WO2014123033A1 - リチウムイオン二次電池セパレータ用不織布基材及びリチウムイオン二次電池セパレータ - Google Patents
リチウムイオン二次電池セパレータ用不織布基材及びリチウムイオン二次電池セパレータ Download PDFInfo
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- WO2014123033A1 WO2014123033A1 PCT/JP2014/051780 JP2014051780W WO2014123033A1 WO 2014123033 A1 WO2014123033 A1 WO 2014123033A1 JP 2014051780 W JP2014051780 W JP 2014051780W WO 2014123033 A1 WO2014123033 A1 WO 2014123033A1
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- Prior art keywords
- nonwoven fabric
- fiber
- binder
- pet
- fibers
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Classifications
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- 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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/55—Polyesters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a nonwoven fabric substrate and a lithium ion secondary battery separator used for a lithium ion secondary battery separator.
- lithium ion secondary battery separator for a lithium ion secondary battery (hereinafter sometimes abbreviated as “battery”)
- battery a lithium ion secondary battery separator
- polyolefins such as polyethylene and polypropylene
- a porous membrane made of a resin has been used.
- the resin porous membrane has a problem that it melts and contracts when the battery abnormally generates heat, and the function of isolating the positive and negative electrodes is lost, resulting in a significant short circuit.
- Non-woven fabric base material for lithium ion secondary battery separators containing polyethylene terephthalate (PET) fibers (hereinafter referred to as “nonwoven fabric base material”) as a separator that hardly melts or shrinks even when the battery is abnormally heated.
- nonwoven fabric base material polyethylene terephthalate (PET) fibers
- separators obtained by coating various inorganic pigments have been proposed (see, for example, Patent Documents 1 to 3).
- Patent Document 1 describes a nonwoven fabric substrate containing fibers having a fiber diameter of 0.1 to 10 ⁇ m.
- Patent Document 2 describes a nonwoven fabric substrate containing crystallized PET fibers and binder PET fibers, and containing short fibers having an average fiber diameter of 3 ⁇ m or less as essential components.
- Patent Document 3 describes a nonwoven fabric base material containing crystallized PET fibers and binder PET fibers, and including fibers having a fiber length of 2 mm or less as crystallized PET fibers.
- the nonwoven fabric substrates of Patent Documents 1 to 3 when a thin separator is to be manufactured, the nonwoven fabric substrate is likely to wrinkle when a coating liquid containing an inorganic pigment is applied. There was a problem of falling.
- Patent Document 1 in order to manufacture a separator using a nonwoven fabric base material having a thickness of 13 ⁇ m, an apparatus having a complicated configuration is used that conveys the nonwoven fabric base material supported by a belt.
- the coating liquid containing the inorganic pigment is applied at an extremely low line speed of 8 m / hr.
- the coating liquid breakthrough occurs and it is difficult to achieve both low internal resistance and high tensile strength.
- JP 2005-536857 A Publication JP 2009-230975 A JP 2011-82148 A
- the present invention is intended to solve the above problems. That is, in a nonwoven fabric base material used for a lithium ion secondary battery separator, when applying a coating liquid containing an inorganic pigment, a nonwoven fabric base material for a lithium ion secondary battery separator that is difficult to wrinkle and has high productivity of the separator. It is something to be offered. In addition, when applying a coating liquid containing an inorganic pigment, an attempt is made to provide a nonwoven fabric base material for a lithium ion secondary battery separator that is difficult to cause back-through of the coating liquid and that has both low internal resistance and high tensile strength. Is. Furthermore, it is intended to provide a nonwoven fabric base material for a lithium ion secondary battery separator that has high strength, good liquid retention, and can reduce the resistance of the separator.
- the nonwoven fabric base material for lithium ion secondary battery separators mainly composed of polyethylene terephthalate fibers
- the nonwoven fabric base material contains polyethylene terephthalate fibers for binder and crystallized polyethylene terephthalate fibers, and the fiber length is 2.5 mm or less.
- the lithium ion secondary battery according to (1) comprising 21 to 60% by mass of polyethylene terephthalate fiber for binder having an average fiber diameter of 14.0 ⁇ m or less and a fiber length of 0.5 to 2.5 mm.
- Nonwoven fabric substrate for separator for separator.
- the nonwoven fabric base material for a lithium ion secondary battery separator according to (1) comprising a total of 80 to 100% by mass of crystallized polyethylene terephthalate fibers, and the crystallized polyethylene terephthalate fibers having an average fiber diameter of 2.0 to 4.0 ⁇ m .
- a nonwoven fabric base material for lithium ion secondary battery separators mainly composed of polyethylene terephthalate fibers, characterized in that it contains polyethylene terephthalate fibers for binders containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component.
- a nonwoven fabric base material for lithium ion secondary battery separators mainly composed of polyethylene terephthalate fibers, characterized in that it contains polyethylene terephthalate fibers for binders containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component.
- a treatment for applying a coating liquid containing an inorganic pigment to a nonwoven fabric base material for a lithium ion secondary battery separator according to any one of (1) to (4), and a coating liquid containing organic particles At least one treatment selected from a treatment comprising: laminating a resin microporous membrane; a treatment comprising forming a fine fiber layer by an electrostatic spinning method; and a treatment applying a solid electrolyte or a gel electrolyte. Lithium ion secondary battery separator.
- the nonwoven fabric substrate of the present invention producing a lithium ion secondary battery separator in which an inorganic pigment is coated on a nonwoven fabric substrate with high productivity is less likely to wrinkle when an inorganic pigment coating solution is applied. Can do.
- a coating liquid containing an inorganic pigment it is possible to produce a lithium ion secondary battery separator that is unlikely to cause back-through of the coating liquid and that has both low internal resistance and high tensile strength.
- the nonwoven fabric base material for lithium ion secondary battery separators which is strong and has good liquid retention can be provided.
- the nonwoven fabric base material for lithium ion secondary battery separators mainly composed of polyethylene terephthalate (PET) fibers contains PET fibers for binders and crystallized PET fibers, and 10 PET fibers for binders having a fiber length of 2.5 mm or less.
- PET polyethylene terephthalate
- the number of binder PET fibers in the nonwoven fabric base material can be increased and evenly distributed in the nonwoven fabric base material. Productivity can be improved.
- a binder PET fiber having an average fiber diameter of 14.0 ⁇ m or less and a fiber length of 0.5 to 2.5 mm is contained, whereby the binder PET fiber in the nonwoven fabric substrate is contained.
- the number of binder PET fibers and the number of bonded PET fibers can be reduced. Both wearing power increases. Therefore, a sufficiently high strength can be expressed with a small content of 10 to 30% by mass, and as a result, a low internal resistance can be obtained.
