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
  • H01M50/489—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
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/52—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
  • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • 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
• • 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
  • H01M50/42—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
  • H01M50/429—Natural polymers
  • H01M50/4295—Natural cotton, cellulose or wood
• • 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
• • 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
• • 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
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/04—Hybrid capacitors
  • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• • 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 an electricity storage device separator and an electricity storage device.
• LiB lithium ion secondary batteries
• an electricity storage device is constructed by impregnating a power generation element with a separator interposed between a positive electrode and a negative electrode with an electrolytic solution.
• This separator has micropores that allow lithium ions to permeate during normal use of the storage device, and block the permeation of lithium ions when the storage device overheats, preventing thermal runaway. It is a thing.
• separator for example, in Patent Document 1, a slurry containing non-conductive particles, a water-soluble polymer having a monomer unit containing an acidic group, and a particulate polymer, wherein the water-soluble polymer is within a predetermined range and the BET specific surface area of the non-conductive particles is within a predetermined range.
• Such separators are said to improve the high-temperature cycle characteristics and safety of lithium-ion secondary batteries.
• Patent Document 1 suppresses heat shrinkage in the electrolyte solution, and is a separator that can ensure safety even when combined with a positive electrode material having a high nickel content. There is room for further improvement.
• the present invention has been made in view of the above-mentioned problems of the prior art, and can suppress thermal contraction in an electrolytic solution and ensure safety even when combined with a positive electrode material having a high nickel content.
• An object of the present invention is to provide a separator for an electricity storage device.
• the present inventors have found that a The present inventors have found that safety can be ensured even when a separator having an interfacial peel strength between adjacent layers within a predetermined range is used in combination with a positive electrode material containing a large amount of nickel, and the present invention has been completed.
• a layer (A) containing polyolefin A layer (B) disposed on at least one surface of the layer (A) and containing an inorganic filler, a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based dispersant;
• a separator for an electricity storage device comprising An electricity storage device separator, wherein the heat shrinkage rate S1 of the electricity storage device separator in propylene carbonate at 140° C. is 5% or less.
• the water-soluble binder contains cellulose ether, A power storage device separator, wherein the interfacial peel strength H between the layer (A) and the layer (B) in propylene carbonate is 3 N/m or more.
• [5] The power storage device separator according to any one of [1], [3], and [4], wherein the heat shrinkage rate S1 is 2.5% or less.
• [6] The power storage device separator according to any one of [1] to [5], wherein the thickness T of the power storage device separator is 3 ⁇ m or more and 16 ⁇ m or less.
• [8] The power storage device separator according to any one of [1] to [7], wherein the power storage device separator has a puncture strength of 200 gf or more.
• the separator for electrical storage devices in any one of ].
• the polyacrylic acid-based dispersant is selected from the group consisting of a neutralized salt of a monovalent metal ion of polyacrylic acid and a copolymer of a neutralized salt of a monovalent metal ion of acrylic acid and acrylic acid.
• the electricity storage device separator according to any one of [1], [3] to [9], which contains one or more selected types.
• a positive electrode containing Li, Co, and Ni a positive electrode containing Li, Co, and Ni; a negative electrode facing the positive electrode; an electricity storage device separator according to any one of [1] to [14], which is arranged between the positive electrode and the negative electrode;
• An electricity storage device comprising An electricity storage device, wherein the content ratios of Co and Ni in metals other than Li in the positive electrode are 20 mol % or less and 60 mol % or more, respectively.
• the present invention it is possible to provide a power storage device separator that suppresses heat shrinkage in an electrolytic solution and ensures safety even when combined with a positive electrode material having a high nickel content.
• (Meth)acryl as used herein means “acryl” and “methacryl” corresponding thereto.
• ⁇ means that the numerical values at both ends are included as the upper limit and the lower limit.
• the power storage device separator according to the first aspect of the present embodiment (hereinafter also referred to as "first separator") is a layer (A) containing polyolefin and disposed on at least one surface of the layer (A). and a layer (B) containing an inorganic filler, a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based dispersant, wherein A heat shrinkage rate S1 at 140° C. is 5% or less. Since the first separator has the above structure, it can suppress heat shrinkage in the electrolytic solution and ensure safety even when combined with a positive electrode material containing a large amount of nickel.
• the power storage device separator includes a layer (A) containing polyolefin and on at least one surface of the layer (A) and a layer (B) containing an inorganic filler, a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based dispersant, wherein the polyacrylic acid-based dispersant is , a neutralized salt of a monovalent metal ion of polyacrylic acid, and a copolymer of a neutralized salt of a monovalent metal ion of acrylic acid and acrylic acid, including one or more selected from the group consisting of
• the water-soluble binder contains cellulose ether, and the interfacial peel strength H between the layer (A) and the layer (B) in propylene carbonate is 3 N/m or more.
• the second separator having the above structure also suppresses heat shrinkage in the electrolyte, and can ensure safety even when combined with a positive electrode material containing a large amount of nickel.
• the following description of the power storage device separator applies to both the first separator and the second separator.
• the "separator for an electricity storage device of the present embodiment" will be described as including the first separator and the second separator.
• the layer (A) contains polyolefin and functions as the base material of the separator for the electricity storage device.
• the layer (A) preferably contains polyolefin as a main component, and the polyolefin content in the layer (A) is preferably 75% by mass or more, more preferably 85% by mass, based on the total mass of the layer (A). % by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
• the upper limit of the content is not particularly limited, and may be 100% by mass.
• the form of the layer (A) is not particularly limited, for example, a microporous body of polyolefin can be mentioned.
• the microporous body of polyolefin is not particularly limited, and examples thereof include polyolefin membranes, polyolefin fiber fabrics (woven fabrics), polyolefin fiber nonwoven fabrics, and the like.
• the polyolefin is not particularly limited, but for example, homopolymers and copolymers obtained using ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene as monomers. Examples include coalescence and multi-stage polymers, and these polymers may be used alone or in combination of two or more.
• the polyolefin may contain at least one selected from the group consisting of polyethylene, polypropylene, and copolymers thereof, from the viewpoint of imparting appropriate melt viscosity, shutdown and meltdown properties as a separator to the layer (A). Preferably, it contains polyethylene.
• the polyolefin may contain polypropylene.
• the polyolefin may contain an ethylene-propylene copolymer or a mixture of polyethylene and polypropylene.
• polyethylene examples include, but are not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high molecular weight polyethylene (HMWPE), and Examples include ultra high molecular weight polyethylene (UHMWPE).
• LDPE low density polyethylene
• LLDPE linear low density polyethylene
• MDPE medium density polyethylene
• HDPE high density polyethylene
• HMWPE high molecular weight polyethylene
• UHMWPE ultra high molecular weight polyethylene
• high molecular weight polyethylene means polyethylene with a viscosity average molecular weight (Mv) of 100,000 or more.
• Mv viscosity average molecular weight
• UHMWPE ultra high molecular weight polyethylene
• HMWPE high molecular weight polyethylene
• high density polyethylene refers to polyethylene having a density of 0.942 to 0.970 g/cm 3 .
• the density of polyethylene refers to a value measured according to D) density gradient tube method described in JIS K7112 (1999).
• polypropylene examples include, but are not particularly limited to, isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene.
• copolymers of ethylene and propylene include, but are not limited to, ethylene-propylene random copolymers and ethylene-propylene rubbers.
• the PE content is 50% by mass or more and 100% by mass or less based on the total mass of the resin components constituting the layer (A), From the viewpoint of fuse characteristics or meltdown characteristics, the content is preferably 85% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 95% by mass or less.
• the PP content is greater than 0% by mass and less than 50% by mass, based on the total mass of the resin components constituting the layer (A), and the melt viscosity And from the viewpoint of fuse characteristics, it is preferably greater than 0% by mass and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less.
• the layer (A) may contain resins other than the polyolefins listed above.
• resins include, but are not particularly limited to, polyethylene terephthalate, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimideamide, polyaramid, polyvinylidene fluoride, nylon, polytetrafluoroethylene, and the like.
• melt index The melt index (MI) of the layer (A) at 190° C. suppresses the high viscosity of the resin composition containing polyolefin (hereinafter also referred to as “polyolefin resin composition”) during film formation, thereby preventing the occurrence of defective products.
• polyolefin resin composition containing polyolefin (hereinafter also referred to as “polyolefin resin composition”) during film formation, thereby preventing the occurrence of defective products.
• it is preferably 0.02 g/10 min to 0.5 g/10 min, more preferably 0.05 g/10 min to 0.3 g/10 min. More specifically, it is preferably 0.02 g/10 min to 0.50 g/10 min, more preferably 0.05 g/10 min to 0.30 g/10 min.
• the piercing strength of the layer (A) when converted to basis weight (g/m 2 ) (hereinafter referred to as “weight-converted piercing strength”) can be, for example, 30 gf/(g/m 2 ) or more, It is preferably 40 gf/(g/m 2 ) or more.
• weight-converted piercing strength can be, for example, 30 gf/(g/m 2 ) or more, It is preferably 40 gf/(g/m 2 ) or more.
• the per unit weight equivalent puncture strength is more preferably 50 gf/(g/m 2 ) or more, and even more preferably. is 60 gf/(g/m 2 ) or more, more preferably 70 gf/(g/m 2 ) or more, still more preferably 80 gf/(g/m 2 ) or more, still more preferably 90 gf/(g/m 2 ) or more. (g/m 2 ) or more.
