US20180047962A1 - Separator for a non-aqueous secondary battery, and non-aqueous secondary battery - Google Patents

Separator for a non-aqueous secondary battery, and non-aqueous secondary battery Download PDF

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US20180047962A1
US20180047962A1 US15/552,847 US201615552847A US2018047962A1 US 20180047962 A1 US20180047962 A1 US 20180047962A1 US 201615552847 A US201615552847 A US 201615552847A US 2018047962 A1 US2018047962 A1 US 2018047962A1
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separator
porous layer
secondary battery
aqueous secondary
adhesive porous
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Susumu Honda
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Teijin Ltd
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Teijin Ltd
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    • H01M2/162—
    • 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
    • H01M50/44—Fibrous material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator for a non-aqueous secondary battery and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries which are represented by lithium ion secondary batteries, are widely spread as power sources for portable electronic devices such as notebook-size personal computers, mobile phones, digital cameras and camcorders.
  • outer packages of non-aqueous secondary batteries have been simplified and lightened with size reduction and weight reduction of portable electronic devices.
  • aluminum cans have been developed in place of stainless cans, and further, aluminum laminated film packages have been developed in place of metallic cans.
  • an aluminum laminated film package is soft, and therefore in a battery having the package as an outer packaging (soft package battery), a gap is easily formed between an electrode and a separator due to external impact, or electrode expansion and shrinkage associated with charge-discharge, as a result of which the cycle life may be reduced.
  • a separator having a porous layer containing a polyvinylidene fluoride-based resin is liable to electrostatically adsorb foreign substances such as dust, and the handling property may be inferior.
  • a technique of applying a surfactant to a porous layer containing a polyvinylidene fluoride-based resin has been proposed (see, for example, Patent Literature 5).
  • a technique using a clay mineral for a separator has been proposed.
  • a porous film containing a polyvinylidene fluoride-based resin and a clay mineral has been proposed, and ion conductivity of such a film is known to be improved (see, for example, Non Patent Literature 1).
  • a separator having a surface layer containing a heat resistant resin, ceramics and a clay mineral modified with an organic modifier on a base material composed of a porous film has been proposed, and the shrinkage resistance of such a separator is improved (see, for example, Patent Literature 6).
  • Non-Patent Literature 1 European Polymer Journal, 2013, 49, 307-318
  • a separator having an adhesive porous layer containing a polyvinylidene fluoride-based resin is adhered well to an electrode by heat-pressing over the electrode. From a viewpoint of improving the battery performance, it is desirable that the electrode and the separator are strongly adhered, whereas the strength of adhesion between the electrode and the separator changes depending on the temperature of the heat-pressing.
  • the temperature range of heat-pressing capable of realizing sufficient adhesiveness between an electrode and the separator is not so wide.
  • Embodiments of the present invention have been made under the above-described circumstances.
  • An embodiment of the present invention aims to provide a separator for a non-aqueous secondary battery having an adhesive porous layer containing a polyvinylidene fluoride-based resin and having a wide temperature range within which sufficient adhesion between an electrode and the separator can be achieved by heat-pressing, and the present invention aims to solve this problem.
  • a separator for a non-aqueous secondary battery comprising:
  • an adhesive porous layer provided on one or both sides of the porous substrate and comprising a polyvinylidene fluoride-based resin
  • the adhesive porous layer would exhibit a ratio of an area intensity of a ⁇ -phase-crystal-derived peak of the polyvinylidene fluoride-based resin to a sum of an area intensity of an ⁇ -phase-crystal-derived peak of the polyvinylidene fluoride-based resin and the area intensity of the ⁇ -phase-crystal-derived peak of the polyvinylidene fluoride-based resin of from 10% to 100% when an x-ray diffraction spectrum is obtained by performing measurement by an x-ray diffraction method.
  • the adhesive porous layer further comprises at least one kind of particles selected from the group consisting of metal hydroxide particles and metal oxide particles;
  • a content of the particles in the adhesive porous layer is 10% by mass or more but less than 80% by mass with respect to a total amount of the polyvinylidene fluoride-based resin and the particles.
  • a separator for a non-aqueous secondary battery comprising:
  • an adhesive porous layer provided on one or both sides of the porous substrate and comprising a polyvinylidene fluoride-based resin and a layered clay mineral,
  • a weight of the adhesive porous layer on one side of the porous substrate being from 0.5 g/m 2 to 2.0 g/m 2 .
  • a non-aqueous secondary battery comprising:
  • the separator for a non-aqueous secondary battery according to any one of [1] to [14], which is disposed between the positive electrode and the negative electrode,
  • the non-aqueous secondary battery being configured to produce an electromotive force by lithium doping/de-doping.
  • a separator for a non-aqueous secondary battery having an adhesive porous layer containing a polyvinylidene fluoride-based resin and having a wide temperature range within which sufficient adhesion between an electrode and the separator can be achieved by heat-pressing is provided.
  • FIG. 1 is a graph showing a relationship between a peel strength between an electrode and a separator and a heat-pressing temperature.
  • the value range shown using the expression “from . . . to . . . ” in this specification is a range including values described before and after the term “to” as a minimum value and a maximum value, respectively.
  • step refers not only to an independent step, but also to a step that cannot be clearly distinguished from other steps as long as an expected action of the step is achieved.
  • the amount of the component in a case in which plural substances corresponding to the component are present in the composition, means a total amount of the plural substances which are present in the composition, unless otherwise specified.
  • machine direction means a longitudinal direction of a long separator
  • transverse direction means a direction orthogonal to the machine direction of the separator.
  • MD direction the “machine direction”
  • TD direction the “transverse direction”
  • PVDF resin polyvinylidene fluoride-based resin
  • an adhesive porous layer is an outermost layer of the separator and is a layer which adheres to an electrode.
  • the area intensity ratio of the ⁇ -phase-crystal-derived peak of the PVDF resin in the X-ray diffraction spectrum of the adhesive porous layer is 10% or more, a) the temperature range of heat-pressing capable of realizing adequate adhesion between an electrode and a separator is wide, b) the dielectric constant of the adhesive porous layer increases, promoting dissociation of an electrolyte, and c) the oxidation resistance of the adhesive porous layer is improved.
  • the area intensity ratio of the ⁇ -phase-crystal-derived peak of the PVDF resin is more preferably 15% or more, and still more preferably 20% or more.
  • the strength of the adhesion between the electrode and the separator can be evaluated, for example, by the peeling strength between the electrode and the separator.
  • the peeling strength between the electrode and the separator is preferably 0.2 N/15 mm or more.
  • the area intensity ratio of the ⁇ -phase-crystal-derived peak of the PVDF resin is 100%.
  • the area intensity ratio of the ⁇ -phase-crystal-derived peak of the PVDF resin is preferably 100%, and from a viewpoint of productivity of the adhesive porous layer, the ratio is preferably 90% or less, and more preferably 80% or less.
  • the area intensity ratio of a ⁇ -phase-crystal-derived peak of a PVDF resin in the X-ray diffraction spectrum of an adhesive porous layer is preferably 35% or less, more preferably 30% or less, and still more preferably 25% or less from a viewpoint of wide temperature range of heat-pressing capable of realizing adequate adhesion between an electrode and the separator.
  • the area intensity ratio of a ⁇ -phase-crystal-derived peak of a PVDF resin in the X-ray diffraction spectrum of an adhesive porous layer is controlled, for example, by promoting transition of the PVDF resin from the ⁇ -phase-crystal to the ⁇ -phase-crystal by any one of the following control methods 1) to 6) to form a crystal form in which an ⁇ -phase-crystal and a ⁇ -phase-crystal coexist in the adhesive porous layer.
  • the control method 3) is preferable from a viewpoint of the productivity, convenience, and cost reduction.
  • Control method 1 Use of a copolymer of vinylidene fluoride and a monomer having a bulky group (for example, trifluoroethylene, chlorotrifluoroethylene) as a PVDF resin for molding an adhesive porous layer.
  • a copolymer of vinylidene fluoride and a monomer having a bulky group for example, trifluoroethylene, chlorotrifluoroethylene
  • Control method 2 Selection of a solvent of a coating liquid for forming an adhesive porous layer, and adjusting conditions for forming the adhesive porous layer (for example, the composition of the coating liquid, the temperature of the coating liquid, the composition of a coagulating liquid, the temperature of a coagulating liquid, the drying temperature, the presence or absence of heat treatment, and the like).
  • Control method 3 Addition of crystal form regulator to a coating liquid for molding an adhesive porous layer. Adjusting the size, dispersibility, compounding amount, and the like of the crystal form regulator.
  • Control method 4 Use of an ionic liquid as a solvent in a coating liquid for molding an adhesive porous layer, and adjusting conditions for crystallizing a PVDF resin (temperature, time, concentration, etc.).
  • Control method 5 Melting and crystallizing a PVDF resin in an adhesive porous layer when an adhesive porous layer is formed by coextrusion of a porous substrate therewith. Adjusting melting and crystallization conditions (temperature, time, pressure, and the like).
  • Control method 6 Mechanically stretching a separator provided with an adhesive porous layer. Adjusting the stretching temperature and stretch ratio when stretching the separator.