- the average fiber diameter of the crystallized PET fiber is 2.0 to 4.0 ⁇ m, the nonwoven fabric substrate is appropriately clogged, the back-through of the coating liquid is reduced, and a low internal resistance is obtained. .
- the nonwoven fabric base material for lithium ion secondary battery separators mainly composed of PET fibers contains PET fibers for binders containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component, whereby the nonwoven fabric base material The fibers can be bonded without excessively closing the voids, and the nonwoven fabric substrate for a lithium ion secondary battery separator having high strength can be obtained without deteriorating the liquid retention.
- the nonwoven fabric substrate (1) is mainly composed of PET fibers, contains PET fibers for binder and crystallized PET fibers, and contains 10 to 60% by mass of PET fibers for binder having a fiber length of 2.5 mm or less. It is a feature.
- Nonwoven fabric substrate (1) contains PET fibers for binder. If the fiber length of the binder PET fiber is longer than 2.5 mm, the nonwoven fabric base material tends to stretch, or the binder PET fibers tend to get entangled with each other, resulting in uneven distribution in the nonwoven fabric base material. Sometimes wrinkles are likely to enter or the strength of the nonwoven fabric substrate may be weakened.
- the fiber length of the binder PET fiber is more preferably 0.5 to 2.5 mm, still more preferably 0.7 to 2.3 mm, and particularly preferably 1.0 to 2.0 mm.
- the content of the PET fiber for binder having a fiber length of 2.5 mm or less is 10 to 60% by mass. When the amount is less than 10% by mass, the strength of the nonwoven fabric substrate is weakened, and wrinkles are easily formed. When the amount is more than 60% by mass, the molten component closes the pores of the nonwoven fabric base material, and the liquid retention of the nonwoven fabric base material deteriorates. Moreover, internal resistance becomes high.
- the content of the PET fiber for binder having a fiber length of 2.5 mm or less is more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass.
- the average fiber diameter of the binder PET fibers is preferably 0.1 to 14.0 ⁇ m.
- the average fiber diameter of the binder PET fiber is more preferably 1.0 to 13.0 ⁇ m, still more preferably 1.5 to 10.0 ⁇ m, and particularly preferably 2.0 to 10.0 ⁇ m. .
- the “average fiber diameter” as used herein refers to an average value of 10 fibers from the smallest of 20 measured equivalent circular diameters of fibers forming the nonwoven fabric substrate from a scanning electron micrograph of the nonwoven fabric substrate cross section. It is. The reason for using only the ten measured values from the smaller one is to exclude the measured values for fibers that have been severely cut off from a right angle to the longitudinal direction of the fibers.
- PET fiber for the binder examples include a core-sheath type, an eccentric type, a side-by-side type, a sea-island type, an orange type, a multi-bimetal type composite fiber, and a single component type.
- a one-component type heat-sealing fiber is preferable.
- Nonwoven fabric substrate (1) contains crystallized PET fibers.
- the content of the crystallized PET fiber is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, further preferably 60 to 80% by mass, and particularly preferably 65 to 75% by mass. Even if the content of the crystallized PET fiber is less than 40% by mass or more than 90% by mass, the strength of the nonwoven fabric substrate may be weakened.
- the average fiber diameter of the crystallized PET fiber is preferably from 0.1 to 10.0 ⁇ m, more preferably from 0.5 to 9.0 ⁇ m, still more preferably from 1.0 to 8.0 ⁇ m. If the average fiber diameter is less than 0.1 ⁇ m, the fibers may be too thin and fall off from the nonwoven fabric substrate. If the average fiber diameter is greater than 10.0 ⁇ m, it may be difficult to make the separator thin.
- the fiber length of the crystallized PET fiber is preferably 1 to 10 mm, more preferably 2 to 7 mm, and further preferably 3 to 5 mm. If the fiber length is shorter than 1 mm, the strength of the nonwoven fabric substrate may be weakened. If the fiber length is longer than 10 mm, the fibers may be entangled and become lumpy, resulting in uneven thickness.
- Nonwoven fabric substrate (1) mainly comprises PET fibers.
- the “main body” means that the content of PET fibers is 70% by mass or more.
- fibers other than PET fiber For example, short fiber and fibrillated solvent-spun cellulose and regenerated cellulose; natural cellulose fiber; pulped and fibrillated natural cellulose fiber; polyolefin, acrylic, wholly aromatic polyester, wholly aromatic polyester amide, polyamide, semi-aromatic polyamide , Wholly aromatic polyamide, wholly aromatic polyether, wholly aromatic polycarbonate, wholly aromatic polyazomethine, polyimide, polyamideimide (PAI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), poly-p-phenylene Single fibers and composite fibers made of resins such as benzobisoxazole (PBO), polybenzimidazole (PBI), polytetrafluoroethylene (PTFE), ethylene-vinyl alcohol copolymer, and
- One kind of these fibers may be contained, or two or more kinds thereof may be contained.
- Semi-aromatic refers to those having, for example, a fatty chain as part of the main chain.
- the wholly aromatic polyamide may be para-type or meta-type.
- the basis weight of the nonwoven fabric base material (1) is preferably 6.0 ⁇ 20.0g / m 2, 8.0 ⁇ 18.0g / m 2 , more preferably, 10.0 ⁇ 16.0g / m 2 and more preferable. If it exceeds 20.0 g / m 2 , it may be difficult to reduce the thickness of the separator, and if it is less than 6.0 g / m 2 , it may be difficult to obtain sufficient strength.
- the basis weight is measured based on the method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
- the thickness of the nonwoven fabric substrate (1) is preferably 10 to 30 ⁇ m, more preferably 13 to 27 ⁇ m, and even more preferably 15 to 25 ⁇ m. If it is less than 10 ⁇ m, sufficient strength of the nonwoven fabric substrate may not be obtained. If it is thicker than 30 ⁇ m, it is difficult to make the separator thin. The thickness is measured with an outer micrometer having a minimum display amount of 0.001 mm as defined in JIS B7502-1994.
- the nonwoven fabric substrate (2) is a PET fiber for binders (hereinafter referred to as “for binder”) having an average fiber diameter of 14.0 ⁇ m or less and a fiber length of 0.5 to 2.5 mm in the nonwoven fabric substrate (1). It is characterized by containing 21 to 60% by mass of PET fiber (I) ”(sometimes abbreviated as“ PET fiber (I) ”).
- the “average fiber diameter” as used herein refers to an average value of 10 fibers from the smallest of 20 measured equivalent circular diameters of fibers forming the nonwoven fabric substrate from a scanning electron micrograph of the nonwoven fabric substrate cross section. It is. The reason for using only the ten measured values from the smaller one is to exclude the measured values for fibers that have been severely cut off from a right angle to the longitudinal direction of the fibers.