• the weight-converted puncture strength is not limited, but may be, for example, 200 gf/(g/m 2 ) or less, 150 gf/(g/m 2 ) or less, or 120 gf/(g /m 2 ) or less.
• the weight-converted puncture strength can be measured by the method described in Examples below.
• the weight-converted puncture strength can be adjusted within the above range, for example, by appropriately adjusting the values of the weight per unit area and the puncture strength by the method described later. More specifically, for example, the above range can be adjusted by adjusting the molecular weight of the polyolefin resin composition, the mixing ratio of the polyolefin resin composition and the plasticizer, the stretching temperature, and the stretching ratio.
• the basis weight of the layer (A) is preferably 1.5 g/m 2 or more, more preferably 2.0 g/m 2 or more, still more preferably 2.5 g/m 2 or more, from the viewpoint of improving strength. From the viewpoint of improving the capacity of the electricity storage device, it is preferably 7.0 g/m 2 or less, more preferably 6.5 g/m 2 or less, and still more preferably 5.5 g/m 2 or less. be.
• the basis weight of the layer (A) can be measured by the method described in Examples below, and can be adjusted, for example, by controlling the die lip interval, the draw ratio in the drawing step, and the like.
• the puncture strength that is not converted to the basis weight of the layer (A) (hereinafter simply referred to as "pierce strength”) is preferably 100 gf or more from the viewpoint of suppressing breakage of the layer (A) in the impact test. More preferably 200 gf or more, still more preferably 250 gf or more, still more preferably 300 gf or more, still more preferably 350 gf or more, still more preferably 400 gf or more, particularly preferably 450 gf or more. From the viewpoint of stability during film formation of the layer (A), the puncture strength is preferably 1000 gf or less, more preferably 900 gf or less.
• the lower limit value of the puncture strength is not limited to the example described above, and any value can be adopted as long as the film formation and battery production can be stably carried out.
• the upper limit value of the puncture strength is not limited to the example described above, and can be appropriately set in balance with other characteristics.
• the puncture strength can be measured by the method described in Examples below. Assuming that the layer (A) is obtained by extruding the polyolefin resin composition, the puncture strength can be increased by increasing the orientation of the molecular chains due to the shearing force or stretching applied to the molded product during extrusion. From the viewpoint of avoiding an increase in residual stress and improving thermal stability, it is preferable to control the orientation of molecular chains by shear force or stretching so as not to increase excessively.
• the thickness of the layer (A) is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, still more preferably 5 ⁇ m or more, from the viewpoint of improving strength and voltage resistance. More specifically, it is preferably 3.0 ⁇ m or more, more preferably 4.0 ⁇ m or more, and even more preferably 5.0 ⁇ m or more. Moreover, from the viewpoint of improving the capacity of the electricity storage device, the thickness of the layer (A) is preferably 12 ⁇ m or less, more preferably 11 ⁇ m or less, and even more preferably 10 ⁇ m or less. More specifically, it is preferably 12.0 ⁇ m or less, more preferably 11.0 ⁇ m or less, and even more preferably 10.0 ⁇ m or less. The thickness of the layer (A) can be measured by the method described in Examples below, and can be adjusted, for example, by controlling the die lip interval, the draw ratio in the drawing step, and the like.
• the porosity of the layer (A) is preferably 20% or more, more preferably 30% or more, and still more preferably 35% or more from the viewpoint of permeability, and from the viewpoint of membrane strength and withstand voltage. , preferably 70% or less, more preferably 60% or less, still more preferably 50% or less.
• the porosity can be measured by the method described in Examples below.
• the porosity is controlled by, for example, the mixing ratio of the polyolefin resin composition and the plasticizer, the stretching temperature, the stretching ratio, the heat setting temperature, the stretching ratio during heat setting, and the relaxation rate during heat setting. and can be adjusted by combining these.
• the air permeability of the layer (A) is preferably 10 sec/100 cm 3 or more, more preferably 50 sec/100 cm 3 from the viewpoint of preventing an excessive current from flowing through the layer (A) between a plurality of electrodes. more preferably 80 sec/100 cm 3 or more, and from the viewpoint of permeability, preferably 1000 sec/100 cm 3 or less, more preferably 300 sec/100 cm 3 or less, still more preferably 200 sec/100 cm 3 or less, and particularly preferably 160 sec/100 cm 3 or less.
• the air permeability can be measured by the method described in Examples below.
• the air permeability can be adjusted by controlling the heat setting temperature, the draw ratio during heat setting, the relaxation rate during heat setting, and the like, or by combining these.
• the absorption peak ratio Before forming the layer (B) on the surface of the layer (A), it is preferable to adjust the surface properties by subjecting the layer (A) to corona discharge treatment, plasma treatment, or the like. Such surface properties can be confirmed by ATR-IR, and more specifically, confirmed by the absorption peak ratio of 1734 cm -1 /2918 cm -1 when the surface of the layer (A) is measured by ATR-IR. be able to.
• the absorption peak ratio at 1734 cm ⁇ 1 /2918 cm ⁇ 1 when the surface of the layer (A) on the layer (B) side is measured by ATR-IR is, for example, 0.010 to 0.180. and preferably 0.025 to 0.125.
• the absorption peak ratio is 0.025 or more, the oxygen atom-containing functional groups mainly composed of carbonyl groups and carboxyl groups formed on the surface of the layer (A) and the water-insoluble binder in the layer (B), And the interaction with the water-soluble binder becomes large, and as a result, there is a tendency that the heat shrinkage in the electrolytic solution can be sufficiently suppressed. Further, when the absorption peak ratio is 0.125 or less, excessive impregnation of the pores of the layer (A) with the resin component contained in the coating liquid when forming the layer (B) is suppressed, resulting in As a result, the permeability tends to improve.
• the absorption peak ratio is more preferably 0.040 to 0.105, still more preferably 0.055 to 0.085.
• the absorption peak ratio can be measured by the method described in Examples below. Further, the absorption peak ratio can be adjusted by, for example, performing corona discharge treatment or plasma discharge treatment under preferable conditions described later.
• the viscosity average molecular weight (Mv) of the layer (A) is preferably 400,000 or more and 1,300,000 or less, more preferably 450,000 or more and 1,200,000 or less, and still more preferably 500,000. 1,150,000 or less.
• Mv viscosity average molecular weight
• the melt tension during melt molding is increased, the moldability is improved, and high film strength tends to be obtained due to the entanglement of the polymers.
• Mv can be determined from the intrinsic viscosity [ ⁇ ] at 135° C. in decalin solvent based on ASTM-D4020.
• the layer (A) has ion conductivity, high resistance to organic solvents, and a pore size from the viewpoint of application to a lithium ion secondary battery separator, particularly a laminate type lithium ion secondary battery separator. fine ones are preferred. Therefore, the average pore size of the layer (A) is preferably 0.03 ⁇ m or more and 0.70 ⁇ m or less, more preferably 0.04 ⁇ m or more and 0.20 ⁇ m or less, still more preferably 0.05 ⁇ m or more and 0.10 ⁇ m or less, still more preferably It is 0.055 ⁇ m or more and 0.09 ⁇ m or less.
• the average pore diameter of the layer (A) is preferably 0.03 ⁇ m or more and 0.70 ⁇ m or less from the viewpoint of ion conductivity and voltage resistance.
• the average pore diameter is, for example, the composition ratio of the polyolefin resin composition, the type of polyolefin or plasticizer, the cooling rate of the extruded sheet, the stretching temperature, the stretching ratio, the heat setting temperature, the stretching ratio during heat setting, and the relaxation during heat setting. Adjustments can be made by controlling the rate, etc., as well as combinations thereof.
• the average pore size can be measured using a perm porometer according to the half dry method.
• the layer (B) is arranged on at least one surface of the layer (A) and contains an inorganic filler, a water-insoluble binder, a water-soluble binder and a polyacrylic acid-based dispersant.
• the layer (B) has a function of suppressing shrinkage due to heat, in particular, in the separator for an electricity storage device.
• the thickness of the layer (B) is preferably 0.5 ⁇ m or more, more preferably 0.6 ⁇ m or more, still more preferably 0.7 ⁇ m or more, and even more preferably 1.0 ⁇ m or more.
• the thickness of the layer (B) is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, and even more preferably 3 ⁇ m or less. More specifically, it is preferably 5.0 ⁇ m or less, more preferably 4.0 ⁇ m or less, and even more preferably 3.0 ⁇ m or less.
• the layer (B) may be formed only on one side of the layer (A), or may be formed on both sides of the layer (A). When the layer (B) is formed on both sides of the layer (A), the total thickness of the layer (B) is preferably within the range described above. The thickness of the layer (B) can be measured by the method described in Examples below. can be adjusted.
• the inorganic filler in the layer (B) is not particularly limited, but preferably has high heat resistance and electrical insulation properties and is electrochemically stable within the range of use of the lithium ion secondary battery.
• examples of such inorganic fillers include, but are not limited to, oxide-based ceramics such as alumina, silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, and iron oxide; silicon nitride, titanium nitride, and Nitride ceramics such as boron nitride; silicon carbide, calcium carbonate, magnesium sulfate, aluminum sulfate, barium sulfate, aluminum hydroxide, aluminum hydroxide oxide or boehmite, potassium titanate, talc, kaolinite, dakite, nacrite, halloysite, Ceramics such as pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, asbestos,
• At least one selected from the group consisting of alumina, boehmite, and barium sulfate is preferable from the viewpoint of stability in the lithium ion secondary battery.
