting functional layer can be further reduced.
• Other monomer units that can be contained in the water-soluble polymer are not particularly limited, and include nitrile group-containing monomer units and (meth)acrylic acid ester monomer units.
• the nitrile group-containing monomer that can form the nitrile group-containing monomer unit is not particularly limited, and an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer can be mentioned.
• ⁇ , ⁇ -ethylenically unsaturated nitrile monomers include acrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -bromoacrylonitrile, methacrylonitrile, ⁇ -ethylacrylonitrile and the like. In addition, these may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
• the content of other monomer units contained in the water-soluble polymer is preferably 5% by mass or less with respect to 100% by mass of all repeating units constituting the water-soluble polymer. This is because the heat resistance of the resulting functional layer can be further enhanced.
• the water-soluble polymer may not contain other monomer units, but when it does contain 0.5% by mass of the total repeating units constituting the water-soluble polymer as 100% by mass. or more.
• the water-soluble polymer preferably has a glass transition temperature of 130° C. or higher, more preferably 150° C. or higher, preferably 300° C. or lower, and further preferably 250° C. or lower. If the glass transition temperature of the water-soluble polymer is at least the above lower limit, the heat resistance of the resulting functional layer can be further enhanced. Moreover, if the glass transition temperature of the water-soluble polymer is equal to or lower than the above upper limit, it is possible to effectively suppress the inorganic particles from falling off from the functional layer when the functional layer is formed.
• the glass transition temperature of the water-soluble polymer can be adjusted based on the composition, molecular weight, and the like.
• the water-soluble polymer can be produced, for example, by polymerizing a monomer composition containing the monomers described above in an aqueous solvent.
• aqueous solvent water, a mixture of water and a water-miscible organic solvent, a water-soluble buffer solution, an acidic aqueous solution, a basic aqueous solution, and the like can be used.
• the polymerization method is not particularly limited, and any method such as solution polymerization method, suspension polymerization method, bulk polymerization method and emulsion polymerization method can be used.
• the reaction form of polymerization may be, for example, ionic polymerization, radical polymerization, living radical polymerization, or the like.
• Additives such as a polymerization initiator, a molecular weight modifier, and a polymerization accelerator used for polymerization may be commonly used ones.
• the amount of these additives used can also be the amount generally used.
• the polymerization conditions can be appropriately adjusted according to the polymerization method, the type of the polymerization initiator, etc., in order to achieve the desired molecular weight distribution.
• the binder composition of the present invention can contain water as a solvent.
• the solvent may be the reaction solvent used for the preparation of the water-soluble polymer.
• the binder composition of the present invention can contain components (other components) other than the above components.
• the binder composition may contain polymer components other than the water-soluble polymers described above, such as known particulate binders such as styrene-butadiene random copolymers and acrylic polymers.
• the binder composition may also contain known additives. Such known additives include, for example, antioxidants, defoamers, surfactants, and the like.
• other components may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
• the binder composition of the present invention is not particularly limited, and can be prepared by mixing the water-soluble polymer and any of the above-described optional components.
• the binder does not contain any components other than the water-soluble polymer and the solvent, the prepared water-soluble polymer can be directly used as the binder composition.
• the slurry composition of the present invention is a composition used for forming a functional layer, and contains inorganic particles having a volume average particle diameter of 0.05 ⁇ m or more and 0.50 ⁇ m or less, a solvent, and the binder composition described above. , may optionally contain other ingredients besides these. Further, since the slurry composition of the present invention contains the binder composition described above, it is possible to form a functional layer having a low water content and excellent heat resistance.
• the binder composition As the binder composition, the binder composition of the present invention described above is used.
• the blending amount of the binder composition is preferably 0.5% by mass or more, more preferably 1.0%, based on the blending amount of the water-soluble polymer in the slurry composition being 100% by mass of the inorganic particles. It can be determined to be not less than mass %, preferably not more than 5.0 mass %, more preferably not more than 3.0 mass %. If the blending amount of the water-soluble polymer in the slurry composition is at least the above lower limit, the heat resistance of the resulting functional layer can be further enhanced. Further, if the blending amount of the water-soluble polymer in the slurry composition is equal to or less than the above upper limit, the water content of the resulting functional layer can be further reduced.
• the inorganic particles should have a volume average particle diameter of 0.05 ⁇ m or more and 0.50 ⁇ m or less, more preferably 0.10 ⁇ m or more and 0.45 ⁇ m or less. If the volume average particle diameter of the inorganic particles is at least the above lower limit, the moisture content of the functional layer can be further reduced. Further, when the volume average particle diameter of the inorganic particles is equal to or less than the above upper limit, it is possible to suppress deterioration of the heat resistance of the functional layer.