- the average fiber diameter of the binder PET fiber (I) is 14.0 ⁇ m or less, the number of fibers in the thickness direction is increased, so that the strength of the nonwoven fabric substrate is increased. If the PET fiber for binder (I) is too thin, it may fall off from the nonwoven fabric substrate, and therefore the average fiber diameter of the PET fiber for binder (I) is preferably 0.1 ⁇ m or more. Further, the average fiber diameter of the PET fiber (I) for binder is more preferably 1.0 to 13.0 ⁇ m, and further preferably 2.0 to 10.0 ⁇ m.
- the fiber length of the binder-use PET fiber (I) When the fiber length of the binder-use PET fiber (I) is shorter than 0.5 mm, the fiber may fall off from the nonwoven fabric substrate. If the length is longer than 2.5 mm, the nonwoven fabric base material tends to stretch, the PET fibers for binder (I) tend to get entangled, and the distribution in the nonwoven fabric base material becomes uneven. Become.
- the fiber length of the binder PET fiber (I) is more preferably 0.7 to 2.3 mm, and still more preferably 1.0 to 2.0 mm.
- the content of the binder-use PET fiber (I) is less than 21% by mass, the strength of the nonwoven fabric substrate may be weakened or wrinkles may be easily formed. When it is more than 60% by mass, the molten component closes the pores of the nonwoven fabric base material, and the liquid retention of the nonwoven fabric base material deteriorates.
- the content of the PET fiber (I) for binder is more preferably 25 to 50% by mass, further preferably more than 30% by mass and 50% by mass or less, and particularly preferably 35 to 45% by mass.
- Nonwoven fabric substrate (2) contains crystallized PET fibers.
- the content of crystallized PET fibers is preferably 40 to 79% by mass, more preferably 50 to 75% by mass, further preferably 50% by mass or more and less than 70% by mass, and particularly preferably 55 to 65% by mass. Even if the content of the crystallized PET fiber is less than 40% by mass or more than 79% by mass, the strength of the nonwoven fabric substrate may be weakened.
- the average fiber diameter of the crystallized PET fiber is preferably from 0.1 to 10.0 ⁇ m, more preferably from 0.5 to 9.0 ⁇ m, still more preferably from 1.0 to 8.0 ⁇ m. If the average fiber diameter is less than 0.1 ⁇ m, the fibers may be too thin and fall off from the nonwoven fabric substrate. If the average fiber diameter is greater than 10.0 ⁇ m, it may be difficult to make the separator thin.
- the fiber length of the crystallized PET fiber is preferably 1 to 10 mm, more preferably 2 to 7 mm, and further preferably 3 to 5 mm. If the fiber length is shorter than 1 mm, the strength of the nonwoven fabric substrate may be weakened. If the fiber length is longer than 10 mm, the fibers may be entangled and become lumpy, resulting in uneven thickness.
- the nonwoven fabric substrate (2) may contain a binder PET fiber other than the binder PET fiber (I), but the content is preferably 20% by mass or less. If the content exceeds 20% by mass, the melted component of the binder PET fiber may block the pores of the nonwoven fabric substrate, and the resistance of the separator may deteriorate.
- PET fiber for the binder examples include a core-sheath type, an eccentric type, a side-by-side type, a sea-island type, an orange type, a multi-bimetal type composite fiber, and a single component type.
- a one-component type heat-sealing fiber is preferable.
- the basis weight of the nonwoven fabric substrate (2) is preferably 6.0 ⁇ 20.0g / m 2, 8.0 ⁇ 18.0g / m 2 , more preferably, 10.0 ⁇ 16.0 g / m 2 and more preferable. If it exceeds 20.0 g / m 2 , it may be difficult to reduce the thickness of the separator, and if it is less than 6.0 g / m 2 , it may be difficult to obtain sufficient strength.
- the basis weight is measured based on the method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
- the thickness of the nonwoven fabric substrate (2) is preferably 10 to 30 ⁇ m, more preferably 13 to 27 ⁇ m, and even more preferably 15 to 25 ⁇ m. If it is less than 10 ⁇ m, sufficient strength of the nonwoven fabric substrate may not be obtained. If it is thicker than 30 ⁇ m, it is difficult to make the separator thin. The thickness is measured with an outer micrometer having a minimum display amount of 0.001 mm as defined in JIS B7502-1994.
- the nonwoven fabric substrate (3) is a nonwoven fabric substrate (1) having an average fiber diameter of 1.5 to 2.8 ⁇ m and a fiber length of 1.0 to 2.5 mm (hereinafter referred to as “binder”). 10-30% by mass) of PET fiber (II) for use as a binder), and 80-100% by mass in total of PET fiber (II) for binder and crystallized PET fiber, and crystallized PET fiber.
- the average fiber diameter is 2.0 to 4.0 ⁇ m.
- the “average fiber diameter” as used herein refers to an average value of 10 fibers from the smallest of 20 measured equivalent circular diameters of fibers forming the nonwoven fabric substrate from a scanning electron micrograph of the nonwoven fabric substrate cross section. It is. The reason for using only the ten measured values from the smaller one is to exclude the measured values for fibers that have been severely cut off from a right angle to the longitudinal direction of the fibers.
- the average fiber diameter of the binder-use PET fibers (II) By setting the average fiber diameter of the binder-use PET fibers (II) to 2.8 ⁇ m or less, the number of the binder-use PET fibers is increased, and the specific surface area of the binder-use PET fibers is increased to improve the binding force. Sufficient strength can be obtained with a small content of 30% by mass or less. However, even if the nonwoven fabric substrate (3) contains a small amount of binder-use PET fibers having a fiber diameter exceeding 2.8 ⁇ m, the effect on the nonwoven fabric substrate (3) is not greatly affected. Here, the “small amount” is 15% by mass or less with respect to the nonwoven fabric substrate.
- the PET fiber for binders having a thin average fiber diameter like the PET fiber for binders (II) when the fiber length exceeds 2.5 mm, the PET fibers for binder are easily entangled with each other in the nonwoven fabric base material. The distribution of the PET fibers for the binder becomes non-uniform, and the binding force is reduced. If the content is as low as 30% by mass or less, sufficient strength cannot be obtained. However, even if the nonwoven fabric substrate (3) contains a small amount of binder-use PET fibers having a fiber length exceeding 2.5 mm, the effect on the nonwoven fabric substrate (3) is not greatly affected.
- the “small amount” herein is 10% by mass or less based on the nonwoven fabric substrate.
- the average fiber diameter of the binder-use PET fibers (II) is 1.5 ⁇ m or more, entanglement between the binder-use PET fibers can be suppressed, and the distribution of the binder-use PET fibers in the nonwoven fabric substrate is made uniform. Therefore, the binding force is improved, and sufficient strength can be obtained with a small content of 30% by mass or less.