• alumina boehmite
• barium sulfate is preferable from the viewpoint of stability in the lithium ion secondary battery.
• boehmite synthetic boehmite is preferable because it can reduce ionic impurities that adversely affect the characteristics of the electrochemical device.
• An inorganic filler may be used individually by 1 type, and may use multiple types together.
• Examples of the shape of the inorganic filler include plate-like, scale-like, polyhedral, needle-like, columnar, granular, spherical, spindle-like, and block-like shapes. good.
• the block shape is preferable from the viewpoint of the balance between permeability and heat resistance.
• the aspect ratio of the inorganic filler is preferably 1.0 or more and 3.0 or less, more preferably 1.1 or more and 2.5 or less.
• the aspect ratio of the inorganic filler can be obtained by image analysis of an image taken with a scanning electron microscope (SEM).
• the specific surface area of the inorganic filler is preferably 5.0 m 2 /g or more and 20 m 2 /g or less, more preferably 5.5.0 m 2 /g or more and 18 m 2 /g or less, still more preferably , 6.0 m 2 /g or more and 16 m 2 /g or less. More specifically, it is preferably 5.0 m 2 /g or more and 20.0 m 2 /g or less, more preferably 5.5 m 2 /g or more and 18.0 m 2 /g or less, still more preferably It is 6.0 m 2 /g or more and 16.0 m 2 /g or less.
• the specific surface area is 20 m 2 /g or less, it is preferable from the viewpoint of reducing the water adsorption amount of the power storage device separator and suppressing capacity deterioration when the cycle is repeated, and the specific surface area is 5.0 m 2 /g or more. In some cases, it is preferable from the viewpoint of suppressing deformation at a temperature exceeding the melting point of the layer (A).
• the specific surface area of the inorganic filler can be measured using the BET adsorption method.
• the volume average particle diameter D50 of the inorganic filler can be, for example, 1.0 ⁇ m or less, preferably 0.10 ⁇ m or more and 0.70 ⁇ m or less.
• D50 is 0.10 ⁇ m or more, it is preferable from the viewpoint of suppressing the amount of water adsorption of the power storage device separator and suppressing capacity deterioration when cycles are repeated. It is preferable from the viewpoint of suppressing deformation at a temperature exceeding the melting point of A).
• D50 is more preferably 0.10 ⁇ m or more and 0.60 ⁇ m or less, still more preferably 0.10 ⁇ m or more and 0.50 ⁇ m or less, and still more preferably 0.10 ⁇ m or more and 0.49 ⁇ m or less. .
• the volume average particle diameter D50 of the inorganic filler can be measured by the method described in Examples below.
• Methods for adjusting the volume average particle diameter D50 of the inorganic filler as described above include, for example, a method of pulverizing the inorganic filler using a ball mill, a bead mill, a jet mill, etc. to obtain a desired particle size distribution, a method of obtaining a desired particle size distribution, and a method of obtaining a desired particle size distribution. Examples include a method of blending after preparing a distribution of fillers.
• the particle size of the inorganic filler redispersed from the layer (B) can be, for example, 1.0 ⁇ m or less, preferably 0.10 ⁇ m or more and 0.70 ⁇ m or less.
• the particle diameter of the inorganic filler redispersed from the layer (B) is 0.10 ⁇ m or more, it is preferable from the viewpoint of suppressing the amount of moisture adsorption of the separator for an electricity storage device and suppressing capacity deterioration when repeated cycles.
• the inorganic filler redispersed from the layer (B) having a particle size of 0.70 ⁇ m or less is preferable from the viewpoint of suppressing deformation at a temperature exceeding the melting point of the layer (A).
• the particle size of the inorganic filler redispersed from the layer (B) is more preferably 0.10 ⁇ m or more and 0.60 ⁇ m or less, still more preferably 0.10 ⁇ m or more and 0.50 ⁇ m or less. It is more preferably 0.10 ⁇ m or more and 0.49 ⁇ m or less.
• the particle size of the inorganic filler re-dispersed from the layer (B) can be measured by the method described in Examples below.
• the inorganic filler is pulverized using a ball mill, bead mill, jet mill, or the like to obtain a desired particle size distribution. method, and a method of blending after preparing fillers with a plurality of particle size distributions.
• the primary particle size of the inorganic filler in the layer (B) can be, for example, 1.0 ⁇ m or less, preferably 0.10 ⁇ m or more and 0.70 ⁇ m or less.
• the primary particle diameter of the inorganic filler in the layer (B) is 0.10 ⁇ m or more, it is preferable from the viewpoint of suppressing the amount of moisture adsorption of the electricity storage device separator and suppressing capacity deterioration when repeated cycles. It is preferable that the primary particle size of the inorganic filler in B) is 0.70 ⁇ m or less from the viewpoint of suppressing deformation at a temperature exceeding the melting point of the layer (A).
• the primary particle size of the inorganic filler in the layer (B) is more preferably 0.10 ⁇ m or more and 0.60 ⁇ m or less, still more preferably 0.10 ⁇ m or more and 0.50 ⁇ m or less, and still more preferably. is 0.10 ⁇ m or more and 0.49 ⁇ m or less.
• the primary particle size of the inorganic filler in the layer (B) can be measured by the method described in Examples below.
• Examples of the method for adjusting the primary particle size of the inorganic filler in the layer (B) as described above include a method of pulverizing the inorganic filler using a ball mill, bead mill, jet mill, or the like to obtain a desired particle size distribution; A method of blending after preparing fillers with a plurality of particle size distributions may be mentioned.
• the maximum particle size of the inorganic filler in the layer (B) is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.5 ⁇ m or less.
• the maximum particle size can be measured by the method described in Examples below.
• the content of the inorganic filler in the layer (B) is preferably 80% by mass or more and 99% by mass or less, more preferably 85% by mass or more and 98% by mass or less, based on the mass of the layer (B). , more preferably 90% by mass or more and 98% by mass or less, and still more preferably 92% by mass or more and 98% by mass or less.
• a content of 80% by mass or more is preferable from the viewpoint of ion permeability and suppression of deformation at temperatures exceeding the melting point of the layer (A). Further, when the content is 99% by mass or less, it is preferable from the viewpoint of maintaining the bonding strength between the inorganic fillers or the interfacial bonding strength between the inorganic filler and the layer (A).
• the water-insoluble binder in layer (B) is defined as a particulate polymer having a glass transition temperature of 10° C. or less, which is dispersed in water in particulate form. Dispersion in the form of particles in water is not limited to the following, but for example, the particle size distribution of the water-insoluble binder can be measured based on the method described in the examples below, and the polymer at 25 ° C. It can be confirmed from the fact that when 1.0 g of the dried product is dissolved in 100 g of water, the insoluble content is 90% by mass or more.
• the water-insoluble binder is considered to bind the inorganic filler in the form of dots in the electrolytic solution, and achieves both heat resistance and permeability.
• water-insoluble binder examples include, but are not limited to, styrene-butadiene-based latex, acrylonitrile-butadiene-based latex, acrylic latex (methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer , and acrylonitrile-acrylate copolymer, etc.).
• Acrylic latex is preferable from the viewpoint of freedom of molecular design.
• acrylic acid esters that can constitute acrylic latex include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl amethacrylate, and the like.
• (Meth)acrylic acid alkyl esters can be mentioned. These acrylic acid esters may be used alone or in combination of two or more.
• the water-insoluble binder may contain a crosslinkable monomer unit from the viewpoint of making the amount of the insoluble matter in the electrolytic solution appropriate.
• the monomer that can constitute the crosslinkable monomer unit is not particularly limited. Examples include monomers having functional groups. These may be used individually by 1 type, or may use 2 or more types together. Specific examples of the above monomers are not particularly limited, but include polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate. , trimethylolpropane trimethacrylate and other polyfunctional (meth)acrylates. These may be used individually by 1 type, or may use 2 or more types together.
• the inorganic filler, the water-soluble binder, the polyacrylic acid-based dispersant, and the layer (A) are secured by hydrogen bonding.
• an acrylic latex having a functional group that hydrogen bonds with a carboxyl group, a carbonyl group, or a hydroxyl group, and/or a self-crosslinking structure during or after polymerization is particularly preferable.
• acrylic latexes include units derived from acrylic acid and the like, units derived from acrylamide and/or glycidyl (meth)acrylate, allyl glycidyl ether, methyl glycidyl acrylate, and the like, in addition to units derived from acrylic acid esters described above. Examples thereof include copolymers having units derived from the above.
• the polymerization method of the above copolymer is not particularly limited, emulsion polymerization is preferred.
• the emulsion polymerization method is not particularly limited, and known methods can be used.
• the method of adding the monomers and other components is not particularly limited, and any of a batch addition method, a divisional addition method, and a continuous addition method can be employed. , or multi-stage polymerization of three or more stages can be employed.
• a water-insoluble binder may be used individually by 1 type, and may use multiple types together.
• the volume average particle size of the water-insoluble binder is preferably 10 to 500 nm from the viewpoint of binding strength and permeability.
• the volume average particle diameter is 10 nm or more, the permeability tends to be improved by preventing excessive clogging of the pores of the layer (A). It tends to prevent a decrease and improve heat resistance.
• the particle size is more preferably 20 to 350 nm, still more preferably 30 to 200 nm.