  • the separator of the present disclosure since the area intensity ratio of a ⁇ -phase-crystal-derived peak of a PVDF resin in the X-ray diffraction spectrum of an adhesive porous layer is from 10% to 100%, it is possible to expand the temperature range of the heat-pressing capable of realizing sufficient adhesion between an electrode and the separator. Since the separator of the present disclosure is excellent in adhesion to an electrode, it is possible to enhance the uniformity of an in-battery reaction during charging and discharging of a secondary battery thereby improving the battery performance.
  • the separator of the present disclosure has a wide temperature range of heat-pressing capable of realizing sufficient adhesion between an electrode and the separator, the separator is suitable for a battery (a so-called soft pack battery) using an aluminum laminate film pack as an outer packaging material.
  • a battery a so-called soft pack battery
  • the separator of the present disclosure formation of a gap between an electrode and the separator, which can be caused by expansion and shrinkage of the electrode accompanying charging and discharging or an impact from the outside, is suppressed, and therefore, the quality stability of a soft pack battery can be improved.
  • the half-width of the endothermic peak preferably ranges from 15° C. to 30° C.
  • the endothermic peak is presumed to be an endothermic peak appearing due to melting of a resin contained in the adhesive porous layer.
  • the half-width of an endothermic peak is obtained from a DSC curve obtained by collecting an adhesive porous layer from a separator and performing DSC under a nitrogen atmosphere at a heating rate of 10° C./min.
  • the half-width is a full width at half maximum.
  • the height of an endothermic peak is the height from a baseline connecting a peak start point and a peak end point.
  • a point at which a sudden change starts obtained by differentiating the DSC curve is set as the peak start point or the peak end point.
  • the half-width of the maximum endothermic peak is preferably from 15° C. to 30° C.
  • the temperature range of the heating press at the time of adhering the separator and an electrode is wider.
  • the half-width of the endothermic peak is more preferably 18° C. or higher, and still more preferably 20° C. or higher.
  • the half-width of the endothermic peak in the DSC curve of the adhesive porous layer is 30° C. or less, the adhesive porous layer is excellent in resistance to dissolution in an electrolytic solution.
  • the half-width of the endothermic peak is more preferably 27° C. or less, and still more preferably 25° C. or less.
  • the half-width of the endothermic peak in the DSC curve of the adhesive porous layer can be controlled by the crystal form of a PVDF resin.
  • the half-width can be broadened by blending a crystal form regulator in a coating liquid for forming an adhesive porous layer, so that transition from an ⁇ -phase-crystal to a ⁇ -phase-crystal of the PVDF resin is promoted and thus a crystal form in which an ⁇ -phase-crystal and a ⁇ -phase-crystal coexist in the adhesive porous layer is formed.
  • porous substrate and the adhesive porous layer included in the separator of the present disclosure are explained below.
  • porous substrate means a substrate having pores or voids inside.
  • a substrate include a microporous membrane; a porous sheet formed of a fibrous material, such as nonwoven fabric or a paper-like sheet; and the like.
  • a microporous membrane is preferable in the present disclosure.
  • the “microporous membrane” means a membrane that has a large number of micropores inside, and has a structure in which these micropores are joined, to allow gas or liquid to pass therethrough from one side to the other side.
  • the porous substrate preferably contain a thermoplastic resin from the viewpoint of imparting a shutdown function to the porous substrate.
  • the term “shutdown function” refers to the following function. Namely, in a case in which the battery temperature increases, the thermoplastic resin melts and blocks the pores of the porous substrate, thereby blocking migration of ions, to prevent thermal runaway of the battery.
  • the thermoplastic resin a resin having a melting temperature of lower than 200° C. is preferable.
  • the thermoplastic resin include: polyesters such as polyethylene terephthalate; and polyolefins such as polyethylene and polypropylene. Among these, polyolefins are preferable.
  • a microporous membrane (referred to as “polyolefin microporous membrane”) including polyolefin is preferable.
  • the polyolefin microporous membrane include those applied to a conventional separator for a non-aqueous secondary battery, and one that has sufficient mechanical characteristic and ion permeability may be preferably selected therefrom.
  • the polyolefin microporous membrane preferably includes polyethylene, and the content of polyethylene is preferably 95% by mass or larger with respect to a mass of an entire of the polyolefin microporous membrane.
  • a polyolefin microporous membrane including polyethylene and polypropylene is preferable.
  • An example of such a polyolefin microporous membrane is a microporous membrane in which polyethylene and polypropylene are present as a mixture in one layer.
  • polyethylene is contained in an amount of 95% by mass or more and polypropylene is contained in an amount of 5% by mass or less, from the viewpoint of achieving both the shutdown function and heat resistance.
  • the polyolefin contained in the polyolefin microporous membrane has a weight average molecular weight (Mw) of from 100,000 to 5,000,000.
  • Mw weight average molecular weight
  • the weight average molecular weight is 100,000 or more, sufficient mechanical characteristics can be ensured.
  • the weight average molecular weight is 5,000,000 or less, the shutdown characteristics are favorable, and it is easy to form a membrane.
  • the polyolefin microporous membrane can be manufactured, for example, by the following method. Namely, the polyolefin microporous membrane can be manufactured by a method in which a molten polyolefin resin is extruded through a T-die to form a sheet, the sheet is subjected to a crystallization treatment, followed by stretching, and further is subjected to a heat treatment, thereby obtaining a microporous membrane.
  • the polyolefin microporous membrane can be manufactured by a method in which a polyolefin resin melted together with a plasticizer such as liquid paraffin is extruded through a T-die, followed by cooling, to form a sheet, the sheet is stretched, the plasticizer is extracted from the sheet, and the sheet is subjected to to a heat treatment, thereby obtaining a microporous membrane.
  • a plasticizer such as liquid paraffin
  • porous sheet formed of a fibrous material examples include a porous sheet formed of a nonwoven fabric formed of fibrous material of a thermoplastic resin, a paper, or the like.
  • the surface of the porous substrate may be subjected to a surface treatment selected from various ones as long as it does not impair characteristics of the porous substrate.
  • a surface treatment selected from various ones as long as it does not impair characteristics of the porous substrate. Examples of the surface treatment include a corona treatment, a plasma treatment, a flame treatment, and an ultraviolet irradiation treatment.
  • a thickness of the porous substrate is preferably from 3 ⁇ m to 25 ⁇ m, and more preferably from 5 ⁇ m to 20 ⁇ m.
  • a Gurley value (JIS P8117(2009)) of the porous substrate is preferably from 50 sec/100 cc to 800 sec/100 cc, more preferably from 50 sec/100 cc to 400 sec/100 cc, and still more preferably from 50 sec/100 cc to 250 sec/100 cc.
  • the porous substrate has a porosity of from 20% to 60%.
  • the porosity of the porous substrate is determined by the following calculation method. That is, setting the constituent materials to a, b, c, . . . , n, the weights of the constituent materials to Wa, Wb, Wc, . . . , Wn (g/cm 2 ), the true densities of the constituent materials da, db, dc, . . . , dn (g/cm 3 ), and the film thickness of a layer of interest to t (cm), the porosity c(%) is determined by the following formula.
  • a piercing strength of the porous substrate is preferably 200 g or more.
  • the piercing strength of the porous substrate refers to a maximum piercing load (g) measured by a piercing test which uses a handy compression tester KES-G5 available from Katotech Co., Ltd., with conditions of a needle having a tip with a radius of curvature of 0.5 mm and a piercing rate of 2 mm/sec.
  • the adhesive porous layer is provided on one side or both sides of a porous substrate, and is a porous layer containing at least a PVDF resin.
  • the adhesive porous layer may further contain another resin that is other than the PVDF resin, or other components such as a filler.
  • the adhesive porous layer has a large number of fine pores inside, and has a structure in which these fine pores are connected, so that gas or liquid can pass from one side to the other side.
  • the adhesive porous layer is provided as an outermost layer of a separator on one side or both sides of a porous substrate, and is a layer which adheres to an electrode when the separator and the electrode are layered and subject to pressing or heat-pressing.
  • the adhesive porous layer is preferably on both sides rather than on only one side of the porous substrate from a viewpoint of superior cycle characteristics (capacity retention rate) of a battery. This is because when an adhesive porous layer is on both sides of a porous substrate, both sides of a separator adhere well to both electrodes via the adhesive porous layer.
  • the separator of the present disclosure is excellent in adhesion to an electrode as the separator has the adhesive porous layer, which includes a PVDF resin, at its outermost later.
  • PVDF resin contained in the adhesive porous layer examples include a homopolymer of vinylidene fluoride (i.e. polyvinylidene fluoride); a copolymer of vinylidene fluoride and other copolymerizable monomer (polyvinylidene fluoride copolymers); and mixtures thereof.
  • monomer polymerizable with vinylidene fluoride include tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, vinyl fluoride and trichloroethylene, one of which or two or more of which may be employed.
  • the PVDF resin is preferably a copolymer in which vinylidene fluoride and at least hexafluoropropylene are copolymerized.