- the nonwoven fabric substrate (3) contains a small amount of binder PET fibers having a fiber diameter of less than 1.5 ⁇ m, the effect on the nonwoven fabric substrate (3) is not greatly affected.
- the “small amount” is 5% by mass or less with respect to the nonwoven fabric substrate.
- the fiber length of the PET fiber for binder (II) is 1.0 mm or more, the PET fiber for binder can be prevented from falling off from the non-woven fabric substrate, and the strength is sufficient with a small content of 30% by mass or less. Is obtained. From such a viewpoint, the fiber length of the binder-use PET fiber (II) is more preferably 1.5 mm or more. However, even if the nonwoven fabric substrate (3) contains a small amount of binder PET fibers having a fiber length of less than 1.0 mm, the effect on the nonwoven fabric substrate (3) is not greatly affected. Here, the “small amount” is 5% by mass or less with respect to the nonwoven fabric substrate.
- the content of the PET fiber (II) for binder is less than 10% by mass, the strength of the nonwoven fabric substrate is weakened. From such a viewpoint, the content of the binder-use PET fiber (II) is more preferably 15% by mass or more. In addition, when the content of the binder fiber having a thin average fiber diameter is more than 30% by mass as in the case of the PET fiber (II) for the binder, the melted component may block the pores of the nonwoven fabric substrate and increase the internal resistance. . From such a viewpoint, the content of the PET fiber for binder (II) is preferably 30% by mass or less, and more preferably 25% by mass or less.
- sea component is eluted from melt-spun sea-island fiber filaments using PET resin as island component and appropriate solvent-soluble resin such as alkaline aqueous solution-soluble polyester resin as sea component.
- a single component type PET fiber for a binder obtained by cutting the fiber having an average fiber diameter of 1.5 to 2.8 ⁇ m obtained by using a suitable cutting device so that the fiber length is 1.0 to 2.5 mm. Staples can be used.
- the sea-island fiber filament may be first cut to have a fiber length of 1.0 to 2.5 mm and then the sea component may be eluted.
- Nonwoven fabric substrate (3) contains 80 to 100% by mass in total of PET fiber (II) for binder and crystallized PET fiber.
- fibers other than PET fiber (II) for binder and crystallized PET fiber may be contained, but the amount is limited to 20% by mass or less.
- the fiber other than the PET fiber for binder (II) and the crystallized PET fiber exceeds 20% by mass, the binding force between the PET fiber for binder (II) and the other fiber decreases.
- a nonwoven fabric substrate with high strength cannot be obtained. From such a viewpoint, it is more preferable that the nonwoven fabric substrate (3) contains 90% by mass or more in total of the PET fiber (II) for binder and the crystallized PET fiber.
- the nonwoven fabric substrate (3) crystallized PET fibers having an average fiber diameter of 2.0 to 4.0 ⁇ m are used. If the average fiber diameter is less than 2.0 ⁇ m, the nonwoven fabric substrate is too clogged and the internal resistance is increased. However, even if the nonwoven fabric substrate (3) contains a small amount of crystallized PET fibers having a fiber diameter of less than 2.0 ⁇ m, the effect on the nonwoven fabric substrate (3) is not greatly affected.
- the “small amount” is 15% by mass or less based on the nonwoven fabric substrate.
- the average fiber diameter of the crystallized PET fiber exceeds 4.0 ⁇ m, the non-woven fabric base material becomes insufficiently clogged, and the coating liquid tends to break through. From such a viewpoint, the average fiber diameter of the crystallized PET fiber is more preferably 3.5 ⁇ m or less. However, even if the nonwoven fabric substrate (3) contains a small amount of crystallized PET fibers having a fiber diameter exceeding 4.0 ⁇ m, the effect on the nonwoven fabric substrate (3) is not greatly affected. Here, the “small amount” is 15% by mass or less with respect to the nonwoven fabric substrate.
- the fiber length of the crystallized PET fiber is preferably 2.5 to 6.0 mm. If the fiber length of the crystallized PET fiber is less than 2.5 mm, sufficient tensile strength may not be obtained, and if it exceeds 6.0 mm, the formation deteriorates due to the entanglement of the fibers, and the separator High-thickness defects that may have an undesirable effect on the use of
- the basis weight of the nonwoven fabric substrate (3) is preferably 6.0 to 12.0 g / m 2 . If it is less than 6.0 g / m 2 , it may be difficult to obtain sufficient strength. If it exceeds 12.0 g / m 2 , it may be difficult to make the separator thin.
- the basis weight is measured based on the method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
- the thickness of the nonwoven fabric substrate (3) is preferably 8 to 18 ⁇ m. If it is less than 8 micrometers, even if it is a nonwoven fabric base material (3), the show-through of a coating liquid may arise easily. If it is thicker than 18 ⁇ m, the internal resistance may increase. In the present invention, the thickness of the nonwoven fabric substrate is measured with an outer micrometer having a minimum display amount of 0.001 mm as defined in JIS B7502-1994.
- the nonwoven fabric substrate (4) is composed mainly of PET fibers and contains 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component, and is abbreviated as “PET fibers for binder (III)”. May be included).
- the average fiber diameter of the binder PET fiber (III) is preferably 0.5 to 14.0 ⁇ m, more preferably 1.0 to 13.0 ⁇ m, and more preferably 2.0 to 10.0 ⁇ m. Further preferred. If the average fiber diameter is thinner than 0.5 ⁇ m, it may fall off from the nonwoven fabric substrate. If it is thicker than 14.0 ⁇ m, the number of fibers in the thickness direction will decrease, and the strength of the nonwoven fabric substrate may be weakened. .
- the “average fiber diameter” as used herein refers to an average value of 10 fibers from the smallest of 20 measured equivalent circular diameters of fibers forming the nonwoven fabric substrate from a scanning electron micrograph of the nonwoven fabric substrate cross section. It is. The reason for using only the ten measured values from the smaller one is to exclude the measured values for fibers that have been severely cut off from a right angle to the longitudinal direction of the fibers.
- the fiber length of the binder PET fiber (III) is preferably 0.5 to 5.0 mm, more preferably 0.7 to 4.0 mm, and further preferably 1.0 to 3.0 mm. preferable. If the fiber length is shorter than 0.5 mm, the fiber may fall off from the nonwoven fabric substrate, and if it is longer than 5.0 mm, the fiber may become entangled and become lumpy, resulting in uneven thickness.
- the content of the PET fiber (III) for binder is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and further preferably 20 to 50% by mass.
- the content is less than 5% by mass, the strength of the nonwoven fabric substrate may be weakened.