• the volume-average particle diameter can be measured by the method described in the examples below. can be adjusted by
• the glass transition temperature (Tg) of the water-insoluble binder is preferably ⁇ 40° C. or higher and 10° C. or lower from the viewpoint of binding properties.
• the glass transition temperature is more preferably -40°C or higher and 0°C or lower, and more preferably -40°C or higher and -5°C or lower.
• the glass transition temperature can be measured by the method described in Examples below.
• the glass transition temperature can be adjusted, for example, by adjusting the polymerization time, polymerization temperature, and raw material composition ratio when producing the water-insoluble binder.
• the content of the water-insoluble binder is preferably 1 to 12% by mass, more preferably 1%, based on 100% by mass of the inorganic filler in the layer (B). 10% by mass, more preferably 2 to 8% by mass, and even more preferably 3 to 6% by mass or less.
• the water-soluble binder in the layer (B) has a weight-average molecular weight of 20,000 or more and an insoluble content of less than 1.0% by mass when 1.0 g of the polymer is dissolved in 100 g of water at 25°C. Defined as a polymer, it binds the inorganic filler in the form of a film in the electrolytic solution and has the function of contributing to heat resistance.
• the water-soluble binder in the first separator layer (B) include, but are not limited to, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), cellulose ether, polyacrylamide, poly(meth)acrylic acid, polyvinylacetamide, polyethyleneimine, polyethylene oxide, polystyrenesulfonic acid, xanthan gum, guar gum and the like.
• PVA polyvinyl alcohol
• PVP polyvinylpyrrolidone
• cellulose ether polyacrylamide
• poly(meth)acrylic acid polyvinylacetamide
• polyethyleneimine polyethyleneimine
• polyethylene oxide polystyrenesulfonic acid
• xanthan gum guar gum
• the water-soluble binder in layer (B) of the second separator comprises cellulose ether.
• Water-soluble binders in the layer (B) of the second separator include, in addition to cellulose ether, PVA, PVP, polyacrylamide, poly(meth)acrylic acid, polyvinylacetamide, polyethyleneimine, polyethyleneoxide, polystyrenesulfonic acid, xanthan gum, It may contain guar gum and the like.
• the water-soluble binder may be used alone or in combination of multiple types.
• the water-soluble binder may be a copolymer of at least one selected from the above and another copolymer component.
• the weight-average molecular weight can be measured by the method described in Examples below, and can be adjusted, for example, by adjusting the polymerization time, polymerization temperature, raw material composition ratio, raw material charging order, stirring speed, etc., when producing the water-soluble binder. can be done.
• the fact that the layer (B) contains a water-soluble binder can be confirmed by, for example, immersing the separator in water, dissolving the water-soluble component in the water layer, filtering the resulting water layer component, and performing gel permeation chromatography or the like.
• the degree of etherification of the cellulose ether is preferably 0.5 or more, more preferably 0.6 or more, and preferably 1.5 or less, more preferably 1.0 or less.
• the degree of etherification refers to the degree of substitution of a hydroxyl group to a carboxymethyl group or the like per anhydroglucose unit in cellulose.
• the degree of etherification can theoretically take values from 0 to 3. When the degree of etherification is within the above range, the cellulose ether tends to be excellent in water solubility and binding strength.
• the degree of etherification can be measured, for example, by neutralization titration of the ash content of the cellulose ether.
• the weight average molecular weight of the water-soluble binder is preferably 20,000 or more, more preferably 50,000 or more, and preferably 600,000 or less, more preferably 400,000 or less.
• the content of the water-soluble binder is 0.05 to 2.4% by mass, with the content of the inorganic filler in the layer (B) being 100% by mass, from the viewpoint of permeability, heat resistance and coatability. is preferable, more preferably 0.1 to 2.4% by mass, still more preferably 0.1 to 2.0% by mass, still more preferably 0.15 to 2.0% by mass, and further It is preferably 0.2 to 1.0% by mass, and more preferably 0.3 to 0.8% by mass.
• the polyacrylic acid-based dispersant in the layer (B) has a weight-average molecular weight of 500 or more and an insoluble content of less than 1.0% by weight when 1.0 g of the polymer is dissolved in 100 g of water at 25°C. Defined as a polymer having an acrylic acid skeleton of 10,000 or less, it adsorbs to the surface of the inorganic filler and contributes to dispersibility and binding in the electrolyte.
• Specific examples of the polyacrylic acid-based dispersant in the first separator layer (B) include, but are not limited to, acrylic acid, sodium acrylate, lithium acrylate, and ammonium acrylate as monomers.
• Examples include homopolymers and copolymers.
• a neutralized salt of a monovalent metal ion of polyacrylic acid and a neutralized salt of a monovalent metal ion of acrylic acid and acrylic acid It is preferable to include one or more selected from the group consisting of a copolymer, and specific examples of such a polyacrylic acid-based dispersant include, but are not limited to, sodium polyacrylate and lithium polyacrylate etc.
• the polyacrylic acid-based dispersant in the second separator layer (B) is a neutralized salt of a monovalent metal ion of polyacrylic acid, and a neutralized salt of a monovalent metal ion of acrylic acid and acrylic acid. Copolymer of, one or more selected from the group consisting of.
• the polyacrylic acid-based dispersant in the second separator layer (B) is a neutralized salt of a monovalent metal ion of polyacrylic acid and a neutralized salt of a monovalent metal ion of acrylic acid and acrylic acid. Aside from polymers, homopolymers and copolymers obtained by using acrylic acid, sodium acrylate, lithium acrylate and ammonium acrylate as monomers may also be included.
• the polyacrylic acid-based dispersant may be used alone or in combination of multiple types.
• the layer (B) contains a polyacrylic acid-based dispersant, for example, by immersing the separator in water, dissolving the water-soluble component in the water layer, filtering the resulting water layer component, and performing gel permeation chromatography It can be detected by measuring the molecular weight by photography or the like, and analyzing the dry matter of the aqueous layer component with an infrared spectrometer, a nuclear magnetic resonance spectrometer, an energy dispersive X-ray spectrometer, or the like.
• the weight average molecular weight of the polyacrylic acid-based dispersant is preferably 500 or more, more preferably 1,000 or more, and preferably 10,000 or less, more preferably 8,000 or less.
• the weight-average molecular weight of the water-soluble binder can be adjusted.
• the content of the polyacrylic acid-based dispersant is 0.1 to 2.4% by mass when the content of the inorganic filler in the layer (B) is 100% by mass, from the viewpoint of improving permeability and dispersibility. is preferably 0.1 to 2.0% by mass, still more preferably 0.2 to 1.0% by mass, and even more preferably 0.3 to 0.8% by mass .
• Thermal shrinkage rate S1 (Physical properties of separator for power storage device) (Thermal shrinkage rate S1)
• the thermal contraction rate S1 of the first separator at 140° C. in propylene carbonate is 5% or less. Since the heat shrinkage rate S1 is 5% or less, deformation due to heating of the separator in the battery is suppressed and short-circuiting between the positive and negative electrodes is prevented even when combined with a positive electrode material having a high nickel content. be able to. From this point of view, the heat shrinkage rate S1 is preferably 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, and even more preferably 3.5%.
• the heat shrinkage rate S1 is not intended to be limited, but from the same viewpoint as above, it is preferably within the range described above. That is, the heat shrinkage S1 of the second separator in propylene carbonate at 140° C. is preferably 5% or less, more preferably 5.0% or less, and still more preferably 4.0% or less.
• the thermal shrinkage rate S1 can be measured by the method described in Examples below.
• the thermal shrinkage rate S1 can be obtained, for example, by subjecting the surface of the layer (A) to a surface treatment such as a corona discharge treatment under preferable conditions described later, and by using a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based binder as the layer (B).
• a surface treatment such as a corona discharge treatment under preferable conditions described later
• a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based binder as the layer (B).
• the heat shrinkage rate S2 of the power storage device separator of the present embodiment at 150° C. in air is preferably 5% or less.
• the heat shrinkage rate S2 is preferably 5.0% or less, more preferably 4.0% or less, even more preferably 3.5% or less, and still more preferably 3.0%. or less, even more preferably 2.5% or less, even more preferably 2.0% or less, even more preferably 1.5% or less, and even more preferably 1.0% It is preferably 0.5% or less, particularly preferably 0.5% or less.
• the thermal shrinkage rate S2 can be measured by the method described in Examples below.
• the heat shrinkage ratio S2 tends to fall within the range described above, for example, by using a combination of a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based dispersant as the layer (B). In addition to the factors described above, the value tends to be further reduced by adjusting the volume average particle diameter D50 of the inorganic filler to the preferable range described above.
• the thickness T of the power storage device separator of the present embodiment is preferably 3 ⁇ m or more and 16 ⁇ m or less from the viewpoint of heat resistance, permeability, and battery capacity. More specifically, it is preferably 3.0 ⁇ m or more and 16.0 ⁇ m or less. When the thickness T is 3 ⁇ m or more, the heat resistance tends to be improved, and when the thickness T is 16 ⁇ m or less, the permeability and battery capacity tend to be improved. From the same point of view, the thickness T is more preferably 3 ⁇ m or more and 15 ⁇ m or less, and still more preferably 3 ⁇ m or more and 14 ⁇ m or less.
• the ratio of the thickness T B to the thickness T of the layer (B) is preferably 0.1 to 0.3 as T B /T. More specifically, it is preferably 0.10 to 0.30.