• the binder composition of the present invention is used in combination with the inorganic particles having a small particle size as described above, thereby reducing the moisture content of the functional layer, improving the heat resistance, and further improving the cycle characteristics of the secondary battery.
• inorganic particles examples include aluminum oxide (alumina), hydrated aluminum oxide (boehmite), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO 3 , ZrO, alumina-silica composite oxide, and the like.
• Nitride particles such as aluminum nitride and boron nitride; covalent crystal particles such as silicon and diamond; sparingly soluble ion crystal particles such as barium sulfate, calcium fluoride and barium fluoride; clay fine particles; and the like. Further, these particles may be subjected to element substitution, surface treatment, solid solution treatment, or the like, if necessary. These can be used singly or in combination of two or more. Among these, alumina, boehmite and barium sulfate are preferred.
• the inorganic particles preferably have a BET specific surface area of 3.5 m 2 /g or more, more preferably 4.0 m 2 /g or more, even more preferably 4.5 m 2 /g or more, It is preferably 20 m 2 /g or less, more preferably 19 m 2 /g or less, even more preferably 17 m 2 /g or less. If the BET specific surface area is at least the above lower limit, the inorganic particles interact with each other in the functional layer to improve the mechanical strength, so that the heat resistance of the functional layer can be further enhanced. If the BET specific surface area is equal to or less than the above upper limit, the moisture content of the functional layer can be further reduced.
• solvent for the slurry composition the same solvent as the optional component of the binder composition can be used.
• the solvent can be used as the solvent for the slurry composition.
• Other components that can be blended into the slurry composition are not particularly limited, and include the same components as other components that can be blended into the binder composition of the present invention.
• another component may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
• nonionic surfactants, anionic surfactants, and cationic surfactants can be contained as surfactants.
• nonionic surfactant includes, for example, polyoxyethylene nonylphenyl ether, polyethylene glycol monostearate, ethylene oxide/propylene oxide co- polymers, sorbitan monostearate, and the like.
• the content thereof is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the inorganic particles. 0% by mass or less is preferable, and 1.0% by mass or less is more preferable. If the content of the surfactant is at least the above lower limit, it is possible to suppress the occurrence of pinholes during the formation of the functional layer. When the surfactant content is equal to or less than the above upper limit, the peel strength and heat resistance of the functional layer can be enhanced.
• a method for preparing the slurry composition is not particularly limited.
• the slurry composition can be prepared by mixing the binder composition, inorganic particles, and optionally other components in the presence of a solvent.
• the aqueous medium used in preparation of the slurry composition also includes those contained in the binder composition.
• the mixing method is not particularly limited, but the mixing is performed using a stirrer or disperser that can be commonly used.
• the slurry composition preferably has a viscosity of 20 mPa s or more, more preferably 50 mPa s or more, even more preferably 80 mPa s or more, preferably 300 mPa s or less, and 250 mPa s. ⁇ s or less, and more preferably 220 mPa ⁇ s or less. If the viscosity of the slurry composition is at least the above lower limit, it is possible to suppress the occurrence of leveling problems when the slurry composition is applied. Further, when the viscosity of the slurry composition is equal to or less than the above upper limit value, the coatability of the slurry composition can be enhanced.
• the battery member of the present invention is a member provided with a functional layer, and specifically includes a separator.
• the functional layer formed from the slurry composition of the present invention is a structure generally called a heat-resistant layer or porous film layer.
• the functional layer of the battery member of the present invention is formed from the slurry composition of the present invention described above.
• the functional layer of the present invention has a low moisture content and excellent heat resistance.
• the functional layer of the present invention can be formed, for example, by applying the slurry composition described above to the surface of an appropriate substrate to form a coating film, and then drying the formed coating film.
• the functional layer of the present invention is made of the dried slurry composition described above, and usually contains at least the water-soluble polymer and inorganic particles described above, and optionally other components.
• the preferred abundance ratio of each component is the preferred existence ratio of each component in the slurry composition. It is the same as ratio.
• the battery member of the present invention may include constituent elements other than the functional layer formed from the slurry composition of the present invention described above and the base material.
• Such constituent elements are not particularly limited, and include various layers that do not fall under the functional layer formed from the slurry composition of the present invention.
• the battery member of the present invention includes the functional layer formed from the slurry composition of the present invention containing the binder composition of the present invention, the battery member improves the cycle characteristics of the secondary battery. be able to.