  • the PVDF resin is prepared by copolymerizing hexafluoropropylene with vinylidene fluoride, crystallinity and heat resistance of the polyvinylidene fluoride-based resin can be regulated to fall within a proper range, as a result of which it becomes possible to inhibit flowing of the adhesive porous layer during a process of bonding of the porous layer to the electrode.
  • a proportion of constituent units derived from hexafluoropropylene in the copolymer is preferably from 0.1 mol % to 10 mol %, (and preferably from 0.5 mol % to 8 mol %).
  • a copolymer of vinylidene fluoride and a monomer having a bulky group is preferably used.
  • the PVDF resin preferably has a weight average molecular weight (Mw) of from 300,000 to 3,000,000.
  • Mw weight average molecular weight
  • the Mw of the PVDF resin is 300,000 or more, mechanical properties by which an adhesive porous layer can withstand an adhesion treatment with an electrode can be ensured, and sufficient adhesiveness can be obtained.
  • the Mw of the PVDF resin is preferably 500,000 or more, more preferably 800,000 or more, and still more preferably 1,000,000 or more.
  • the Mw of the PVDF resin is 3,000,000 or less, the viscosity of a coating liquid for coating and molding an adhesive porous layer does not become too high, and the moldability and crystal formation are favorable, whereby the adhesive porous layer is favorably made porous.
  • the Mw of the PVDF resin is more preferably equal to or less than 2,500,000, and still more preferably equal to or less than 2,000,000.
  • Examples of a method of manufacturing the PVDF resin include emulsion polymerization and suspension polymerization.
  • a commercially available PVDF resin can also be used.
  • a content of the PVDF resin contained in the adhesive porous layer based on a total amount of all the resins contained in the adhesive porous layer is preferably 95% by mass or more, more preferably 97% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass.
  • the adhesive porous layer may contain a resin other than the PVDF resin.
  • the resin other than the PVDF resin examples include acrylic resins, fluorine-containing rubbers, styrene-butadiene copolymers, homopolymers or copolymers of vinylnitrile compounds (such as acrylonitrile, or methacrylonitrile), carboxymethyl cellulose, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, and polyethers (such as polyethylene oxide or polypropylene oxide).
  • acrylic resins fluorine-containing rubbers
  • styrene-butadiene copolymers homopolymers or copolymers of vinylnitrile compounds (such as acrylonitrile, or methacrylonitrile), carboxymethyl cellulose, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, and polyethers (such as polyethylene oxide or polypropylene oxide).
  • acrylic resin examples include a polymer obtained by homopolymerizing or copolymerizing an acrylic acid ester such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate or hydroxypropyl acrylate; a polymer obtained by homopolymerizing or copolymerizing a methacrylic acid ester such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, or diethylaminoethyl methacrylate; a copolymer of at least one acrylate ester and at least
  • PMMA polymethyl methacrylate
  • PMMA may be a polymer obtained by homopolymerizing methyl methacrylate or a copolymer obtained by copolymerizing a monomer other than methyl methacrylate.
  • Such other monomer to be copolymerized is preferably at least one selected from methyl acrylate, an acrylic acid, and a methacrylic acid.
  • a weight average molecular weight (Mw) of the acrylic resin is preferably from 300,000 to 3,000,000.
  • Mw of the acrylic resin is 300,000 or more, the mechanical properties of an adhesive porous layer are more excellent and the adhesive property to an electrode is excellent.
  • Mw of the acrylic resin is 3,000,000 or less, the viscosity of a coating liquid for coating and molding an adhesive porous layer does not become too high, the moldability and crystal formation are favorable, whereby the adhesive porous layer is favorably made porous.
  • the weight average molecular weight of the acrylic resin is more preferably from 300,000 to 2,000,000.
  • the crystal form regulator examples include organic fillers and inorganic fillers.
  • the inorganic filler may be surface-modified with a silane coupling agent or the like.
  • One type of the crystal form regulator may be used alone, or two or more types of the crystal form regulator may be used in combination.
  • an organic filler or an inorganic filler having a large aspect ratio is preferable.
  • a carbon nanotube or a layered clay mineral is preferable, and a layered clay mineral is more preferable.
  • the aspect ratio of the crystal form regulator is preferably from 5 to 1,000, and more preferably from 10 to 500.
  • the crystal form regulator is a clay mineral which is an inorganic compound having a layered structure, a so-called layered clay mineral.
  • the adhesive porous layer preferably contains a layered clay mineral from a viewpoint of controlling the crystal form of the PVDF resin and controlling the area intensity ratio of the ⁇ -phase-crystal-derived peak.
  • layered clay mineral examples include layered silicate (Si—Al-based, Si—Mg-based, Si—Al—Mg-based, Si—Ca-based or the like).
  • the layered clay mineral contained in the adhesive porous layer may be in a single layer state or in a multilayer state.
  • the layered clay mineral preferably has a cation exchange ability and further exhibits a property of swelling by incorporating water between layers, and preferred examples thereof include smectite clay mineral and swelling mica.
  • smectite clay mineral examples include hectorite, saponite, stevensite, beidellite, montmorillonite (these may be natural or chemically synthesized), and substitutes, derivatives, or mixtures thereof.
  • swelling mica examples include synthetic swellable mica which is chemically synthesize and having Li ions or Na ions between layers, and substitutes, derivatives, or mixtures thereof.
  • layered clay minerals in which particles of the layered clay mineral are treated with an intercalating agent are preferable.
  • intercalating agent a compound containing an organic onium ion is preferable.
  • the layered clay mineral having an organic onium ion between layers (herein, sometimes referred to as “organic onium ion modified layered clay mineral”) is excellent in dispersibility in a PVDF resin, it is presumed that: a) the uniformity of the higher order structure of the adhesive porous layer is increased, whereby the adhesion of the adhesive porous layer to an electrode is further strengthened; b) charging of the adhesive porous layer is further suppressed; and c) transition from ⁇ -type-crystal to ⁇ -type-crystal of the PVDF resin is promoted.
  • the compound containing an organic onium ion used as the intercalating agent is preferably selected from a salt (so-called quaternary ammonium compound) of a quaternary ammonium ion, (that is, a cation) having a chemical structure represented by the following Formula (1) and an anion.
  • R 1 , R 2 , R 3 , and R 4 each independently represent an alkyl group having from 1 to 30 carbon atoms or a hydroxypolyoxyethylene group represented by —(CH 2 CH 2 O) n H (n is an integer of from 1 to 30).
  • R 1 , R 2 , R 3 , and R 4 are preferably an alkyl group having from 1 to 30 carbon atoms, and more preferably an alkyl group having from 1 to 18 carbon atoms.
  • Examples of the quaternary ammonium compound preferable as the intercalating agent include dodecyltrimethylammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dioleyl dimethyl ammonium chloride, dodecyl diethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, hexadecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, oleyl dimethyl benzy
  • Examples of a method of treating a layered clay mineral particle with a compound containing an organic onium ion include a method in which 1 part by mass of layered clay mineral and 1 part by mass to 10 parts by mass of a compound containing an organic onium ion are mixed in water and then the mixture is dried.
  • An amount of the water to be used (on a mass basis) is preferably from 1 time to 100 times the layered clay mineral.
  • a temperature at the time of mixing is preferably from 30° C. to 70° C., and the mixing time is preferably from 0.5 hours to 2 hours.
  • a general method such as hot air drying, vacuum drying, freeze drying or the like can be used, although not limited thereto.
  • Layered clay minerals are generally plate-like particles with a large aspect ratio.
  • the aspect ratio of the layered clay mineral is preferably from 5 to 1,000, more preferably from 10 to 500, from a viewpoint of easily exhibiting a function of controlling the crystal form of a PVDF resin.
  • a major axis length of the layered clay mineral is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • An average layer thickness of the layered clay mineral contained in the adhesive porous layer is preferably 500 nm or less, more preferably 200 nm or less, and still more preferably 150 nm or less.
  • the average layer thickness of the layered clay mineral is 500 nm or less, the non-uniformity of the porous structure of the adhesive porous layer is suppressed, whereby the load characteristics of a secondary battery are further improved.
  • the average layer thickness of the layered clay mineral contained in the adhesive porous layer means an average value of the layer thicknesses of 20 arbitrarily selected layered clay minerals measured by observing a cross section of the adhesive porous layer with an electron microscope.
  • the average layer thickness of the layered clay mineral contained in the adhesive porous layer can be controlled by a particle diameter and an addition amount of the layered clay mineral used for preparation of a coating liquid.
  • a mass ratio of the PVDF resin to the layered clay mineral contained in the adhesive porous layer is preferably from 99.9:0.1 to 90.0:10.0.
  • the mass ratio of the layered clay mineral is preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.5 or more, and still more preferably 1.0 or more.
  • the mass ratio of the layered clay mineral is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 4.0 or less, and still more preferably 3.0 or less.
  • the mass ratio of the PVDF resin to the layered clay mineral contained in the adhesive porous layer is preferably from 99.9:0.1 to 90.0:10.0, more preferably from 99.9:0.1 to 95.0:5.0, still more preferably from 99.8:0.2 to 95.0:5.0, still more preferably from 99.8:0.2 to 96.0:4.0, still more preferably from 99.5:0.5 to 96.0:4.0, still more preferably from 99.0:1.0 to 96.0:4.0, and still more preferably from 99.0:1.0 to 97.0:3.0.