• T B /T is 0.3 or less, strength tends to improve, and when T B /T is 0.1 or more, safety tends to improve.
• T B /T is more preferably 0.14 to 0.27, still more preferably 0.18 to 0.25.
• the thickness T and T B /T can be measured by the method described in Examples below.
• the puncture strength of the power storage device separator of the present embodiment is preferably 100 gf or more, more preferably 200 gf or more, still more preferably 250 gf or more, from the viewpoint of suppressing breakage of the separator in an impact test. It is more preferably 300 gf or more, still more preferably 350 gf or more, still more preferably 400 gf or more, and particularly preferably 450 gf or more. From the viewpoint of stability during film formation of the layer (A), the puncture strength is preferably 1000 gf or less, more preferably 900 gf or less. The puncture strength can be measured by the method described in Examples below. The puncture strength can be adjusted by, for example, the molecular weight of the polyolefin resin composition of the layer (A), the mixing ratio of the polyolefin resin composition and the plasticizer, the stretching temperature, and the stretching ratio.
• the weight-converted puncture strength of the power storage device separator of the present embodiment is 20 gf/(g/m 2 ) or more.
• the layer (A) tends to be difficult to break in an impact test of the electricity storage device.
• the weight-converted puncture strength is more preferably 25 gf/(g/m 2 ) or more, and even more preferably.
• the weight-converted puncture strength is not limited, but may be, for example, 150 gf/(g/m 2 ) or less, 130 gf/(g/m 2 ) or less, or 100 gf/(g /m 2 ) or less.
• the above weight-converted piercing strength can be calculated by measuring the piercing strength and weight per unit area according to the method described in Examples below.
• the basis weight equivalent puncture strength can be adjusted by, for example, the molecular weight of the polyolefin resin composition of the layer (A), the mixing ratio of the polyolefin resin composition and the plasticizer, the stretching temperature, the stretching ratio, and the basis weight of the layer (B). .
• the air permeability of the power storage device separator of the present embodiment is preferably 30 to 500 seconds/100 cc from the viewpoint of reducing battery resistance while ensuring safety.
• the air permeability is 30 sec/100 cc or more, the flow of large current can be effectively prevented, and when the air permeability is 500 sec/100 cc or less, the resistance of the battery tends to decrease.
• the air permeability is more preferably 50 to 500 seconds/100 cc, still more preferably 50 to 400 seconds/100 cc, and even more preferably 50 to 300 seconds/100 cc.
• the air permeability can be measured by the method described in Examples below.
• the air permeability is, for example, the air permeability of the layer (A), the thickness of the layer (B), the volume average particle size of the inorganic filler, the water-insoluble binder, the water-soluble binder, and the content of the polyacrylic acid-based dispersant. It can be adjusted by the amount or the like.
• the interfacial peel strength H between the layer (A) and the layer (B) in the propylene carbonate of the second separator is 3 N/m or more from the viewpoint of heat resistance. From the same point of view, the interfacial peel strength H of the second separator is preferably 4 N/m or more, more preferably 5 N/m or more, still more preferably 8 N/m or more, and still more preferably 10 N /m or more, and more preferably 12 N/m or more. Moreover, the interfacial peel strength H of the second separator is preferably 40 N/m or less from the viewpoint of permeability.
• the interfacial peel strength H is more preferably 35 N/m or less, still more preferably 25 N/m or less.
• the reason why the second separator can suppress thermal shrinkage in the electrolytic solution and ensure safety even when combined with a positive electrode material containing a large amount of nickel is not limited to the following reasons. It is estimated as follows. That is, since the second separator has an interfacial peel strength H of 3 N/m or more, when applied as a separator for an electric storage device, the layer (B) is strongly bonded to the layer (A) even in the electrolyte.
• the layer (B) containing a predetermined polyacrylic acid-based dispersant and a water-soluble binder to more effectively exhibit the ability to suppress heat shrinkage, and is therefore safe even for high-nickel positive electrodes. It is thought that it is possible to ensure the reliability.
• the interfacial peel strength H is not intended to be limited, it is preferably within the above range from the same viewpoint as above. That is, the interfacial peel strength H between the layer (A) and the layer (B) in the propylene carbonate of the first separator is preferably 3 N/m or more from the viewpoint of heat resistance.
• the interfacial peel strength H of the first separator is more preferably 4 N/m or more, still more preferably 5 N/m or more, still more preferably 8 N/m or more, and still more preferably It is 10 N/m or more, and more preferably 12 N/m or more.
• the interfacial peel strength H of the first separator is preferably 40 N/m or less from the viewpoint of permeability. From the same point of view, the interfacial peel strength H of the first separator is more preferably 35 N/m or less, still more preferably 25 N/m or less.
• the interfacial peel strength H can be measured by the method described in Examples below.
• the interfacial peel strength H can be obtained, for example, by subjecting the surface of the layer (A) to a surface treatment such as corona discharge treatment under the preferable conditions described later, and using a water-insoluble binder, a water-soluble binder and polyacrylic acid as the layer (B).
• a surface treatment such as corona discharge treatment under the preferable conditions described later
• a water-insoluble binder, a water-soluble binder and polyacrylic acid as the layer (B).
• a system dispersant etc.
• it tends to fall within the range described above.
• it can be adjusted by the volume average particle size of the inorganic filler, the content of the water-insoluble binder, the water-soluble binder, the polyacrylic acid-based dispersant, and the like.
• the method for producing the separator for an electricity storage device of the present embodiment is not particularly limited, and can include a step of producing a layer (A) and a step of forming a layer (B) on at least one surface of the layer (A). .
• Various known methods can be employed in the step of producing the layer (A), for example, (1) A method of melt-kneading a polyolefin resin composition and a pore-forming material to form a sheet, stretching the sheet if necessary, and extracting the pore-forming material to form a porous sheet; (2) A method of melt-kneading a polyolefin resin composition, extruding it at a high draw ratio, and then exfoliating the polyolefin crystal interface by heat treatment and stretching to make it porous; (3) A method in which a polyolefin resin composition and an inorganic filler are melt-kneaded to form a sheet, and then the interface between the polyolefin and the inorganic filler is exfoliated by stretching to make the sheet porous. (4) A method of dissolving a polyolefin resin composition and then immersing it in a poor solvent for polyolefin to solidify the polyolefin and at the same time remove the solvent to
• the method for producing the layer (A) As an example of the method for producing the layer (A), a method of melt-kneading the polyolefin resin composition and the pore-forming material to form a sheet, and then extracting the pore-forming material will be described below.
• the polyolefin resin composition and the pore-forming material are melt-kneaded.
• a melt-kneading method for example, a polyolefin resin and, if necessary, other additives are introduced into a resin kneading device such as an extruder, a feeder, a Laboplastomill, a kneading roll, a Banbury mixer, etc., while heating and melting the resin component.
• a method of introducing and kneading a pore-forming material in an arbitrary ratio can be mentioned.
• Pore formers can include plasticizers, inorganic materials, or combinations thereof.
• plasticizers include, but are not limited to, nonvolatile solvents capable of forming a uniform solution above the melting point of polyolefin, such as hydrocarbons such as liquid paraffin and paraffin wax; esters such as dioctyl phthalate and dibutyl phthalate. class: higher alcohols such as oleyl alcohol and stearyl alcohol;
• liquid paraffin has high compatibility with polyethylene and/or polypropylene when the polyolefin resin is polyethylene and/or polypropylene. It is preferable because it tends to be easier to carry out stretching.
• the inorganic material is not particularly limited, and examples include oxide-based ceramics such as alumina, silica (silicon oxide), titania, zirconia, magnesia, ceria, yttria, zinc oxide, and iron oxide; silicon nitride, titanium nitride, nitride Nitride ceramics such as boron; silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite , asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, silica sand, and other ceramics; and glass fiber. These are used individually by 1 type or in combination of 2 or more types. Among these inorganic materials, silica, alumina, and titania are preferred from the viewpoint of electrochemical stability, and silica is particularly
• the melted and kneaded material is formed into a sheet.
• the method for producing the sheet-shaped molding is not particularly limited, but for example, the melt-kneaded product is extruded into a sheet through a T-die or the like, brought into contact with a heat conductor, and heated sufficiently above the crystallization temperature of the resin component.
• a method of solidifying by cooling to a low temperature can be mentioned.
• the heat conductor used for cooling and solidification is not particularly limited, but examples thereof include metal, water, air, plasticizer, and the like. Among these, it is preferable to use a metal roll because the efficiency of heat conduction is high.
• the die lip interval when extruding the melt-kneaded material from the T-die into a sheet is preferably 200 ⁇ m or more and 3,000 ⁇ m or less, more preferably 500 ⁇ m or more and 2,500 ⁇ m or less.
• die buildup and the like are reduced, the influence of streaks, defects, and the like on film quality is small, and the risk of film breakage, etc. in the subsequent stretching process tends to be reduced.
• the die lip interval is 3,000 ⁇ m or less, the cooling rate is high, and uneven cooling can be prevented, and there is a tendency to maintain the thickness stability of the sheet.
• the sheet-like compact may be rolled.
• Rolling can be performed, for example, by a press method using a double belt press machine or the like.
• Rolling tends to increase the orientation of the surface layer portion in particular.
• the rolling surface ratio is preferably more than 1 times and 3 times or less, and more preferably more than 1 time and 2 times or less.
• the rolling ratio exceeds 1, the plane orientation tends to increase and the film strength of the finally obtained layer (A) tends to increase.