• the substrate to which the slurry composition is applied is not limited, for example, a coating film of the slurry composition is formed on the surface of the release substrate, and the coating film is dried to form a functional layer, and the functional layer You may make it peel off a mold release base material from.
• 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 separator base material it is preferable to use the separator base material as the base material. Specifically, it is preferable to apply the slurry composition onto the separator substrate.
• the separator substrate is not particularly limited, but includes known separator substrates such as organic separator substrates.
• the organic separator base material is a porous member made of an organic material. Examples of the organic separator base material include polyolefin resins such as polyethylene and polypropylene, and microporous membranes or non-woven fabrics containing aromatic polyamide resins. A polyethylene microporous film or non-woven fabric is preferable because of its excellent strength.
• Examples of the method for forming a functional layer on the base material described above to produce a battery member include the following methods. 1) A method of applying the slurry composition of the present invention to the surface of a substrate and then drying; 2) a method of immersing a substrate in the slurry composition of the present invention and then drying it; and 3) coating the slurry composition of the present invention on a release substrate and drying to produce a functional layer, a method of transferring the formed functional layer to the surface of the substrate.
• the method 1) is particularly preferable because the layer thickness of the functional layer can be easily controlled.
• the method 1) includes a step of applying the slurry composition onto the substrate (application step) and a step of drying the slurry composition applied onto the substrate to form a functional layer (function layer forming step).
• the method of applying the slurry composition onto the substrate is not particularly limited, and examples thereof include doctor blade method, reverse roll method, direct roll method, gravure method, extrusion method, brush coating method, and the like. method.
• the method for drying the slurry composition on the substrate is not particularly limited, and a known method can be used. Drying methods include, for example, drying with warm air, hot air, low humidity air, vacuum drying, and drying by irradiation with infrared rays, electron beams, or the like.
• a secondary battery of the present invention includes the above-described battery member of the present invention. More specifically, the secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and the separator is the battery member described above. And the secondary battery of the present invention is excellent in cycle characteristics.
• ⁇ Positive electrode and negative electrode> Known positive and negative electrodes can be used as the positive and negative electrodes without any particular limitation.
• the separator used in the secondary battery of the present invention is the battery member of the present invention described above.
• 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 salts include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi. , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi and the like.
• LiPF 6 , LiClO 4 and CF 3 SO 3 Li are preferable because they are easily dissolved in a solvent and exhibit a high degree of dissociation.
• an electrolyte may be used individually by 1 type, and may be used in combination of 2 or more types.
• lithium ion conductivity tends to increase as a supporting electrolyte with a higher degree of dissociation is used, so the lithium ion conductivity can be adjusted depending on the type of supporting electrolyte.
• the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
• 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 by the type of solvent.
• concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate. Further, known additives may be added to the electrolytic solution.
• the positive electrode and the negative electrode are superimposed with a separator interposed therebetween, and if necessary, this is rolled, folded, compressed, etc. and put into a battery container, and the electrolyte solution is placed in the battery container. can be produced by injecting and sealing.
• At least one of the positive electrode, the negative electrode, and the separator is the battery member of the present invention having a functional layer formed from the slurry composition of the present invention.
• expanded metal, fuses, overcurrent protection elements such as PTC elements, lead plates, etc. may be placed in the battery container to prevent pressure rise inside the battery and overcharge/discharge.
• the shape of the battery may be, for example, coin-shaped, button-shaped, sheet-shaped, cylindrical, rectangular, or flat.
• ⁇ Weight average molecular weight and 10% molecular weight of water-soluble polymer> The aqueous solutions containing the water-soluble polymers produced in Examples and Comparative Examples were diluted to adjust the concentration to 0.5%. Samples were then prepared by diluting to 0.025% with the following eluent. This sample was analyzed by gel permeation chromatography under the following conditions to create two types of molecular weight distribution curves to determine the weight average molecular weight and 10% molecular weight of the water-soluble polymer. Specifically, the weight average molecular weight was calculated based on a differential molecular weight distribution curve according to a standard method.
• ⁇ Change rate of storage elastic modulus of water-soluble polymer> The aqueous solutions of the water-soluble polymers obtained in Examples and Comparative Examples were dried at room temperature to form films with a thickness of 0.05 to 0.3 mm. A strip having a width of 10 mm was punched out from the film to obtain a test piece. Using the following device, strain due to elongation was applied to the sample, and the dynamic viscoelasticity was measured at the following temperature and humidity. In the measurement, the measurement sample was attached to a jig and allowed to stand for 30 minutes under the set humidity conditions, and then the measurement was performed. Based on the obtained measurement results, the change in storage modulus due to humidity was determined.