- the content is more than 60% by mass, the molten component closes the pores of the nonwoven fabric substrate and the liquid retention of the nonwoven fabric substrate deteriorates. Or the resistance of the separator may increase.
- the binder PET fiber (III) is preferably a single-component heat-sealing fiber from the viewpoint of obtaining uniformity.
- the PET fiber (III) for binder may contain alkyl glycol and its derivatives as copolymerization components other than 3,5-dicarbomethoxybenzenesulfonic acid.
- alkyl glycol and its derivatives diethylene glycol is preferred.
- the nonwoven fabric substrate (4) preferably contains crystallized PET fibers in addition to the binder PET fibers (III).
- the content of crystallized PET fiber is preferably 40 to 95% by mass, more preferably 45 to 90% by mass, and further preferably 50 to 80% by mass. Even if the content of the crystallized PET fiber is less than 40% by mass or more than 95% by mass, the strength of the nonwoven fabric substrate may be weakened.
- the average fiber diameter of the crystallized PET fiber is preferably 0.5 to 10.0 ⁇ m, more preferably 0.7 to 8.0 ⁇ m, and further preferably 1.0 to 6.0 ⁇ m. If the average fiber diameter is less than 0.5 ⁇ m, the fibers may be too thin and fall off from the nonwoven fabric substrate. If the average fiber diameter is greater than 10.0 ⁇ m, it may be difficult to make the separator thin.
- the fiber length of the crystallized PET fiber is preferably 1 to 10 mm, more preferably 2 to 7 mm, and further preferably 3 to 5 mm. If the fiber length is shorter than 1 mm, the strength of the nonwoven fabric substrate may be weakened. If the fiber length is longer than 10 mm, the fibers may be entangled and become lumpy, resulting in uneven thickness.
- the nonwoven fabric substrate (4) may contain binder PET fibers other than the binder PET fibers (III), but the content is preferably 20% by mass or less. If the content exceeds 20% by mass, the melted component of the binder PET fiber may block the voids of the nonwoven fabric substrate, resulting in deterioration of liquid retention and separator resistance.
- Nonwoven fabric substrate (4) mainly comprises PET fibers.
- the “main body” means that the content of the PET fiber is 70% by mass or more.
- fibers other than PET fiber For example, short fiber and fibrillated solvent-spun cellulose and regenerated cellulose; natural cellulose fiber; pulped and fibrillated natural cellulose fiber; polyolefin, acrylic, wholly aromatic polyester, wholly aromatic polyester amide, polyamide, semi-aromatic polyamide , Wholly aromatic polyamide, wholly aromatic polyether, wholly aromatic polycarbonate, wholly aromatic polyazomethine, polyimide, polyamideimide (PAI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), poly-p-phenylene Single fibers and composite fibers made of resins such as benzobisoxazole (PBO), polybenzimidazole (PBI), polytetrafluoroethylene (PTFE), ethylene-vinyl alcohol copolymer,
- One kind of these fibers may be contained, or two or more kinds thereof may be contained.
- Semi-aromatic refers to those having, for example, a fatty chain as part of the main chain.
- the wholly aromatic polyamide may be para-type or meta-type.
- the basis weight of the nonwoven fabric substrate (4) is preferably 6.0 ⁇ 20.0g / m 2, 8.0 ⁇ 18.0g / m 2 , more preferably, 10.0 ⁇ 16.0g / m 2 and more preferable. If it exceeds 20.0 g / m 2 , it may be difficult to reduce the thickness of the separator, and if it is less than 6.0 g / m 2 , it may be difficult to obtain sufficient strength.
- the basis weight is measured based on the method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
- the thickness of the nonwoven fabric substrate (4) is preferably 10 to 30 ⁇ m, more preferably 13 to 27 ⁇ m, and even more preferably 15 to 25 ⁇ m. If it is less than 10 ⁇ m, sufficient strength of the nonwoven fabric substrate may not be obtained. If it is thicker than 30 ⁇ m, it is difficult to make the separator thin. The thickness is measured with an outer micrometer having a minimum display amount of 0.001 mm as defined in JIS B7502-1994.
- the nonwoven fabric substrates (1) to (4) of the present invention are preferably used for the production of a separator formed by coating a coating solution containing an inorganic pigment on a nonwoven fabric substrate.
- the nonwoven fabric substrates (1) to (4) of the present invention are made of resin fine particles such as separators, polyethylene microporous membranes, and polypropylene microporous membranes, which are obtained by coating a nonwoven fabric substrate with a coating liquid containing organic particles.
- the nonwoven fabric substrates (1) to (4) of the present invention are precursor sheets for lithium ion secondary battery separators.
- Inorganic pigments include alumina, gibbsite, boehmite, magnesium oxide, magnesium hydroxide, silica, titanium oxide, barium titanate, zirconium oxide and other inorganic oxides, aluminum nitride and silicon nitride inorganic nitrides, aluminum compounds, zeolites And mica.
- Organic particles include particles of polyethylene, polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polystyrene, polyvinylidene fluoride, ethylene-vinyl monomer copolymer, polyolefin wax, and the like.
- the medium for preparing a coating liquid containing inorganic pigments and organic particles is not particularly limited as long as it can uniformly dissolve or disperse binders, inorganic pigments, organic particles, etc.
- aromatic carbonization such as toluene Hydrogen, tetrahydrofuran such as tetrahydrofuran, ketones such as methyl ethyl ketone, alcohols such as isopropyl alcohol, N-methyl-2-pyrrolidone (NMP), dimethylacetamide, dimethylformamide, dimethyl sulfoxide, water, etc. are used as necessary. be able to. Moreover, you may mix and use these media as needed.
- the medium to be used is preferably a medium that does not expand or dissolve the nonwoven fabric substrate.
- Examples of methods for applying a coating liquid containing inorganic pigments and organic particles onto a nonwoven fabric substrate include various coating methods such as blades, rods, reverse rolls, lips, dies, curtains, and air knives, flexo, screen, and offset.
- Various printing methods such as gravure and inkjet, transfer methods such as roll transfer and film transfer, pulling methods such as dipping, and the like can be selected and used as necessary.
- the porous film is not particularly limited as long as it is a resin capable of forming a film, but polyolefin resins such as polyethylene resins and polypropylene resins are preferable.
- the polyethylene resin include a resin of a single polyethylene resin such as ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, or ultra high density polyethylene.
- the mixture of an ethylene propylene copolymer, a polyethylene-type resin, and another polyolefin resin is mentioned.
- Polypropylene resins include homopropylene (propylene homopolymer), propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Examples thereof include a random copolymer or block copolymer with ⁇ -olefin.
- the lithium ion secondary battery in the present invention is a general term for secondary batteries in which lithium ions in the electrolyte solution are responsible for electrical conduction.