• the rolling ratio is 3 times or less, the orientation difference between the surface layer portion and the center portion is small, and there is a tendency that a uniform porous structure can be formed in the thickness direction of the film.
• the pore-forming material is removed from the sheet-like compact to form a layer (A).
• a method for removing the pore-forming material for example, there is a method of immersing the sheet-like molding in an extraction solvent to extract the pore-forming material, followed by sufficiently drying.
• the method of extracting the pore-forming material may be batch or continuous.
• the amount of the pore-forming material remaining in the layer (A) is preferably less than 1% by mass with respect to the total mass of the layer (A).
• the extraction solvent used for extracting the pore-forming material it is preferable to use a solvent that is a poor solvent for the polyolefin resin, a good solvent for the pore-forming material, and has a boiling point lower than the melting point of the polyolefin resin.
• extraction solvents include, but are not limited to, hydrocarbons such as n-hexane and cyclohexane; halogenated hydrocarbons such as methylene chloride and 1,1,1-trichloroethane; hydrofluoroethers and hydrofluorocarbons.
• extraction solvents such as ethanol and isopropanol; ethers such as diethyl ether and tetrahydrofuran; and ketones such as acetone and methyl ethyl ketone.
• extraction solvents may be recovered by an operation such as distillation and reused.
• an aqueous solution of sodium hydroxide, potassium hydroxide, or the like can be used as an extraction solvent.
• Stretching may be performed before extracting the pore-forming material from the sheet-like compact.
• the layer (A) obtained by extracting the pore-forming material from the sheet-like formed body may be treated. Further, the treatment may be performed before and after extracting the pore-forming material from the sheet-like compact.
• biaxial stretching is preferable from the viewpoint of improving the strength of the resulting layer (A).
• the sheet-shaped molding is stretched in the biaxial direction at a high magnification, the molecules are oriented in the plane direction, and the finally obtained layer (A) becomes difficult to tear and has a high puncture strength.
• stretching methods include simultaneous biaxial stretching, sequential biaxial stretching, multistage stretching, and multiple stretching.
• simultaneous biaxial stretching is preferable from the viewpoints of improvement in puncture strength, uniformity of stretching, and shutdown properties.
• Sequential biaxial stretching is preferable from the viewpoint of ease of control of plane orientation.
• the simultaneous biaxial stretching means that stretching in the MD (the machine direction during continuous molding of the layer (A)) and stretching in the TD (the direction crossing the MD of the layer (A) at an angle of 90°) are performed at the same time. It refers to the stretching method used, and the stretching ratio in each direction may be different. Sequential biaxial stretching refers to a stretching method in which MD and TD stretching are independently applied, and when stretching is carried out in MD or TD, the other direction is unconstrained or fixed at a fixed length. state.
• the draw ratio is preferably in the range of 20 times or more and 100 times or less, and more preferably in the range of 25 times or more and 70 times or less.
• the draw ratio in each axial direction is preferably in the range of 4 to 10 times in MD, 4 to 10 times in TD, 5 to 8 times in MD, and 5 to 8 times in TD. is more preferably in the range of When the total area magnification is 20 times or more, the obtained layer (A) tends to have sufficient strength. Productivity tends to be obtained.
• the layer (A) is preferably heat-treated for the purpose of heat setting.
• a stretching operation performed at a predetermined temperature atmosphere and a predetermined stretching rate, and / or for the purpose of reducing stretching stress, relaxation performed at a predetermined temperature atmosphere and a predetermined relaxation rate. operations.
• the relaxation operation may be performed after the stretching operation.
• the stretching operation is performed by stretching the MD and/or TD of the membrane by 1.1 times or more, more preferably 1.2 times or more, from the viewpoint of obtaining a layer (A) with further high strength and high porosity. preferable.
• a relaxation operation is a reduction operation to MD and/or TD of a membrane.
• the relaxation rate is the value obtained by dividing the dimension of the membrane after the relaxation operation by the dimension of the membrane before the relaxation operation. When both MD and TD are relaxed, it is a value obtained by multiplying the relaxation rate of MD and the relaxation rate of TD.
• the relaxation rate is preferably 1.0 or less, more preferably 0.97 or less, even more preferably 0.95 or less.
• the relaxation rate is preferably 0.5 or more from the viewpoint of film quality.
• the relaxation operation may be performed in both MD and TD, or may be performed in either MD or TD.
• the stretching and relaxation operations after the extraction of the plasticizer are preferably performed in the TD.
• the temperature in the stretching and relaxation operations is preferably lower than the melting point (hereinafter also referred to as "Tm") of the polyolefin resin, more preferably in the range of 1°C to 25°C lower than Tm. It is preferable from the viewpoint of the balance between reduction in heat shrinkage and porosity that the temperature in the stretching and relaxation operations is within the above range.
• layer (B) is formed on at least one surface of layer (A).
• a coating liquid for forming the layer (B) is applied to the layer (A).
• the surface of the layer (A) on the layer (B) side is subjected to corona discharge.
• Hydrophilization by treatment or the like is preferable.
• the hydrophilization treatment is preferably corona discharge treatment or plasma treatment, and more preferably corona discharge treatment.
• the absorption peak ratio at 1734 cm ⁇ 1 /2918 cm ⁇ 1 when the surface of the layer (A) on the layer (B) side is measured by ATR-IR is 0.025 to 0.125.
• the treatment conditions are such that Such treatment conditions are not particularly limited, but can be adjusted by adjusting the strength of the corona treatment, the distance between the discharge electrode and the layer (A), and the like.
• the intensity of corona treatment is preferably 1 W/(m 2 /min) to 50 W/(m 2 /min). When the corona treatment intensity is 1 W/(m 2 /min) or more, there is a tendency that the discharge to the layer (A) is stably performed.
• the absorption peak ratio is more preferably 3 W/(m 2 /min) to 45 W/(m 2 /min), still more preferably 5 W/(m 2 /min) to 35 W/(m 2 /min), more preferably 7 W/(m 2 /min) to 30 W/(m 2 /min), still more preferably 9 W/(m 2 /min) to 25 W/(m 2 /min) ), more preferably 11 W/(m 2 /min) or more and less than 20 W/(m 2 /min), particularly preferably 13 W/(m 2 /min) to 15 W/(m 2 /min) be.
• the hydrophilization can also be carried out by plasma treatment.
• the plasma treatment conditions are such that the absorption peak ratio at 1734 cm ⁇ 1 /2918 cm ⁇ 1 when the surface of the layer (A) on the layer (B) side is measured by ATR-IR is 0.025 to 0. It is preferable that the processing conditions are such that 0.125 is obtained.
• Such treatment conditions are not particularly limited, but, for example, the conditions can be appropriately adjusted in consideration of the fact that the value of the absorption peak ratio tends to increase by increasing the applied voltage during plasma processing.
• the coating liquid for forming the layer (B) one containing an inorganic filler, a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based dispersant can be used. By using these components together, a layer (B) containing an inorganic filler, a water-insoluble binder, a water-soluble binder, and a polyacrylic acid-based dispersant is formed, and as a result, 140 The heat shrinkage rate S1 at °C becomes 5% or less. After coating the layer (A) with the coating liquid, the layer (A) is dried to remove the solvent of the coating liquid, form the layer (B), and obtain the power storage device separator of the present embodiment.
• the coating liquid preferably contains water from the viewpoint of uniformly dispersing and dissolving the inorganic filler, water-insoluble binder, water-soluble binder, and polyacrylic acid-based dispersant.
• water in addition to water, solvents such as methanol, ethanol, and isopropyl alcohol may be contained within a range that does not impair the solubility and dispersibility.
• the coating liquid may contain a surfactant or the like in order to stabilize dispersion or improve coatability, adjust the contact angle of the surface of the layer (B), and crosslink the binder for the purpose of improving heat resistance.
• Wetting agents; antifoaming agents; pH adjusters containing acids and alkalis; and various additives such as cross-linking agents may be added.
• the total amount of these additives to be added is preferably 20 parts by mass or less for the active ingredient (the mass of the dissolved additive component when the additive is dissolved in a solvent) per 100 parts by mass of the inorganic filler. , more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less is.
• Additives include anionic surfactants such as higher fatty acid salts, alkylsulfonates, alpha olefinsulfonates, alkanesulfonates, alkylbenzenesulfonates, sulfosuccinates, alkyl sulfates, alkyl Ether sulfate, alkyl phosphate, alkyl ether phosphate, alkyl ether carboxylate, alpha sulfo fatty acid methyl ester, methyl taurate and the like.
• anionic surfactants such as higher fatty acid salts, alkylsulfonates, alpha olefinsulfonates, alkanesulfonates, alkylbenzenesulfonates, sulfosuccinates, alkyl sulfates, alkyl Ether sulfate, alkyl phosphate, alkyl ether phosphate, alkyl ether carboxylate, alpha sul
• nonionic surfactants include glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene -polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, fatty acid alkanolamides, alkyl glucosides and the like.
• Amphoteric surfactants include, for example, alkylbetaines, fatty acid amidopropylbetaines, alkylamine oxides, and the like.
• Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts and the like.
• polymer surfactants such as fluorine-based surfactants, cellulose derivatives, polycarboxylates, polystyrenesulfonates, and the like can be used.
• Examples of cross-linking agents include epoxy-based cross-linking agents, oxazoline-based cross-linking agents, and metal chelate-based cross-linking agents.