  • One embodiment of the separator of the present disclosure includes a porous substrate and an adhesive porous layer including the PVDF resin and the layered clay mineral provided on one side or both sides of the porous substrate, and a weight of the adhesive porous layer is 0.5 g/m 2 to 2.0 g/m 2 on one side of the porous substrate. This embodiment is excellent in adhesion to an electrode and excellent in handling property.
  • the adhesive porous layer may contain a filler made of an inorganic material or an organic material and other additives for the purpose of improving the slipping property and heat resistance of a separator.
  • a filler made of an inorganic material or an organic material and other additives for the purpose of improving the slipping property and heat resistance of a separator.
  • the filler content is preferably less than 80% by mass based on a total amount of the PVDF resin and the filler, and when the content is less than 80% by mass, the adhesion of the adhesive porous layer to an electrode is improved and the battery performance is improved. From the above viewpoint, the filler content is more preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, based on the total amount of the PVDF resin and the filler. When a filler is contained in the adhesive porous layer, the filler content is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, based on the total amount of the PVDF resin and the filler.
  • An average particle size of the filler is preferably from 0.01 ⁇ m to 10 ⁇ m.
  • the lower limit value thereof is more preferably 0.1 ⁇ m or more, and the upper limit value thereof is more preferably 5 ⁇ m or less.
  • a particle size distribution of the filler is preferably 0.1 ⁇ m ⁇ d90-d10 ⁇ 3 ⁇ m.
  • d10 represents a particle diameter ( ⁇ m) of cumulative 10%
  • d90 represents a particle diameter ( ⁇ m) of cumulative 90%, in the weight cumulative particle size distribution calculated from the small particle side.
  • a laser diffraction type particle size distribution measuring apparatus MASTERSIZER 2000 manufactured by Sysmex Corporation
  • water is used as a dispersion medium
  • a trace amount of nonionic surfactant TRITON X-100 is used as a dispersant.
  • the inorganic filler in the present disclosure is preferably one that is stable with respect to an electrolytic solution and is electrochemically stable.
  • the inorganic filler examples include: a particle of a metal hydroxide such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, cerium hydroxide, nickel hydroxide or boron hydroxide; a metal oxide such as silica, alumina, zirconia or magnesium oxide; a carbonate such as calcium carbonate or magnesium carbonate; and a sulfate such as barium sulfate or calcium sulfate.
  • a metal hydroxide such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, cerium hydroxide, nickel hydroxide or boron hydroxide
  • a metal oxide such as silica, alumina, zirconia or magnesium oxide
  • a carbonate such as calcium carbonate or magnesium carbonate
  • a sulfate such as barium sulfate or calcium sulfate.
  • the inorganic filler preferably includes at least one of a metal hydroxide particle or a metal oxide particle, and from the viewpoint of impartment of flame retardancy and an electricity eliminating effect, the inorganic filler more preferably includes a metal hydroxide particle, and particularly preferably includes a magnesium hydroxide particle.
  • the inorganic filler may be one that is surface-modified with a silane coupling agent.
  • a particle shape of the filler is not limited, and may be any of a spherical-like shape or a plate-like shape.
  • the filler is preferably in the form of plate-like shaped particles, or in the form of non-aggregated primary particles from the viewpoint of inhibiting a short-circuit of the battery.
  • the inorganic filler content is, with respect to the total amount of PVDF resin and the inorganic filler, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably less than 80% by mass, more preferably 70% by mass or less, still more preferably 65% by mass or less, and still more preferably 60% by mass or less.
  • Examples of an organic filler in the present disclosure include cross-linked acrylic resins such as cross-linked polymethylmethacrylate, cross-linked polystyrene, and cross-linked polymethylmethacrylate is preferable.
  • the adhesive porous layer in the present disclosure may contain an additive such as a dispersant like a surfactant, a wetting agent, a defoaming agent, or a pH adjusting agent.
  • the dispersant is added to a coating liquid for forming the adhesive porous layer for the purpose of improving dispersibility, coating property, and storage stability.
  • the wetting agent, the defoaming agent, and the pH adjusting agent are added to a coating liquid for forming an adhesive porous layer for the purposes of, for example, improvement of compatibility with the porous substrate, suppression of air biting into the coating liquid, or pH adjustment.
  • a weight of the adhesive porous layer is preferably from 0.5 g/m 2 to 2.0 g/m 2 on one side of the porous substrate from a viewpoint of load characteristics of a battery.
  • the weight is 0.5 g/m 2 or more on one side of the porous substrate, adhesion between the separator and an electrode is favorable, and the load characteristics of the battery is excellent.
  • the weight is 2.0 g/m 2 or less on one side of the porous substrate, the ion permeability of the separator is excellent and the load characteristics of the battery is excellent.
  • the weight of the adhesive porous layer is more preferably from 0.75 g/m 2 to 2.0 g/m 2 on one side of the porous substrate, and more preferably from 1.0 g/m 2 to 2.0 g/m 2 .
  • the weight of the adhesive porous layer is, as a total of both sides of the porous substrate, preferably from 1.0 g/m 2 to 4.0 g/m 2 , more preferably from 1.5 g/m 2 to 4.0 g/m 2 , and still more preferably from 2.0 g/m 2 to 4.0 g/m 2 .
  • the difference in weight between the weight of the adhesive porous layer on one side and the weight of the adhesive porous layer on the other side is preferably 20% by mass or less with respect to the total weight of the adhesive porous layer on both sides.
  • the weight difference is 20% by mass or less, a separator hardly curls, and therefore, the handling property is further improved.
  • the thickness of the adhesive porous layer is preferably from 0.5 ⁇ m to 4 ⁇ m on one side of the porous substrate.
  • the thickness of the adhesive porous layer is more preferably 1 ⁇ m or more on one side of the porous substrate.
  • the thickness of the adhesive porous layer is more preferably 3 ⁇ m or less, and still more preferably 2.5 ⁇ m or less, on one side of the porous substrate.
  • the adhesive porous layer preferably has a sufficiently porous structure from a viewpoint of ion permeability.
  • the porosity is preferably from 30% to 80%.
  • the porosity is 80% or less, mechanical properties capable of withstanding a pressing step for adhering to an electrode can be secured, and the surface opening ratio is not too high, which is suitable for securing sufficiently strong adhesion.
  • the porosity of 30% or more is preferable from a viewpoint of improving ion permeability.
  • a method of determining the porosity of the adhesive porous layer in the present disclosure is the same as the method of determining the porosity of the porous substrate.
  • the adhesive porous layer preferably has an average pore diameter of from 10 nm to 200 nm.
  • the average pore diameter of 200 nm or less is preferable from viewpoints that non-uniformity of pores is suppressed, adhesion points are uniformly scattered, and adhesion to an electrode is further improved.
  • the average pore diameter of 200 nm or less is preferable from the viewpoint of high uniformity of movement of ions and further improvement of cycle characteristics and load characteristics.
  • the average pore diameter is 10 nm or more, when the adhesive porous layer is impregnated with the electrolytic solution, a resin which forms the adhesive porous layer less likely inhibits the ion permeability by swelling and thereby blocking pores.
  • the average pore diameter (nm) of the adhesive porous layer is calculated by the following Equality, assuming that all the pores are cylindrical.
  • d represents the average pore diameter (diameter) of the adhesive porous layer
  • V represents a pore volume per 1 m 2 of the adhesive porous layer
  • S represents a pore surface area per 1 m 2 of the adhesive porous layer.
  • the pore volume V per 1 m 2 of the adhesive porous layer is calculated from the porosity of the adhesive porous layer.
  • the pore surface area S of the pores per 1 m 2 of the adhesive porous layer is obtained by a method as set forth below.
  • a specific surface area (m 2 /g) of a porous substrate and the specific surface area (m 2 /g) of the separator are calculated from a nitrogen gas adsorption amount by applying the BET equation to the nitrogen gas adsorption method.
  • the specific surface areas (m 2 /g) are multiplied by each basis weight (g/m 2 ) to calculate the pore surface areas per 1 m 2 respectively.
  • the pore surface area per 1 m 2 of the porous base material is subtracted from the pore surface area per 1 m 2 of the separator to calculate the pore surface area S per 1 m 2 of the adhesive porous layer.
  • a thickness of the separator of the present disclosure is preferably 30 ⁇ m or less, and more preferably 25 ⁇ m or less from a viewpoint of energy density and output characteristics of a battery.
  • the thickness of the separator of the present disclosure is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more from a viewpoint of mechanical strength.
  • a puncture strength of the separator of the present disclosure is preferably from 250 g to 1000 g, and more preferably from 300 g to 600 g.
  • a method of measuring the puncture strength of the separator is the same as the method of measuring the puncture strength of the porous substrate.
  • a porosity of the separator of the present disclosure is preferably from 30% to 60% from viewpoints of adhesion to the electrode, handling property, ion permeability, and mechanical properties.
  • a method of determining the porosity of the separator in the present disclosure is the same as the method of obtaining the porosity of the porous substrate.