• Apparatus manufactured by Anton Paar, product name "MCR302”, convection temperature control system "CTD 180 Humidity Ready”, measurement jig universal elongation measurement system “UXF”, humidity generator "MHG100” Setting temperature range: 50°C Set humidity: 5%, 50% Shear strain: 0.05% Frequency: 1Hz Modulus change: (storage modulus E5 at 5% RH - storage modulus E50 at 50% RH)/(storage modulus E5 at 5 % RH)
• ⁇ Glass transition temperature of water-soluble polymer> The aqueous solutions containing the water-soluble polymers prepared in Examples and Comparative Examples were pre-dried for 3 days in an environment with a humidity of 50% and a temperature of 23 to 26 ° C., and further dried in a vacuum dryer at a temperature of 120 ° C. for 10 days. A measurement sample was obtained by drying for a period of time. Weigh 5 to 10 mg from the obtained measurement sample, seal it in a sealed aluminum pan, and measure it with a differential thermal analysis measuring device (manufactured by SII, DSC7200) at a temperature range of -50 ° C. to 200 ° C. at a heating rate.
• SII differential thermal analysis measuring device
• BET specific surface area of inorganic particles was measured using a flow-type specific surface area measuring device (manufactured by Shimadzu Corporation, "Flowsorb III 2305").
• volume-average particle diameter D50 of the functional layer slurry compositions prepared in Examples and Comparative Examples was measured immediately after preparation and after standing still for 10 days, and the change was observed.
• 1 kg of the functional layer slurry composition prepared in Examples and Comparative Examples was placed in a 1 L plastic bottle, allowed to stand for 10 days, and then stirred for 30 minutes together with the plastic bottle using a mix rotor. was used.
• the amount of change in volume average particle diameter D50 was measured according to the following criteria.
• SALD-7100 laser diffraction particle size distribution analyzer
• B Thermal shrinkage rate is 10% or more and less than 20%
• C Thermal shrinkage rate is 20% or more
• Example 1 ⁇ Preparation of water-soluble polymer A> 600 g of ion-exchanged water, 117 g of acrylamide as an amide group-containing monomer, and 24 g of diallyldimethylammonium chloride as an ionic group-containing monomer were added to a 1 L flask equipped with a septum, stirred and mixed, and nitrogen at a flow rate of 50 mL/min. The inside of the flask was replaced with gas bubbling. Next, the temperature was raised to 40° C., and 17 g of a 2.0% aqueous solution of L-ascorbic acid as a polymerization accelerator was injected into the flask with a syringe.
• Alumina particles manufactured by Sumitomo Chemical Co., Ltd., product name “AKP-20”, volume average particle diameter: 0.42 ⁇ m
• Alumina particles 100 parts of the inorganic particles, 2.5 parts of the solid content of the aqueous solution containing the water-soluble polymer obtained as described above, and ion-exchanged water were mixed, and a bead mill (manufactured by Ashizawa Fine Tech Co., Ltd., product name "LMZ015") was mixed. ) for 1 hour to obtain a dispersion.
• separator base material a separator base material made of polyethylene (manufactured by Asahi Kasei Corporation, product name “ND412”, thickness: 12 ⁇ m) was prepared.
• the functional layer slurry composition prepared above was applied using a gravure coater at a rate of 10 m/min, and then dried in a drying oven at 50°C to form a heat-resistant layer on one side.
• a separator (a separator with a heat-resistant layer; the thickness of the heat-resistant layer is 2 ⁇ m) was obtained.
• the heat shrinkage resistance and moisture content of the heat-resistant layer were evaluated. Table 1 shows the results.
• the mixture was cooled to terminate the polymerization reaction to obtain a mixture containing a particulate binder (styrene-butadiene copolymer).
• a particulate binder styrene-butadiene copolymer
• pH 8
• unreacted monomers were removed by heating under reduced pressure distillation.
• the mixture was cooled to 30° C. or less to obtain an aqueous dispersion containing the negative electrode binder.
• a slurry composition for a negative electrode mixture layer was prepared.
• the slurry composition for the negative electrode mixture layer was applied with a comma coater to the surface of a copper foil having a thickness of 15 ⁇ m as a current collector in an amount of 11 ⁇ 0.5 mg/cm 2 .
• the copper foil coated with the slurry composition for the negative electrode mixture layer is conveyed at a speed of 400 mm / min in an oven at a temperature of 80 ° C. for 2 minutes and further in an oven at a temperature of 110 ° C.