- Battery negative electrode active materials include natural graphite, artificial graphite, carbon materials such as hard carbon and coke; metal lithium; alloys of metals such as silicon, aluminum, tin, nickel and lead; lithium; lithium titanate, tin oxide Examples thereof include complex oxides of lithium and metal such as lithium silicate.
- the positive electrode active material examples include lithium cobaltate, lithium manganate, lithium nickelate, lithium titanate, lithium nickel manganese oxide, etc .; transition metal and lithium composite oxide; olivine type lithium iron phosphate; nickel-cobalt-manganese -One or more transition metals such as lithium complex oxide, nickel-cobalt-manganese-lithium complex oxide, nickel-cobalt-aluminum-lithium complex oxide, iron-manganese-nickel-lithium complex oxide And lithium composite oxide, or one or more transition metals, one or more typical metals, and lithium composite oxide.
- a solution obtained by dissolving a lithium salt in an organic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, dimethoxymethane, or a mixed solvent thereof is used.
- the lithium salt include lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ). If necessary, additives such as vinylene carbonate and boric acid esters may be added.
- a gelled electrolytic solution obtained by dissolving a polymer such as polyethylene glycol or a derivative thereof, polymethacrylic acid derivative, polysiloxane or a derivative thereof, or polyvinylidene fluoride can be used.
- a method for producing the nonwoven fabric substrates (1) to (4) a method can be used in which a nonwoven fabric is produced by forming a fiber web and bonding, fusing, or intertwining the fibers in the fiber web.
- the obtained nonwoven fabric may be used as it is or may be used as a laminate comprising a plurality of sheets.
- the method for producing the fiber web include a dry method such as a card method, an air lay method, a spun bond method, and a melt blow method; a wet method such as a paper making method; and an electrostatic spinning method.
- the fiber web obtained by a wet method is homogeneous and dense, and can be suitably used as a nonwoven fabric substrate for a lithium ion secondary battery separator.
- the wet method is a method in which fibers are dispersed in water to form a uniform papermaking slurry, and this papermaking slurry is obtained using a papermaking machine having at least one of a wire such as a circular net, a long net, and an inclined type to obtain a fiber web. is there.
- a hydroentanglement method As a method for producing a nonwoven fabric from a fibrous web, a hydroentanglement method, a needle punch method, a binder adhesion method, or the like can be used.
- a wet method when used with emphasis on uniformity, it is preferable to bond the PET fibers for the binder by performing a binder bonding method.
- a uniform nonwoven fabric is formed from a uniform fiber web by the binder bonding method.
- the thickness or make the thickness uniform it is preferable to adjust the thickness or make the thickness uniform by pressurizing the nonwoven fabric thus manufactured with a calendar or the like.
- a lithium ion secondary battery separator having a thickness of 25 ⁇ m or less which is difficult to manufacture with high productivity due to wrinkles generated during coating and back-through of the coating liquid. It is possible to manufacture. In particular, it is also possible to produce a lithium ion secondary battery separator having a thickness of 22 ⁇ m or less. Of course, a lithium ion secondary battery separator having a thickness of more than 25 ⁇ m can also be easily manufactured. On the other hand, an extremely thin separator having a thickness of less than 10 ⁇ m is difficult to manufacture according to the present invention. The thickness is measured with an outer micrometer having a minimum display amount of 0.001 mm as defined in JIS B7502-1994.
- PET fiber A2 for binder Single-component unstretched PET fiber (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 4.3 ⁇ m and a fiber length of 1.5 mm was designated as PET fiber A2 for binder.
- PET fiber A3 for binder Single-component unstretched PET fiber (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 4.3 ⁇ m and a fiber length of 2.5 mm was designated as PET fiber A3 for binder.
- PET fiber A4 for binder Single-component unstretched PET fibers (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 14.0 ⁇ m and a fiber length of 2.5 mm were designated as PET fibers A4 for binders.
- PET fiber A5 for binder Single-component unstretched PET fiber (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 1.0 ⁇ m and a fiber length of 1.0 mm was designated as PET fiber A5 for binder.
- PET fiber A6 for binder A core-sheath type heat-fusible PET fiber (sheath part melting point: 110 ° C., core part: 250 ° C.) having an average fiber diameter of 7.2 ⁇ m and a fiber length of 2.0 mm was designated as PET fiber A6 for binder.
- PET fiber A7 for binder A single-component unstretched PET fiber (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 4.3 ⁇ m and a fiber length of 0.3 mm was designated as PET fiber A7 for binder.
- PET fiber A8 for binder Single-component unstretched PET fibers (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 4.3 ⁇ m and a fiber length of 3.0 mm were used as PET fibers A8 for binders.
- PET fiber A9 for binder Single-component unstretched PET fiber (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 15.0 ⁇ m and a fiber length of 2.5 mm was designated as PET fiber A9 for binder.
- a papermaking slurry was prepared according to the fiber raw materials and fiber blending ratio shown in Table 1.
- “B1” in Table 1 is a crystallized PET fiber having an average fiber diameter of 2.5 ⁇ m and a fiber length of 3 mm
- “B2” is a crystallized PET fiber having an average fiber diameter of 3.2 ⁇ m and a fiber length of 3 mm
- “B3” is a crystallized PET fiber having an average fiber diameter of 5.5 ⁇ m and a fiber length of 3 mm
- “B4” is a crystallized PET fiber having an average fiber diameter of 7.8 ⁇ m and a fiber length of 5 mm
- “C1” is a fineness of 0.75 dtex.
- Wholly aromatic polyamide fiber having a fiber length of 3 mm (copoly (para-phenylene-3,4'-oxydiphenylene terephthalamide, copolymer (para-phenylene-3,4'-oxydiphenylethylene amide)), "C2" has a fineness 0.10 dtex, fiber length 3 mm acrylic fiber (acrylonitrile, methyl acrylate, methacrylic acid derivative It means consisting of components acrylonitrile copolymer).
- Example 1 to 3, 5 to 13 Slurries 1 to 3, 5 to 12 and 14 were wet-made at a speed of 18 m / min using a circular net / tilted combination paper machine, and the nonwoven fabric bases of Examples 1 to 3, 5 to 12 and 14 shown in Table 2 were used.
- a material was prepared. The thickness was determined by using a heat calender device having a configuration of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
- a heat calender device having a configuration of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and
- Example 4 Slurry 4 was subjected to wet paper making at a speed of 18 m / min using a circular mesh / tilted combination paper machine to produce a separator of Example 4 shown in Table 2.
- the thickness was determined by using a heat calender device having a structure of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 100 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
- Comparative Examples 1 and 3 Slurries 13 and 16 were subjected to wet paper making at a speed of 18 m / min using a circular net / tilted combination paper machine to produce separators of Comparative Examples 1 and 2 shown in Table 2.