  • the Gurley value (JIS P8117:2009) of the separator of the present disclosure is preferably from 50 sec/100 cc to 800 sec/100 cc, more preferably from 50 sec/100 cc to 400 sec/100 cc, and still more preferably from 100 sec/100 cc to 300 sec/100 cc.
  • a value obtained by subtracting the Gurley value of the porous substrate from the Gurley value of the separator (in a state in which the adhesive porous layer is formed on the porous substrate) is preferably 90 sec/100 cc or less, more preferably 80 sec/100 cc or less, and still more preferably 70 sec/100 cc or less.
  • the value is 90 seconds/100 cc or less, the adhesive porous layer does not become too dense, ion permeability is favorably maintained, and excellent battery characteristics are obtained.
  • a lower limit of the value is not particularly limited and is 0 sec/100 cc or more.
  • a peeling strength between the adhesive porous layer and the porous substrate is preferably from 0.20 N/12 mm to 1.20 N/12 mm from viewpoints of adhesion to the electrode and ion permeability.
  • the peel strength is 0.20 N/12 mm or more, adhesion between the adhesive porous layer and the porous substrate is excellent, and as a result, the adhesion between the electrode and the separator is improved.
  • the peeling strength is preferably 0.20 N/12 mm or more, and more preferably 0.25 N/12 mm or more.
  • the peeling strength is 1.20 N/12 mm or less, the ion permeability of a separator is excellent.
  • the peeling strength is preferably 1.20 N/12 mm or less, more preferably 1.10 N/12 mm or less, still more preferably 1.00 N/12 mm or less, and still more preferably 0.50 N/12 mm or less.
  • a film resistance of the separator of the present disclosure is preferably from 1 ohm ⁇ cm 2 to 10 ohm ⁇ cm 2 from a viewpoint of load characteristics of a battery.
  • the film resistance is a resistance value when the separator is impregnated with an electrolytic solution, and is measured by an alternating current method.
  • the value of the film resistance differs depending on the kind and temperature of the electrolytic solution, the value is one that is measured at 20° C. using 1 mol/L LiBF 4 -propylene carbonate:ethylene carbonate (mass ratio 1:1) as the electrolytic solution.
  • a tortuosity of the separator of the present disclosure is preferably from 1.5 to 2.5 from a viewpoint of ion permeability.
  • the tortuosity of the separator is a value determined by the following Equality.
  • ⁇ is the tortuosity of the separator
  • R is a film resistance (ohm ⁇ cm 2 ) of the separator when impregnated with an electrolytic solution
  • r is a resistivity (ohm ⁇ cm) of the electrolytic solution
  • ⁇ is the porosity (%) of the separator
  • t is a film thickness (cm) of the separator.
  • electrolytic solution 1 mol/L LiBF 4 -propylene carbonate:ethylene carbonate (mass ratio 1:1) is used. The film resistance is measured at 20° C.
  • a chargeability of the separator of the present disclosure can be checked by a half-life measurement method described in JIS L1094:1997. Note that since the use environment of the separator is a dry environment, it is desirable to check the chargeability in consideration of the environment.
  • a half-life measured under an environment with a temperature 50° C. below a dew point by after keeping a sample for one hour or more under an environment of a temperature 50° C. below a dew point to adjust the humidity is used as an indicator of chargeability.
  • the half-life measured by such a method is preferably as small as possible, and the smaller the half-life is, the higher the antistatic effect is.
  • the antistatic effect is dramatically improved by including a layered clay mineral in the adhesive porous layer.
  • a water content (on a mass basis) in the separator of the present disclosure is preferably 1,000 ppm or less.
  • the water content (on a mass basis) contained in the separator is more preferably 800 ppm or less, and still more preferably 500 ppm or less.
  • the separator of the present disclosure is manufactured by, for example, a method in which a coating liquid containing at least the PVDF resin is coated on the porous substrate to form a coating layer, and then the PVDF resin contained in the coating layer is solidified to form the adhesive porous layer on the porous substrate.
  • the adhesive porous layer can be formed by, for example, a wet coating method set forth below.
  • a crystal form regulator in an adhesive porous layer will be described as an example.
  • the wet coating method is a film forming method in which (i) a coating liquid preparation step of preparing a coating liquid by dissolving or dispersing a PVDF resin and a crystal form regulator (preferably a layered clay mineral) in a solvent, (ii) a coating step of applying the coating liquid on one side or both sides of a porous substrate to form a coating layer, (iii) a coagulation step of obtaining a composite film having an adhesive porous layer containing the PVDF resin and a crystal form regulator (preferably a layered clay mineral) on one side or both sides of a porous substrate by solidifying the PVDF resin by bringing the coating layer into contact with a coagulation liquid, (iv) a water washing step of washing the composite film with water, and (v) a drying step of removing water from the composite film are performed to form an adhesive porous layer on the porous substrate.
  • a coating liquid preparation step of preparing a coating liquid by dissolving or dispersing a PVDF resin and a
  • the coating liquid preparation step is a step of preparing a coating liquid containing a PVDF resin and a crystal form regulator (preferably a layered clay mineral).
  • the coating liquid is prepared, for example, by dissolving the PVDF resin in a solvent and further dispersing the crystal form regulator (preferably a layered clay mineral).
  • the solvent to be used in preparation of the coating liquid for dissolving the PVDF resin include polar amide solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide and dimethylformamide.
  • a phase separation agent that induces phase separation is mixed with the good solvent from the viewpoint of forming a porous layer having a favorable porous structure.
  • the phase separation agent include water, methanol, ethanol, propyl alcohol, butyl alcohol, butanediol, ethylene glycol, propylene glycol and tripropylene glycol.
  • the phase separation agent is mixed with the good solvent in an amount in a range which ensures that a viscosity suitable for coating can be secured.
  • the solvent to be used for preparation of the coating liquid is preferably a mixed solvent which contains the good solvent in an amount of 60% by mass or more and the phase separation agent in an amount of 40% by mass or less, from the viewpoint of forming a favorable porous structure.
  • a concentration of the resin in the coating liquid is preferably from 1% by mass to 20% by mass from the viewpoint of forming a favorable porous structure.
  • the filler and other components may be dissolved or dispersed in the coating liquid.
  • a total concentration of the layered clay mineral and the filler in the coating liquid is preferably from 0.01% by mass to 20% by mass with respect to a mass of the coating liquid.
  • the coating liquid may contain a dispersant such as a surfactant, a thickener, a wetting agent, a defoaming agent, a pH adjusting agent, and the like. These additives may be remained as long as they are electrochemically stable under use conditions of a non-aqueous secondary battery and do not inhibit an in-battery reaction.
  • a dispersant such as a surfactant, a thickener, a wetting agent, a defoaming agent, a pH adjusting agent, and the like.
  • the coating step is a step of applying the coating liquid to one side or both sides of a porous substrate to form a coating layer.
  • Conventional coating means such as Mayer bar, die coater, reverse roll coater, and gravure coater may be applied to coat the porous substrate.
  • the adhesive porous layer is formed on both sides of the porous substrate, it is preferable from the viewpoint of productivity that the coating liquid is applied to the substrate simultaneously on both sides.
  • the coagulation step is a step of bringing the coating layer into contact with a coagulation liquid to solidify the PVDF resin while inducing phase separation. Specifically, in the coagulation step, it is preferable to immerse the porous substrate having the coating layer in the coagulation liquid, and it is more preferable to pass the porous substrate through a tank (coagulation tank) containing the coagulation liquid.
  • the coagulation liquid is generally composed of a good solvent and a phase separation agent used for preparing a coating liquid and water. From a viewpoint of production, it is preferable to adjust a mixing ratio of the good solvent and the phase separation agent to that of a mixed solvent used for preparing the coating liquid. From a viewpoint of forming a porous structure and productivity, it is appropriate that a content of water in the coagulation liquid is from 40% by mass to 90% by mass. By controlling the content of water, the phase separation rate can be adjusted, and the crystal structure of the PVDF resin in the adhesive porous layer can be controlled.
  • a temperature of the coagulating liquid is, for example, 20° C. to 50° C.
  • the water washing step is a step performed for the purpose of removing the solvent (the solvent forming the coating liquid and the solvent forming the coagulation liquid) contained in the composite film. Specifically, it is preferable that the water washing step is carried out by conveying the composite film in a water bath.
  • the temperature of water for washing is, for example, from 0° C. to 70° C.
  • the drying step is a step of removing water from the composite film after the water washing step.
  • the drying method is not limited, and examples thereof include a method of bringing the composite film into contact with a heat generating member; a method of conveying the composite film in a chamber adjusted in temperature and humidity; and a method of applying hot air to the composite film.
  • the adhesive porous layer can also be produced by a dry coating method.
  • the dry coating method is a method in which a coating liquid containing at least a PVDF resin is applied to a porous substrate and the coating layer is dried to volatilize and remove the solvent to obtain an adhesive porous layer. Since a porous layer tends to become dense in the dry coating method as compared with the wet coating method, the wet coating method is more preferable from a viewpoint of obtaining a good porous structure.