• Examples of the metal chelate-based cross-linking agent include, but are not particularly limited to, ammonium zirconium carbonate.
• the method of dispersing or dissolving the inorganic filler and the polyacrylic acid-based dispersant in the medium of the coating liquid is not particularly limited as long as it can realize the dispersion characteristics of the coating liquid necessary for the coating process.
• examples include ball mills, bead mills, planetary ball mills, vibrating ball mills, sand mills, colloid mills, attritors, roll mills, high-speed impeller dispersion, dispersers, homogenizers, high-speed impact mills, ultrasonic dispersion, and mechanical stirring using stirring blades.
• the method of applying the coating liquid to the layer (A) is not particularly limited as long as it can achieve the required layer thickness or coating area.
• Examples include gravure coater method, small diameter gravure coater method, reverse roll Coater method, transfer roll coater method, kiss coater method, dip coater method, knife coater method, air doctor coater method, blade coater method, rod coater method, squeeze coater method, cast coater method, die coater method, screen printing method, spray coating construction method, etc.
• the method for removing the solvent from the coating film after coating is not particularly limited as long as it does not adversely affect the layer (A). Examples thereof include a method of drying at a temperature below the melting point of the material constituting the layer (A) while fixing the layer (A), a method of drying under reduced pressure at a low temperature, and the like. Part of the solvent may also remain as long as it does not significantly affect the device characteristics.
• the power storage device separator described above may further have an optional layer on the surface of either the layer (A) or the layer (B). That is, when the layer (B) is arranged on one side of the layer (A), an optional layer is further provided on the surface of the layer (B), and an optional layer is provided on the surface of the layer (A).
• This embodiment includes both the embodiment in which the layer is provided and the embodiment in which any layer is provided on both the layers (A) and (B). Further, in the case where the layer (B) is arranged on both sides of the layer (A), an embodiment in which an arbitrary layer is further provided on the surface of one layer (B), and both layers (B) Any aspect in which an arbitrary layer is provided on the surface of is included in the present embodiment.
• Optional layers include, for example, thermoplastic polymer-containing layers that can function as adhesive layers.
• the existence form (pattern) of the thermoplastic polymer-containing layer may be, for example, a state in which the thermoplastic polymer exists in a mutually dispersed state over the entire surface of the multilayer porous membrane, or a state in which the thermoplastic polymer exists in a sea-island pattern.
• the arrangement pattern includes, for example, dots, stripes, grids, stripes, tortoise shells, random patterns, and combinations thereof.
• the optional layer includes a porous layer that does not correspond to the layer (B) in this embodiment.
• the type, total number, existence form (pattern), and thickness of these arbitrary layers are not particularly limited, and can be appropriately adjusted in consideration of being within a range that does not impair the effects of the present embodiment. .
• the power storage device of the present embodiment includes the power storage device separator of the present embodiment.
• a typical example of the configuration of the electricity storage device of the present embodiment includes, but is not limited to, a positive electrode, an electricity storage device separator, a negative electrode, and optionally an electrolytic solution.
• Specific examples of electricity storage devices include lithium batteries, lithium secondary batteries, lithium ion secondary batteries, sodium secondary batteries, sodium ion secondary batteries, magnesium secondary batteries, magnesium ion secondary batteries, and calcium secondary batteries. , calcium ion secondary battery, aluminum secondary battery, aluminum ion secondary battery, nickel metal hydride battery, nickel cadmium battery, electric double layer capacitor, lithium ion capacitor, redox flow battery, lithium sulfur battery, lithium air battery, zinc air battery etc.
• lithium batteries lithium secondary batteries, lithium ion secondary batteries, nickel hydride batteries, or lithium ion capacitors are preferable, and lithium ion secondary batteries are more preferable, from the viewpoint of practicality.
• the positive electrode the negative electrode, the electrolytic solution, and other members of the electric storage device, various known ones can be appropriately used according to the type of the electric storage device.
• the power storage device separator of the present embodiment can ensure safety even when combined with a positive electrode material having a high nickel content
• the power storage device of the present embodiment including the power storage device separator has a nickel content of It is preferable to apply a positive electrode material with a large amount to the positive electrode. That is, the power storage device separator of this embodiment is arranged between a positive electrode containing Li, Co, and Ni, a negative electrode facing the positive electrode, and the positive electrode and the negative electrode.
• An electricity storage device comprising the electricity storage device separator according to any one of the above items, wherein the content ratios of Co and Ni in metals other than Li in the positive electrode are 20 mol% or less and 60 mol% or more, respectively. Preferably.
• the content ratio of Co is preferably 0.1 to 20 mol % from the viewpoint of battery stability and cost.
• the content ratio of Co is 20 mol % or less, there is a tendency that the production cost can be reduced.
• the content ratio of Co is more preferably 1 to 15 mol %, still more preferably 3 to 10 mol %.
• the Ni content is preferably 60 to 99 mol %.
• the content ratio of Ni is more preferably 70 to 97 mol %, still more preferably 80 to 95 mol %.
• G-B2 registered trademark
• [Absorption peak ratio] 670-IR manufactured by Agilent Technologies Inc. was used for the surface of the layer (A) after corona treatment, germanium was used for the prism, and a single reflection ATR method was used at an incident angle of 45 degrees. , 256 integrations, and IR spectra were collected at a resolution of 4 cm ⁇ 1 .
• the resulting chart was subjected to linear type baseline correction using analytical software Agilent Resolution Pro with correction points of 1600 cm ⁇ 1 , 1900 cm ⁇ 1 , 2700 cm ⁇ 1 and 3000 cm ⁇ 1 .
• a peak is detected from the obtained spectrum, and the absorption peak intensity at 1734 cm ⁇ 1 derived from the carbonyl group formed by the surface treatment and the absorption peak intensity at 2918 cm ⁇ 1 derived from the polyethylene contained in the layer (A) are absorbed. peak ratio.
• the coating liquid was subjected to laser particle size distribution measurement. That is, the volume average particle size distribution of the inorganic filler was measured using a measuring device manufactured by Microtrac Bell Co., Ltd. (trade name “Microtrac MT3300EX”). If necessary, the particle size distribution of the inorganic filler was adjusted using the particle size distribution of the water or water-insoluble binder as a baseline. The particle size (D50 particle size) at which the cumulative frequency is 50% was defined as the volume average particle size of the inorganic filler.
• the inorganic filler in layer (B) of the separator was redispersed and subjected to laser particle size distribution measurement. Specifically, ammonium polycarboxylate ( “SN Dispersant 5468” manufactured by SAN NOPCO Co., Ltd.) as a dispersing agent was added to 10 mL of an aqueous solution adjusted to have a solid content of 1 wt%. After being immersed for a period of time, the layer (B) was scraped off with a spatula or the like to obtain a sample. The particle size distribution of the inorganic filler was measured using a measuring device manufactured by Microtrac Bell Co., Ltd.
• Primary particle size of inorganic filler in layer (B) The separator is freeze-fractured, conducting treatment is performed with C paste and Os coating, and then a surface scanning electron microscope (Hitachi High Technology HITACHI S-4800) is used. was arbitrarily set according to the particle diameter so that the number of particles was observed), and an electron image of a cross-sectional SEM image of the layer (B) was photographed in three fields at an accelerating voltage of 1.0 kV.
• the "primary particle size” was defined as the particle size of individual particles dispersed in a matrix alone, or the smallest particle size of aggregated particles. Ten diameters of circles circumscribing each inorganic filler present in the observed visual field were randomly measured, and the average value was adopted.
• Maximum particle size of inorganic filler in layer (B) The separator is freeze-fractured, conducting treatment is performed with C paste and Os coating, and then a surface scanning electron microscope (Hitachi High Technology HITACHI S-4800) is used. was arbitrarily set according to the particle diameter so that the number of particles was observed), and an electron image of a cross-sectional SEM image of the layer (B) was photographed in three fields at an accelerating voltage of 1.0 kV. The diameter of a circle circumscribing each inorganic filler present in the observed field of view was measured, and the maximum value was taken as the maximum particle diameter of the inorganic filler.
• volume average particle size of water-insoluble binder A water dispersion containing a water-insoluble binder was subjected to particle size measurement by a light scattering method. That is, the volume-average particle size distribution of the water-insoluble binder was measured using a measuring device manufactured by LEED & NORTHRUP (trade name: "MICROTRAC UPA150"). The particle size (D50 particle size) at which the cumulative frequency is 50% was defined as the volume average particle size of the water-insoluble binder.
• the glass transition temperature (Tg) was defined as the intersection of a straight line obtained by extending the base line of the obtained DSC curve to the high temperature side and the tangent line at the point of inflection.
• Weight-average molecular weight of water-soluble binder and polyacrylic acid-based dispersant A water-soluble binder or a polyacrylic acid-based dispersant was dried at 130° C. for 5 hours to prepare a sample. After dissolving 0.1 g of a sample in 100 mL of an eluent, the solution was filtered using a membrane filter to obtain a measurement sample. The weight average molecular weight (Mw) of each measurement sample was measured by gel permeation chromatography (manufactured by Hitachi High-Tech Science Co., Ltd., "Chromaster").
• the layer (B) is cut while controlling a speed of 0.1 ⁇ m/s in the vertical direction and 2 ⁇ m/s in the horizontal direction with a diamond cutting blade having a width of 1 mm. ) was pre-cut until a thickness of .