• the slurry composition on the copper foil was dried to obtain a negative electrode raw sheet in which a negative electrode mixture layer was formed on a current collector.
• the negative electrode mixture layer side of the negative electrode raw fabric thus prepared was roll-pressed under conditions of a temperature of 25 ⁇ 3° C. and a linear pressure of 11 t (tons), resulting in a negative electrode having a negative electrode mixture layer density of 1.60 g/cm 3 . got
• a planetary mixer was charged with 96 parts of a Co—Ni—Mn lithium composite oxide-based active material NMC532 (LiNi 0.5 Mn 0.3 Co 0.2 O 2 ) as a positive electrode active material, and acetylene as a conductive material.
• 2 parts of black manufactured by Denka Co., Ltd., product name "HS-100”
• 2 parts of polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd., product name "KF-1100" as a binder are added, and a dispersion medium is added.
• NMP N-methyl-2-pyrrolidone
• the slurry composition on the aluminum foil is dried, and the current collector A positive electrode raw sheet having a positive electrode mixture layer formed thereon was obtained.
• the positive electrode material layer side of the positive electrode raw material prepared was roll-pressed under the conditions of a linear pressure of 14 t (tons) in an environment of a temperature of 25 ⁇ 3 ° C., and a positive electrode with a positive electrode material layer density of 3.20 g / cm 3 got
• Example 2 When preparing the water-soluble polymer, except that the amount of the monomers to be blended was changed so that the content ratio of the various monomer units in the resulting water-soluble polymer was as shown in Table 1. Various operations, measurements, and evaluations similar to those in Example 1 were performed. Table 1 shows the results. Regarding the water-soluble polymer prepared in each example, Example 2 is indicated as water-soluble polymer B, and Example 4 is indicated as water-soluble polymer D.
• Example 3 When preparing the water-soluble polymer, the weight average molecular weight and 10% molecular weight of the resulting water-soluble polymer C are as shown in Table 1, except that the amount of ammonium persulfate as a polymerization initiator is reduced. Various operations, measurements, and evaluations similar to Example 1 were performed. Table 1 shows the results.
• Examples 5-6 In the preparation of the functional layer slurry composition, in Example 5, boehmite particles (manufactured by Nabaltec, product name “ACTILOX 200SM”, volume average particle diameter: 0.30 ⁇ m, BET specific surface area: 17 m 2 /g) were used as inorganic particles. , In Example 6, except that barium sulfate particles (manufactured by Takehara Chemical Co., Ltd., product name “TS-2”, volume average particle diameter: 0.36 ⁇ m, BET specific surface area: 7.5 m 2 /g) were blended Various operations, measurements, and evaluations similar to Example 1 were performed. Table 1 shows the results.
• Example 7 When preparing the water-soluble polymer, change the amount and/or type of the monomers to be blended so that the content ratio of each monomer unit in the resulting water-soluble polymer is as shown in Table 1. Various operations, measurements, and evaluations were performed in the same manner as in Example 1, except that Table 1 shows the results.
• the prepared water-soluble polymer was designated as water-soluble polymer E.
• Aam indicates an acrylamide unit
• AA indicates an acrylic acid unit
• DMDMAC denotes a diallyldimethylammonium chloride unit
• AN indicates an acrylonitrile unit
• EO-PO indicates an ethylene oxide-propylene oxide copolymer.
• the 10% molecular weight is 100,000 or less
• the storage elastic modulus E5 at a temperature of 50 ° C. and a relative humidity of 5% and the storage elastic modulus E50 at a temperature of 50 ° C. and a relative humidity of 50% are specified.
• a functional layer was formed using a non-aqueous secondary battery functional layer binder composition containing a water-soluble polymer that satisfies the relationship
• a functional layer having a small water content and excellent heat resistance was formed. It turns out that it was possible to form.
• Comparative Example 1 in which a functional layer was formed using a binder composition for a non-aqueous secondary battery functional layer containing a water-soluble polymer in which the value of (E 5 ⁇ E 50 )/E 5 exceeded 0.990
• Comparative Example 2 in which the functional layer was formed using the binder composition for the non-aqueous secondary battery functional layer containing a water-soluble polymer having a 10% molecular weight exceeding 100,000, had a low water content and excellent heat resistance. It can be seen that the functional layer could not be formed.
• the binder composition for non-aqueous secondary battery functional layers and the slurry composition for non-aqueous secondary battery functional layers which can form the functional layer which has little water content and is excellent in heat resistance are provided. be able to.

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