  • a stretching step may be provided before and/or after the (iv) water washing step or (v) drying step for the purpose of controlling the area intensity ratio of the ⁇ -phase-crystal-derived peak and the half-width of an endothermic peak of the adhesive porous layer.
  • the stretching temperature is preferably from 20° C. to 130° C., and the stretching magnification is preferably from 1.01 times to 1.10 times.
  • a non-aqueous secondary battery of the present disclosure is a non-aqueous secondary battery which is configured to produce an electromotive force by doping/de-doping of lithium, the non-aqueous secondary battery including a positive electrode, a negative electrode, and the separator for a non-aqueous secondary battery of the present disclosure.
  • the doping means absorption, holding, adsorption or insertion, which means a phenomenon in which lithium ions enter an active material of an electrode such as a positive electrode.
  • the non-aqueous secondary battery of the present disclosure has, for example, a structure in which a battery element with a negative electrode and a positive electrode facing each other with a separator interposed therebetween is enclosed in an outer packaging material together with an electrolytic solution.
  • the non-aqueous secondary battery of the present disclosure is suitable as a non-aqueous electrolyte secondary battery, particularly a lithium ion secondary battery.
  • One embodiment of the non-aqueous secondary battery of the present disclosure includes the separator including the adhesive porous layer including the PVDF resin and the layered clay mineral.
  • the adhesive porous layer of the separator contains the PVDF resin, its adhesion to an electrode is excellent, and since the layer contains the layered clay mineral, it is less likely to charge, and therefore, reduction of internal resistance of the battery is achieved, and thus the battery output is excellent.
  • One embodiment of the non-aqueous secondary battery of the present disclosure includes the separator which includes the porous substrate, the adhesive porous layer including the PVDF resin and the layered clay mineral provided on one side or both sides of the porous substrate, a weight of the adhesive porous layer being from 0.5 g/m 2 to 2.0 g/m 2 on one side of the porous substrate.
  • adhesion between an electrode and the separator is excellent, and as a result, an in-battery reaction during charging and discharging is made uniform, and the load characteristics are excellent.
  • the positive electrode has, for example, a structure in which an active material layer containing a positive electrode active material and a binder resin is formed on a current collector.
  • the active material layer may further contain a conductive assistant.
  • the positive electrode active material include lithium-containing transition metal oxides, specific examples of which including LiCoO 2 , LiNiO 2 , LiMn 1/2 Ni 1/2 O 2 , LiCo 1/3 Mn 1/3 Ni 1/3 O 2 , LiMn 2 O 4 , LiFePO 4 , LiCo 1/2 Ni 1/2 O 2 and LiAl 1/4 Ni 3/4 O 2 .
  • the binder resin include PVDF resins.
  • the conductive assistant include carbon materials such as acetylene black, ketjen black and graphite powders.
  • the current collector include aluminum foils, titanium foils and stainless foils having a thickness of, for example, from 5 ⁇ m to 20 ⁇ m.
  • the adhesive porous layer is excellent in oxidation resistance, disposition of the adhesive porous layer of the separator on the positive electrode side enables to easily apply, as a positive electrode active material, one that is capable of operating at a high voltage of 4.2 V or more, such as LiMn 1/2 Ni 1/2 O 2 or LiCo 1/3 Mn 1/3 Ni 1/3 O 2 .
  • the negative electrode may have, for example, a structure in which an active material layer containing a negative active material and a binder resin is formed on a current collector.
  • the active material layer may further contain a conductive assistant.
  • the negative active material include materials capable of electrochemically absorbing lithium, specific examples of which including: carbon materials; and alloys of lithium and silicon, tin, aluminum or the like.
  • the binder resin include PVDF resins and styrene-butadiene copolymers.
  • the conductive assistant include carbon materials such as acetylene black, ketjen black and graphite powders.
  • Examples of the current collector include copper foils, nickel foils and stainless foils having a thickness of, for example, from 5 ⁇ m to 20 ⁇ m.
  • a metal lithium foil may be used as a negative electrode.
  • the electrolytic solution is, for example, a solution obtained by dissolving a lithium salt in a non-aqueous solvent.
  • the lithium salt include LiPF 6 , LiBF 4 and LiClO 4 .
  • the non-aqueous solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and fluorine-substituted products thereof; and cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone. They may be used singly, or in combination of two or more kinds thereof.
  • the electrolytic solution is preferably one obtained by mixing a cyclic carbonate and a chain carbonate at a mass ratio (cyclic carbonate:chain carbonate) of from 20:80 to 40:60, and dissolving a lithium salt therein in an amount of from 0.5 mol/L to 1.5 mol/L.
  • Examples of the outer packaging material include metal cans and aluminum laminated film packages.
  • Examples of a shape of the battery include a rectangular shape, a circular-cylindrical shape and a coin shape, and the separator of the present disclosure is suitable for any shape.
  • Examples of a manufacturing method of the non-aqueous secondary battery of the present disclosure include: a manufacturing method including impregnating a separator with an electrolytic solution, performing a heat-pressing treatment (referred to as “wet heat-press” in the present specification)) to adhere the separator to an electrode; and a manufacturing method including performing a heat-pressing treatment (referred to as “dry heat-press” in the present specification) without impregnating the separator with the electrolytic solution to adhere the separator to an electrode.
  • the non-aqueous secondary battery of the present disclosure can be manufactured by manufacturing a layered body in which the separator of the present disclosure is disposed between a positive electrode and a negative electrode and then using the layered body, for example, in accordance with any one of the following manufacturing methods 1) to 3).
  • Manufacturing method 1 The electrodes and the separator are adhered by heat-pressing (dry heat-press) to form a layered body, then the layered body is placed in an outer packaging material (for example, pack made of aluminum laminate film. The same applies below), and the electrolytic solution is injected therein. The layered body is further heat-pressed (wet heat-press) from above the outer packaging material to adhere the electrode and the separator and seal the outer packaging material.
  • dry heat-press dry heat-press
  • an outer packaging material for example, pack made of aluminum laminate film. The same applies below
  • the electrolytic solution is injected therein.
  • the layered body is further heat-pressed (wet heat-press) from above the outer packaging material to adhere the electrode and the separator and seal the outer packaging material.
  • Manufacturing method 2 The layered body is housed in an outer packaging material, an electrolytic solution is injected therein, and the layered body is heat-pressed (wet heat-pressed) from above the outer packaging material to adhere the electrode and the separator and seal the outer packaging material.
  • the layered body is heat-pressed (dry heat-pressed) to adhere the electrode and the separator, and then the layered body is housed in an outer packaging material, an electrolytic solution is injected therein, and the outer packaging material is sealed.
  • a method of disposing the separator between the positive electrode and the negative electrode in production of a non-aqueous secondary battery may be a method in which at least one positive electrode, at least one separator and at least one negative electrode are layered in this order one on another (so called a stacking method), or a method in which the positive electrode, the separator, the negative electrode and the separator are superimposed one on another in this order, and wound in the length direction.
  • a condition of the heat-pressing in the manufacturing methods 1) to 3) may include, in both of the dry heat-press and the wet heat-press, a pressure of from 0.1 MPa to 20 MPa and a temperature of from 60° C. to 130° C., (which being preferably from 70° C. to 110° C.).
  • the separator of the present disclosure can be bonded to an electrode when superimposed on the electrode. Therefore, the pressing is not an essential step in production of a battery, while it is preferable to perform the pressing in view of improving adherence between the electrode and the separator. It is preferable to perform the pressing in parallel with heating (heat-pressing) for further improving adherence between the electrode and the separator.
  • separator and the non-aqueous secondary battery of the present disclosure will be described further in detail below by way of Examples.
  • the materials, amounts, ratios, procedures and so on can be appropriately modified as long as it does not depart from the spirit of the present disclosure. Accordingly, the scope of the separator and the non-aqueous secondary battery of the present disclosure cannot be interpreted as being limited by way of examples below.
  • a weight average molecular weight of a resin was measured by using a gel permeation chromatograph apparatus (G-900, manufactured by JASCO Corporation), two pieces of column TSKGEL SUPER AWM-H (manufactured by TOSOH CORPORATION) and N,N-dimethylformamide at a condition of a temperature of 40° C. and a flow rate of 10 mL/min, the measured value being expressed in terms of polystyrene.
  • G-900 gel permeation chromatograph apparatus
  • a thickness ( ⁇ m) of each of the porous substrate and the separator was determined by measuring the thickness at 20 selected spots using a contact-type thickness meter (LITEMATIC manufactured by Mitutoyo Corporation), and averaging the measured values.
  • a contact-type thickness meter LITEMATIC manufactured by Mitutoyo Corporation
  • As a measurement terminal one having a circular-cylindrical shape with a diameter of 5 mm was used, and an adjustment was made so that a load of 7 g was applied during the measurement.
  • a total weight thereof on both sides of a porous substrate was determined by subtracting a basis weight of the porous substrate from a basis weight of a separator.
  • the basis weight (weight per 1 m 2 ) was determined by cutting out a separator or the porous substrate into a size of 10 cm ⁇ 30 cm, weighing the weight, and dividing the weight by the area.