- the thickness was determined by using a heat calender device having a configuration of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
- Comparative Example 2 Slurry 15 was subjected to wet paper making at a speed of 18 m / min using a circular mesh / tilted combination paper machine to produce a separator of Comparative Example 2 shown in Table 2.
- the thickness was determined by using a heat calender device having a structure of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 100 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
- the liquid retention rate is measured twice or more for one sample, and the average value of the measured values is “A” if it is 300% or more, “B” if it is 270% or more and less than 300%, and if it is less than 270%. Represented by “C”.
- a 100% part by weight boehmite having a volume average particle size of 0.9 ⁇ m and a BET specific surface area of 5.5 m 2 / g is dispersed in 150 parts by weight of water. 75 parts by mass of a 2% by weight aqueous solution of methylcellulose sodium salt was added and mixed with stirring.
- the coating liquid A is 47 g / m 2 as a liquid at a line speed of 30 m / min.
- One side of the coating was applied.
- the coated nonwoven fabric substrate was dried by blowing hot air at 90 ° C. with a floating air dryer directly connected to a reverse gravure coater to obtain a separator.
- the separator was classified into the following three stages according to the state of occurrence of wrinkles when the separator was wound up by 500 m with a reeler.
- ⁇ Wrinkles are not observed during coating. ⁇ : Less wrinkling during coating. ⁇ : Many wrinkles occur during coating.
- the nonwoven fabric substrates produced in Examples 1 to 13 are mainly composed of PET fibers, contain PET fibers for binders and crystallized PET fibers, and have a fiber length of 2.5 mm or less.
- a lithium ion secondary battery separator coated with an inorganic pigment could be manufactured.
- the nonwoven fabric base materials produced in Examples 1 to 11 mainly consist of PET, have an average fiber diameter of 14.0 ⁇ m or less, and have a fiber length of 0.5 to 2.5 mm. It is also a nonwoven fabric substrate (2) containing 21 to 60% by mass. Therefore, the elongation of the nonwoven fabric substrate is small, and the distribution of the PET fibers for binder in the nonwoven fabric substrate is uniform. Therefore, even when compared with the nonwoven fabric substrates prepared in Examples 12 to 13, Generation
- the nonwoven fabric base material produced in Example 12 has a fiber length of the PET fibers for binders shorter than 0.5 mm, a slight dropout from the nonwoven fabric base material is seen, and the nonwoven fabric base material produced in Examples 1 to 11 However, the tensile strength was weakened.
- the nonwoven fabric substrate produced in Example 13 has an average fiber diameter of 14.0 ⁇ m thicker than the PET fiber for the binder, so the number of fibers in the thickness direction is reduced, and the nonwoven fabric substrate produced in Examples 1 to 11 However, the tensile strength was weakened.
- the nonwoven fabric base material produced in Comparative Example 1 has a fiber length of the PET fiber for the binder longer than 2.5 mm, the nonwoven fabric base material is easily stretched and entangled between the binder PET fibers, so wrinkles are included. Easy and inferior in productivity.
- the non-woven fabric base material produced in Comparative Example 2 had a PET fiber for binder content of less than 10% by mass, so that wrinkles at the time of coating were likely to occur and the separator productivity was poor. Since the nonwoven fabric base material produced in Comparative Example 3 had a content of PET fiber for binder of more than 60% by mass, the melted component blocked the pores, resulting in poor liquid retention.
- the nonwoven fabric base materials produced in Examples 1 to 11 will be compared. Since the nonwoven fabric substrate produced in Example 1 has a slightly short fiber length of the PET fiber for binder, the nonwoven fabric substrate produced in Example 4 has a slightly thick fiber diameter of the PET fiber for binder. Since the basis weight of the nonwoven fabric substrate produced in 9 was slightly low, the tensile strength was slightly weaker than that of the nonwoven fabric substrates produced in Examples 2, 3, 5 to 8, 10, and 11.
- the nonwoven fabric base material produced in Example 8 has an average fiber diameter of 14.0 ⁇ m or less and a slightly higher content of PET fibers (I) for binders having a fiber length of 0.5 to 2.5 mm. As compared with the nonwoven fabric base materials produced in Examples 1 to 7 and 9 to 11, the liquid retention was slightly deteriorated.
- the nonwoven fabric substrate produced in Example 3 has a slightly longer fiber length of the PET fiber for binder
- the nonwoven fabric substrate produced in Example 4 has an average fiber diameter of 14.0 ⁇ m or less and a fiber length. Since the content of the PET fiber for binder having a thickness of 0.5 to 2.5 mm was slightly smaller, the wrinkles were slightly more likely to occur during coating than the nonwoven fabric substrates prepared in Examples 1, 2, and 5 to 11.
- ⁇ PET fiber for binder (average fiber diameter 1.6 ⁇ m)>
- a binder fiber having an average fiber diameter of 1.6 ⁇ m was produced by cutting a filament produced by eluting sea components from sea-island fibers into a predetermined length.
- ⁇ PET fiber for binder (average fiber diameter 2.8 ⁇ m)>
- a binder fiber having an average fiber diameter of 2.8 ⁇ m was produced by cutting a filament produced by eluting sea components from sea-island fibers into a predetermined length.
- ⁇ PET fiber for binder (average fiber diameter 4.3 ⁇ m)>
- a binder fiber having an average fiber diameter of 4.3 ⁇ m was produced by cutting a filament produced by a melt spinning method into a predetermined length.
- ⁇ Crystalline PET fiber 24 Crystallized PET staple (softening point 250 ° C.) obtained by melt spinning and having a mean fiber diameter of 2.4 ⁇ m cut to a length of 3.0 mm was used as the stretched crystallized PET fiber 24.
- Crystallized PET staple (softening point 250 ° C.) obtained by cutting a filament having an average fiber diameter of 1.6 ⁇ m produced by eluting sea components from sea-island fibers into a length of 3.0 mm is used as stretched crystallized PET fiber 16 It was.
- ⁇ Crystalline PET fiber 43 > Crystallized PET staples (softening point 250 ° C.) prepared by melt spinning and having filaments with an average fiber diameter of 4.3 ⁇ m cut to a length of 3.0 mm were used as stretched crystallized PET fibers 43.
- ⁇ Cellulose fiber> Using a double disk refiner, lyocell (solvent-spun cellulose) fibers beaten to a Canadian standard freeness of 50 mL were used.
- ⁇ Aramid fiber> Para-aramid fibers beaten to a Canadian standard freeness of 250 mL using a double disc refiner were used.