• the coating layer is peeled off for 10 seconds at a speed of 2 ⁇ m / s in the horizontal direction, and the cutting blade unit width is measured at the time of peeling.
• the average value of horizontal force was taken as the value of interfacial peel strength H between layer (A) and layer (B) in propylene carbonate.
• Thermal shrinkage rate S1 (%) The separator was cut to 50 mm in the MD direction and 50 mm in the TD direction, and sandwiched between Teflon sheets (thickness: 100 ⁇ m, 60 mm square). This laminate is housed in a package (thickness 35 ⁇ m, 100 mm square) composed of an aluminum laminate film, 0.5 mL of propylene carbonate is injected, the separator is soaked with propylene carbonate, the remaining piece is sealed, and a sample is obtained. did. After the sample was stored stationary for 24 hours, it was placed in an oven at 140° C. for 1 hour.
• a positive electrode (positive electrode sheet) was prepared by using a rectangular sheet with a short side of 90 mm and a long side of 150 mm, and a lead tab made of aluminum foil not coated with an active material and having a length of 20 mm on the upper part of the short side (positive electrode sheet).
• a negative electrode (negative electrode sheet) was prepared on a rectangular sheet having a short side of 90 mm and a long side of 150 mm, and a lead tab of a copper foil not coated with an active material and having a length of 20 mm on the short side.
• An electrode plate laminate was produced by alternately stacking 73 positive electrode sheets and 74 negative electrode sheets and separating them with separators.
• the separator was a strip-shaped separator having a width of 155 mm, and was alternately folded in a 90-fold manner to produce an electrode plate laminate. After pressing the electrode plate laminate into a flat plate, the laminate was placed in an aluminum laminate film and heat-sealed on three sides. The positive electrode lead tab and the negative electrode lead tab were led out from one side of the laminate film. Further, after drying, the above non-aqueous electrolyte was poured into the container, and the remaining one side was sealed.
• the lithium ion secondary battery manufactured in this manner was designed to have a capacity of 40 Ah.
• the lithium ion secondary battery produced as described above was charged to a battery voltage of 4.2 V at a discharge current of 0.5 C under an environment of 25°C.
• the charged battery was placed in an oven, heated from room temperature to 150° C. at a rate of 5° C./min, left at 150° C. for a predetermined time, and checked for ignition.
• the test results were evaluated based on the following criteria. S: No ignition occurred even after standing for 90 minutes or more.
• B Ignited when left for 50 minutes or more and less than 70 minutes.
• C Ignited when left for 30 minutes or more and less than 50 minutes.
• D Ignition occurred during temperature rise or after standing for less than 30 minutes.
• the surface temperature of the battery was the temperature measured with a thermocouple (K type seal type) at a position 1 cm from the bottom side of the battery exterior body.
• D Fired in one or more cells.
• the lithium ion secondary battery produced in the above safety evaluation 1 is charged at 25 ° C. with a discharge current of 0.5 C to a battery voltage of 4.2 V, and further the current value is increased from 3 mA while maintaining 4.2 V.
• the initial charge after the battery production was performed for a total of about 6 hours by the method of starting throttling, and then the battery was discharged to a battery voltage of 3.0 V with a current.
• the total time is about 3 hours.
• Rate characteristics (%) at 10C (10C discharge capacity/1C discharge capacity) x 100 Rate characteristics at 10C were evaluated according to the following criteria.
• Example 1 Preparation of layer (A) 1 part by mass of pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] as an antioxidant for 100 parts by mass of polyethylene having a viscosity average molecular weight of 800,000
• a mixture of polymers and the like was obtained by adding and dry-blending using a tumbler blender. The resulting mixture was purged with nitrogen and then supplied to a twin-screw extruder through a feeder under a nitrogen atmosphere.
• Liquid paraffin (kinematic viscosity at 37.78° C.
• the gel sheet was led to a simultaneous biaxial tenter stretching machine and biaxially stretched.
• the set stretching conditions were MD magnification of 7.0 times, TD magnification of 6.4 times, and set temperature of 127°C.
• it was introduced into a methylene chloride tank and fully immersed in methylene chloride to extract and remove liquid paraffin, and then dried to remove methylene chloride to obtain a porous body.
• the porous body was guided to a TD tenter and heat-set.
• the heat setting temperature was 126° C.
• the maximum TD magnification was 1.5 times
• the relaxation rate was 0.86 to obtain a layer (A) having a thickness of 9.0 ⁇ m.
• aluminum hydroxide oxide aluminum hydroxide oxide
• D50 0.40 ⁇ m
• dispersant 1 sodium polyacrylate; weight average molecular weight 6,000; 1 0.0 g dissolved in 100 g of water (less than 1.0% by mass of insoluble matter
• Acrylic latex 1 (80% by mass of units derived from butyl acrylate, 16% by mass of units derived from methyl methacrylate, 3% by mass of units derived from acrylic acid, and 3% by mass derived from acrylamide) was added to the mixed solution after treatment as a water-insoluble binder.
• One surface of layer (A) was subjected to corona discharge treatment at a treatment intensity of 15 W/(m 2 /min).
• a coating liquid was applied to the surface after such treatment using a gravure coater. Thereafter, the coating solution on layer (A) was dried at 60° C. to remove water, and layer (B) having a thickness of 3.0 ⁇ m was formed on one surface of layer (A) to obtain a separator. .
• Table 1 shows the physical properties of the obtained separator and the evaluation results of the battery including the separator.
• Examples 2 to 68 and Comparative Examples 1 to 14 The electricity storage device separator was produced and evaluated in the same manner as in Example 1, except that the layers (A) and (B) shown in Tables 1 to 12 were used.
• the weight of the layer (A) is determined by controlling the thickness of the gel sheet to be cast, and the porosity and air permeability are controlled by controlling the biaxial stretching temperature and the heat setting temperature. were adjusted to the numerical values shown in each table by controlling the biaxial stretching temperature and the biaxial stretching ratio.
• a layer (B) having a thickness of 1.5 ⁇ m was formed on both sides of the layer (A) (the total thickness of the layer (B) was 3.5 ⁇ m). 0 ⁇ m).
• Example 69 The exposed surface of the layer (A) of Example 33 was subjected to corona discharge treatment at a treatment intensity of 10 W/(m 2 /min).
• a water dispersion of the following acrylic latex 5 (solid content: 30% by mass) was pattern-coated on the surface after such treatment using a gravure roll with a dot diameter of 200 ⁇ m and a dot pattern of 5 ⁇ m deep, and dried at 60°C. to remove water from the coating liquid.
• a separator having thermoplastic polymer-containing layers on both sides was obtained by performing the same process on the layer (B) side, except for the corona discharge treatment.
• the diameter of the dots formed on the separator was 250 ⁇ m, and the interval between the dots was 300 ⁇ m.
• Example 70 Acrylic latex 5 was applied using a gravure roll in which a dot diameter of 200 ⁇ m and a depth of 5 ⁇ m were printed on both the surface where the layer (A) of Example 53 was exposed and the surface where the layer (B) was exposed.
• a water dispersion (solid content: 30% by mass) was pattern-coated and dried at 60° C. to remove water from the coating liquid to obtain a separator having thermoplastic polymer-containing layers on both sides.
• the diameter of the dots formed on the separator was 250 ⁇ m, and the interval between the dots was 300 ⁇ m.
• the maximum particle diameters of the inorganic filler in the layer (B) were measured from cross-sectional observation, and the maximum particle diameters were 0.85 ⁇ m and 1.92 ⁇ m, respectively.
• acrylic latexes 2-4 The following materials were used as acrylic latexes 2-4, dispersants 2-6, water-soluble polymers 2-3, and additives 2-3 in each table.
• Dispersant 2 Lithium polyacrylate (weight average molecular weight 6,000; less than 1.0% by mass of insoluble matter when 1.0 g is dissolved in 100 g of water)
• Dispersant 3 A copolymer having 50% by mass of units derived from sodium acrylate and 50% by mass of units derived from acrylonitrile (weight average molecular weight 6,000; insoluble when 1.0 g is dissolved in 100 g of water less than 1.0% by mass)
• Dispersant 4 A copolymer containing 89% by mass of units derived from sodium acrylate and 11% by mass of units derived from sodium 3-allyloxy-2-hydroxypropanesulfonate (weight average molecular weight of 6000; 1.0 g of water in 100 g Less than 1.0% by mass of insoluble matter when dissolved in Dispersant 5: ammonium polyacrylate (weight average molecular weight 6,000; less than 1.0% by mass of insoluble matter when 1.0 g is dissolved in 100 g of water)
• Water-soluble polymer 2 Polyvinyl alcohol (weight average molecular weight 150,000; less than 1.0% by mass of insoluble matter when 1.0 g is dissolved in 100 g of water)
• Water-soluble polymer 3 polyvinylpyrrolidone (weight average molecular weight 360,000; less than 1.0% by mass of insoluble content when 1.0 g is dissolved in 100 g of water)
• Additive 2 Polyoxyethylene alkylene alkyl ether (Emulgen LS-110 manufactured by Kao Corporation; 0.10% by mass with respect to the amount of inorganic filler) and ammonium zirconium carbonate (metal chelate-based cross-linking agent; 1.0% with respect to the amount of inorganic filler 0% by mass)
• Additive 3 Polyoxyethylene alkylene alkyl ether (Emulgen LS-110 manufactured by Kao Corporation; 0.50% by mass relative to the amount of inorganic filler)

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