  • An adhesive porous layer was peeled off from a separator to obtain 100 mg of powdery sample, and X-ray diffraction measurement was carried out as described below.
  • an area intensity ratio of the ⁇ -phase-crystal derived peak was determined according to the following Formula.
  • Area intensity ratio of ⁇ -phase-crystal-derived peak [%] area intensity of ⁇ -phase-crystal-derived peak ⁇ (area intensity of ⁇ -phase-crystal-derived peak+area intensity of ⁇ -phase-crystal-derived peak) ⁇ 100
  • the adhesive porous layer was peeled off from the separator, and 5 mg of powdery sample was obtained.
  • a differential scanning calorimeter (TA Instruments Japan Inc., Q20)
  • measurement was carried out under alumina powder as a reference material under a nitrogen atmosphere at a heating rate of 10° C./min to obtain a DSC curve. From the DSC curve, a half-width of an endothermic peak was determined.
  • An adhesive tape (product No. 550R-12 manufactured by Scotch Company) having a width of 12 mm and a length of 15 cm was attached to a surface of an adhesive porous layer on one side of the separator, and the separator was cut in conformity with the width and the length of the adhesive tape to obtain a measurement sample.
  • a length direction was made coincident with an MD direction of the separator.
  • the adhesive tape was used as a support for separating the adhesive porous layer on one side.
  • the measurement sample was left standing in an atmosphere at a temperature of 23 ⁇ 1° C. and a relative humidity of 50 ⁇ 5% for 24 hours or more, and the following measurement was made in the same atmosphere.
  • Separation of 10 cm of the adhesive tape was performed together with the adhesive porous layer which is immediately below the adhesive tape, so that the separator was separated by about 10 cm into a laminated body (1) of the adhesive tape and the adhesive porous layer and a laminated body (2) of the porous substrate and the other adhesive porous layer.
  • An end of the laminated body (1) was fixed to an upper chuck of a Tensilon (RTC-1210A manufactured by ORIENTEC CORPORATION), and an end of the laminated body (2) was fixed to a lower chuck of the Tensilon.
  • the measurement sample was suspended in the gravity direction to ensure that the tension angle (angle of the laminated body (1) to the measurement sample) was 180°.
  • the laminated body (1) was drawn at a tension speed of 20 mm/min, and the load in separation of the laminated body (1) from the porous substrate was measured.
  • the load was taken at intervals of 0.4 mm between the points of 10 mm and 40 mm from the start of the measurement, and an average of the loads was defined as a peel strength.
  • the charge decay half-life (seconds) of the separator was measured using a charge charge attenuation measurement device (Shishido Electrostatic, Ltd., HONESTMETER ANALYZER V1).
  • a sample was allowed to stand in a dry room at a temperature 50° C. below a dew point for one day to adjust the humidity, and the sample after the standing was measured in a dry room at a temperature 50° C. below a dew point.
  • Gurley values (sec/100 cc) of a porous substrate and a separator were measured using a Gurley type densometer (Toyo Seiki Seisaku-sho, Ltd., G-B2C) in accordance with JIS P8117:2009.
  • Table 2 lists the value obtained by subtracting the Gurley value of the porous substrate from the Gurley value of the separator as “ ⁇ Gurley value”.
  • the positive electrode (coated on one side) obtained as above and an aluminum foil (thickness: 20 ⁇ m) were respectively cut to a width of 1.5 cm and a length of 7 cm, and each separator obtained in Examples and Comparative Examples as set forth below was cut to a width of 1.8 cm and a length of 7.5 cm.
  • the positive electrode, the separator and the aluminum foil were layered in this order to prepare a laminated body.
  • the laminated body was impregnated with an electrolytic solution (1 mol/L LiBF 4 -ethylene carbonate:propylene carbonate [mass ratio 1:1]), and put into an aluminum laminated film package.
  • the package was then unsealed, the laminated body was taken out from the package, and the aluminum foil was removed from the laminated body to obtain a measurement sample.
  • a non-coated side of the positive electrode of the measurement sample was fixed to a metal plate with a double-sided tape, and the metal plate was fixed to a lower chuck of a Tensilon (STB-1225S manufactured by A&D Company, Limited).
  • the metal plate was fixed to the Tensilon in such a manner that the length direction of the measurement sample was coincident with the gravity direction.
  • the separator was separated from the positive electrode by about 2 cm from the lower end, and the end was fixed to an upper chuck to ensure that the tension angle (angle of the separator to the measurement sample) was 180°.
  • the separator was drawn at a tension speed of 20 mm/min, and the load in separation of the separator from the positive electrode was measured.
  • the load was measured at intervals of 0.4 mm between the points of 10 mm and 40 mm from the start of the measurement, an average of the loads was defined as a peel strength between the electrode and the separator (N/15 mm).
  • the measured values were plotted on a graph in which the vertical axis represents the peel strength between the electrode and the separator and the horizontal axis represents the heat-pressing temperature, adjacent plots were connected by a straight line, and the lower limit value and the upper limit value of the temperature range where the peel strength was 0.2 N/15 mm or more, and a difference (temperature gap) between the lower limit value and the upper limit value was obtained.
  • the peel strength (1) a range of the heat-pressing temperature where the peel strength is 0.2 N/15 mm or more is referred to as a “wet adhering temperature range”.
  • a positive electrode was prepared in the similar manner as in “Peel Strength (1) between Electrode and Separator” described above.
  • the positive electrode (coated on one side) and an aluminum foil (thickness: 20 ⁇ m) were respectively cut to a width of 1.5 cm and a length of 7 cm, and each separator obtained in Examples and Comparative Examples as set forth below was cut to a width of 1.8 cm and a length of 7.5 cm.
  • the positive electrode, the separator and the aluminum foil were layered in this order to prepare a laminated body.
  • the laminated body was put into an aluminum laminated film package.
  • the measured values were plotted on a graph in which the vertical axis represents the peel strength between the electrode and the separator and the horizontal axis represents the heat-pressing temperature, adjacent plots were connected by a straight line, and the lower limit value and the upper limit value of the temperature range where the peel strength was 0.02 N/15 mm or more, and a difference (temperature gap) between the lower limit value and the upper limit value was obtained.
  • the peel strength (2) a range of the heat-pressing temperature where the peel strength is 0.02 N/15 mm or more is referred to as a “dry adhering temperature range”
  • a positive electrode was prepared in the similar manner as in “Peel Strength (1) between Electrode and Separator” described above.
  • 300 g of artificial graphite as a negative electrode active material, 7.5 g of a water-soluble dispersion including a modified form of a styrene-butadiene copolymer in an amount of 40% by mass as a binder, 3 g of carboxymethyl cellulose as a thickener, and a proper quantity of water were stirred using a double-arm mixer, thereby preparing a slurry for forming a negative electrode.
  • the slurry for forming a negative electrode was coated on a copper foil having a thickness of 10 ⁇ m as a negative electrode current collector, and the resulting coated membrane was dried, followed by pressing, to produce a negative electrode having a negative electrode active material layer.
  • Two separators (width: 108 mm) obtained in the following Examples and Comparative Examples were prepared and stacked, and one end in the MD direction was used to wrap around a stainless steel core.
  • a positive electrode (width: 106.5 mm) welded with a lead tab was sandwiched between the two separators, a negative electrode (width: 107 mm) welded with a lead tab was arranged on one separator, and this layered body was wound to continuously manufacture 60 wound electrode bodies.
  • the obtained wound electrode body was housed in a pack made of an aluminum laminate film, impregnated with an electrolytic solution (1 mol/L LiPF6-ethylene carbonate:ethyl methyl carbonate [mass ratio 3:7]), and sealed using a vacuum sealer.
  • the aluminum laminate film pack housing the wound electrode body and the electrolytic solution was heat-pressed with a heat-pressing machine to obtain a battery. Conditions of heat-pressing were as follows.
  • the battery was charged and discharged for 100 cycles. In this test, charging was performed at constant current and constant voltage charging of 0.5 C. and 4.2 V, and discharging was performed at constant current discharge of 0.5 C. and 2.75 V cutoff. After 100 cycles of charging and discharging, the battery was disassembled, and lithium dendrite precipitated on a negative electrode was observed. A case in which lithium dendrite was not observed was judged as acceptable, and a case in which lithium dendrite was observed was judged as unacceptable. Then, the number proportion (%) of the acceptable batteries was calculated and classified as follows.
  • a positive electrode was prepared in the similar manner as in “Peel Strength (1) between Electrode and Separator” described above.
  • the positive electrode (coated on one side) and an aluminum foil (thickness: 20 ⁇ m) were respectively cut to a width of 1.5 cm and a length of 7 cm, and each separator obtained in Examples and Comparative Examples as set forth below was cut to a width of 1.8 cm and a length of 7.5 cm.
  • the positive electrode, the separator and the aluminum foil were layered in this order to prepare a laminated body.
  • the laminated body was impregnated with an electrolytic solution (1 mol/L LiBF 4 -ethylene carbonate:propylene carbonate [mass ratio 1:1]), and put into an aluminum laminated film package. Next, an inside of the package was brought into a vacuum state using a vacuum sealer, and the laminated body was heat-pressed together with the package using a heat-pressing machine, thereby bonding the positive electrode and the separator to each other.
  • a positive electrode was prepared in the similar manner as in “Peel Strength (1) between Electrode and Separator” described above.
  • a negative electrode was prepared in the similar manner as in “Production yield of Battery” described above.
  • a lead tab was welded to each of the positive electrode and negative electrode. Then, the positive electrode, each separator obtained in Examples and Comparative examples shown below, and the negative electrode were stacked in this order to produce a stacked body.
  • the laminated body was put into an aluminum laminated film pack and impregnated with an electrolytic solution (1 mol/L LiPF 6 -ethylene carbonate: ethyl methyl carbonate [mass ratio 3:7]) by pouring the electrolytic solution thereto.
  • an electrolytic solution (1 mol/L LiPF 6 -ethylene carbonate: ethyl methyl carbonate [mass ratio 3:7]
  • the inside of the pack was made vacuum, and the pack was tentatively sealed, and, using a heat press machine, the stacked body together with the pack was heat-pressed in a direction of the stacking, thereby bonding the electrode and the separator and sealing the pack.
  • the heat pressing conditions were as set forth below.
  • the battery was charged and discharged in an environment of 25° C., the discharge capacity when discharged at 0.2 C and the discharge capacity when discharged at 2 C. were measured, and the value (%) obtained by dividing the latter by the former was taken as the load characteristics.
  • Charging conditions were constant current constant voltage charging of 0.2 C. and 4.2 V for 8 hours, and discharging conditions were constant current discharge of 2.75 V cutoff
  • a PVDF resin and a layered clay mineral were dissolved or dispersed in a solvent to prepare a coating liquid. Equal amounts of the coating liquid were applied to both sides of a porous substrate, and the coated porous substrate was immersed in a coagulation liquid for solidification to obtain a composite film. Next, the composite film was washed with water and dried to obtain a separator having adhesive porous layers formed on both sides of a porous substrate. Details of the materials are as follows.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 1 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 98:2.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 1 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 95:5.
  • a PVDF resin was dissolved in a solvent to prepare a coating liquid. Equal amounts of the coating liquid were applied to both sides of a porous substrate. The coated porous substrate was subject to drying at 60° C. for 12 minutes and immersed in a coagulation liquid for solidification to obtain a composite film. Next, the composite film was washed with water and dried to obtain a separator having adhesive porous layers formed on both sides of a porous substrate. Details of the materials are as follows.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the similar manner as in Example 1 except that the coating liquid was prepared without adding the layered clay mineral.
  • a PVDF resin and a layered clay mineral were dissolved or dispersed in a solvent to prepare a coating liquid. Equal amounts of the coating liquid were applied to both sides of a porous substrate, and the coated porous substrate was immersed in a coagulation liquid for solidification to obtain a composite film. Next, the composite film was washed with water and dried to obtain a separator having adhesive porous layers formed on both sides of a porous substrate. Details of the materials are as follows.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 5 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 98:2.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 5 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 96:4.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the similar manner as in Example 5 except that the coating liquid was prepared without adding the layered clay mineral.
  • a peeling strength (1) thereof did not become equal to or more than a standard value.
  • a maximum value of the peeling strength (1) thereof is shown in Table 2.
  • a PVDF resin and a layered clay mineral were dissolved or dispersed in a solvent to prepare a coating liquid. Equal amounts of the coating liquid were applied to both sides of a porous substrate, and the coated porous substrate was immersed in a coagulation liquid for solidification to obtain a composite film. Next, the composite film was washed with water and dried to obtain a separator having adhesive porous layers formed on both sides of a porous substrate. Details of the materials are as follows.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 98:2.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 96:4.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 94:6.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 92:8.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the coating amount of the coating liquid was changed.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the coating amount of the coating liquid was changed. Both of peeling strengths (1) and (2) thereof did not become equal to or more than a standard value. Maximum values of the peeling strengths (1) and (2) thereof are shown in Table 2.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the layered clay mineral was changed to LUCENTITE STN (Katakura & Co-op Agri Corporation, organic onium ion modified hectorite, aspect ratio: 30).
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 15 except that the coating amount of the coating liquid was changed.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 15 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 98:2.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 15 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 96:4.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 15 except that the content ratio of PVDF resin and layered clay mineral contained in the coating liquid was changed to 92:8.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the layered clay mineral was changed to LUCENTITE SPN (Katakura & Co-op Agri Corporation, organic onium ion modified hectorite, aspect ratio: 30).
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the layered clay mineral was changed to SOMASIF MEE (Katakura & Co-op Agri Corporation, fluoromica, aspect ratio: 50).
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 8 except that the layered clay mineral was changed to SOMASIF MTE (Katakura & Co-op Agri Corporation, organic onium ion modified swellable mica, aspect ratio: 50).
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the similar manner as in Example 23 except that the coating liquid was prepared without adding the layered clay mineral.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the similar manner as in Example 8 except that the coating liquid was prepared without adding the layered clay mineral.
  • a PVDF resin and a layered clay mineral were mixed in a solvent, dispersed by using a bead mil with a diameter of 0.65 mm, and further dispersed with adding alumina thereto to prepare a coating liquid.
  • the coating liquid was applied to one side of a porous substrate, and the coated porous substrate was dried, immersed in water for 15 minutes to cause phase separation, and dried by subjecting to hot wind to obtain a separator having an adhesive porous layer (film thickness: 2.25 ⁇ m) formed on one side of a porous substrate.
  • film thickness film thickness: 2.25 ⁇ m
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the same manner as in Example 15 except that the coating liquid was prepared to have a content ratio of the PVDF resin and the magnesium hydroxide particles of 40:60 by adding magnesium hydroxide particles (KISUMA 5P, Kyowa Chemical Industry Co., Ltd., average particle diameter: 0.8 ⁇ m, BET specific surface area: 6.8 m 2 /g).
  • magnesium hydroxide particles KISUMA 5P, Kyowa Chemical Industry Co., Ltd., average particle diameter: 0.8 ⁇ m, BET specific surface area: 6.8 m 2 /g.
  • a separator having adhesive porous layers formed on both sides of a polyethylene microporous film was obtained in the similar manner as in Example 24 except that the coating liquid was prepared without adding the layered clay mineral.
  • a peeling strength (2) thereof did not become equal to or more than a standard value.
  • a maximum value of the peeling strength (2) thereof is shown in Table 2.
  • Example 1 1,130,000 2.4 5.0 SEN 1 — 2.2 20.9 17.0 1.03 800
  • Example 2 1,130,000 2.4 5.0 SEN 2 — 2.1 24.0 21.0 0.33 560
  • Example 3 1,130,000 2.4 5.0 SEN 5 — 2.2 36.0 23.0 0.21 130
  • Example 4 1,130,000 2.4 5.0 — — 2.2 15.0 15.0 0.91 1000
  • Example 5 1,130,000 2.4 3.8 STN 1 — 2.2 11.0 17.0 1.01 350
  • Example 6 1,130,000 2.4 3.8 STN 2 — 2.2 19.6 19.0 0.32
  • Example 7 1,130,000 2.4 3.8 STN 4 — 2.2 24.9 23.0 0.20 15 Comparative 1,130,000 2.4 3.8 — — 2.2 1.8 12.0 0.87 1000
  • Example 8 1,930,000 1.1 3.8 SEN 1 — 2.2 30.7 15.0 0.45 640
  • Example 9 1,930,000 1.1
  • Example 1 12 197 45 82 95 13 78 102 24 85/90/95 A 90 0.31 92
  • Example 2 12 193 41 83 97 14 79 104 25 85/90/95 A 90 0.32 93
  • Example 3 12 195 43 83 97 14 82 98 16 85/90/95 B 90 0.33 91
  • Example 4 12 203 51 83 95 12 82 95 13 85/90/95 B 90 0.30 90 Comparative 12 194 42 83 93 10 83 95 12 85/90/95 C 90 0.30 84
  • Example 5 12 194 42 79 100 21 78 104 26 85/90/95 A 90 0.29 92
  • Example 6 12 194 42 81 95 14 78 105 27 85/90/95 A 90 0.24 93
  • Example 7 12 199 47 82 95 13 79 104 25 85/90/95 A 90 0.27 91
  • Comparative 12 194 42 0.13 N/15 mm 83 95 12 85/90/95 C 90 0.13 84
  • Example 2 Example
  • FIG. 1 illustrates a relationship between the peeling strength (1) between an electrode and a separator and the heat-pressing temperature for Example 1, Example 2, and Comparative Example 1.
  • the wet adhering temperature range (the range of the heat-pressing temperature where the peel strength is 0.2 N/15 mm or more) has the lower limit value of 82° C. and the upper limit value of 95° C., and the gap therebetween is 13° C.
  • the wet adhering temperature range has the lower limit value of 83° C. and the upper limit value of 97° C., and the gap therebetween is 14° C.
  • the wet adhering temperature range has the lower limit value of 83° C.
  • the present embodiment having an area intensity ratio of the ⁇ -phase-crystal-derived peak of the PVDF resin in the adhesive porous layer of from 10% to 100% has a wide wet adhering temperature range.
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