- Papermaking slurries were prepared according to the fiber raw materials and contents shown in Tables 4-5. These were made at a speed of 8 m / min using an inclined wire paper machine so that the basis weight after drying was 9.0 g / m 2 , dried by a cylinder dryer, and then a metal roll-resin roll (Shore hardness D92 ) With a metal roll temperature of 195 ° C., a linear pressure of 100 kN / m, a processing speed of 5 m / min, and a nip (nip) of a non-woven fabric base having a thickness of 13 ⁇ m. I got the material.
- Non-volatile concentration of 40 containing 100 parts by mass of magnesium hydroxide having an average particle size of 1.0 ⁇ m, 1.5 parts by mass of styrene-butadiene latex, and 1.0 part by mass of sodium carboxymethylcellulose in the nonwoven fabric base materials of Examples and Comparative Examples
- the coating solution of mass% was applied using a rod coater so that the coating amount after drying was 10 g / m 2 . At this time, black color image paper was used as the mount.
- Tables 4 to 5 show the results of classification into the following four stages according to the amount of the coating liquid that has adhered to the black drawing paper used as the backing sheet through the nonwoven fabric substrate in the separator preparation.
- a The coating liquid is not attached to the mount.
- a lithium ion secondary battery for evaluation having a capacity of 30 mAh (electrode area: 15 cm 2 , positive electrode: lithium manganate, negative electrode: hard carbon, electrolyte: 1M lithium hexafluorophosphate (LiPF 6 ) using each separator produced.
- Ethylene carbonate (EC) / diethyl carbonate (DEC) 3/7 (volume ratio) mixed solvent solution, pouch type battery) was prepared.
- Tables 4 to 5 show the internal resistances obtained by the following (Equation 2) from the inter-terminal voltage E 0 after the battery was fully charged and the inter-terminal voltage E 1 immediately after discharging at 150 mA for 10 seconds.
- the nonwoven fabric base materials produced in Examples 14 to 30 are mainly composed of PET fibers, contain PET fibers for binders and crystallized PET fibers, and 10 to 60 masses of PET fibers for binders having a fiber length of 2.5 mm or less. % Containing nonwoven fabric substrate (1). For this reason, wrinkles at the time of coating did not occur or even if they occurred, it was possible to correct by adjusting the lateral tension. On the other hand, since the nonwoven fabric base material of Comparative Example 4 contains only 5% by mass of the binder PET fibers, the nonwoven fabric base material of Comparative Example 5 has a fiber length of 3. 3% for the binder PET fibers. Since it was as long as 0 mm, wrinkles occurred and it was difficult to correct the wrinkles.
- the nonwoven fabric base materials produced in Examples 14 to 21 are 10 to 30 masses of PET fiber (II) for binder having an average fiber diameter of 1.5 to 2.8 ⁇ m and a fiber length of 1.0 to 2.5 mm.
- the nonwoven fabric substrate of Example 22 has a tensile strength of 400 N / m because the fiber diameter of the PET fiber for binder is as thin as 1.3 ⁇ m, which is lower than the nonwoven fabric substrate prepared in Examples 14-21.
- the nonwoven fabric base material of Example 23 has a tensile strength of 420 N / m because the fiber diameter of the PET fiber for binder is as thick as 4.3 ⁇ m.
- the nonwoven fabric base material prepared in Examples 14 to 21 Low Since the nonwoven fabric base material of Example 24 has a high content of PET fiber for binder as 40% by mass, the internal resistance of the lithium ion battery separator produced using this is 4.8 ⁇ .
- Examples 14 to 21 It is high compared with the lithium ion battery separator produced using the nonwoven fabric substrate produced in 1.
- the nonwoven fabric substrate of Example 25 has a tensile strength of 330 N / m because the fiber length of the binder PET fiber is as short as 0.5 mm, which is lower than that of the nonwoven fabric substrate produced in Examples 14-21.
- the nonwoven fabric base materials of Example 26 and Example 27 contain fibers other than PET fibers in excess of 20% by mass, so that the tensile strengths are 300 and 280 N / m, respectively. Low compared to the nonwoven fabric substrate.
- the fiber diameter of the crystallized PET fiber is as thin as 1.6 ⁇ m.
- the internal resistance of the lithium ion battery separator produced using this is 4.8 ⁇ , and Examples 14 to 21 It is high compared with the non-woven fabric base material made in In the nonwoven fabric substrate of Example 29, the fiber diameter of the crystallized PET fiber is as thick as 4.3 ⁇ m, so that the coating liquid does not show through compared with the nonwoven fabric substrates prepared in Examples 14-21.
- PET fiber A11 for binder Single-component unstretched PET fiber having an average fiber diameter of 0.5 ⁇ m and a fiber length of 0.5 mm containing 3,5-dicarbomethoxybenzenesulfonic acid and diethylene glycol as a copolymerization component (softening point 120 ° C., melting point 230 ° C. ) was designated as PET fiber A11 for binder.
- PET fiber A12 for binder As a copolymerization component, a single-component unstretched PET fiber containing 3,5-dicarbomethoxybenzenesulfonic acid and diethylene glycol and having an average fiber diameter of 1.0 ⁇ m and a fiber length of 1.0 mm (softening point 120 ° C., melting point 230 ° C. ) was designated as PET fiber A12 for binder.
- PET fiber A13 for binder As a copolymerization component, a single-component unstretched PET fiber containing 3,5-dicarbomethoxybenzenesulfonic acid and diethylene glycol and having an average fiber diameter of 2.0 ⁇ m and a fiber length of 2.0 mm (softening point 120 ° C., melting point 230 ° C. ) was designated as PET fiber A13 for binder.
- PET fiber A14 for binder As a copolymerization component, a single-component unstretched PET fiber having an average fiber diameter of 4.3 ⁇ m and a fiber length of 3.0 mm containing 3,5-dicarbomethoxybenzenesulfonic acid and diethylene glycol (softening point 120 ° C., melting point 230 ° C. ) was designated as PET fiber A14 for binder.
- PET fiber A15 for binder Single-component unstretched PET fiber having an average fiber diameter of 10.0 ⁇ m and a fiber length of 4.0 mm containing 3,5-dicarbomethoxybenzenesulfonic acid and diethylene glycol as a copolymerization component (softening point 120 ° C., melting point 230 ° C. ) was designated as PET fiber A15 for binder.
- PET fiber A16 for binder Single-component unstretched PET fiber having an average fiber diameter of 14.0 ⁇ m and a fiber length of 5.0 mm containing 3,5-dicarbomethoxybenzenesulfonic acid and diethylene glycol as a copolymerization component (softening point 120 ° C., melting point 230 ° C. ) was designated as PET fiber A16 for binder.
- ⁇ PET fiber a17 for binder> As a copolymer component, a single-component unstretched PET fiber (softening point 120 ° C., melting point 230 ° C.) having an average fiber diameter of 10.5 ⁇ m and a fiber length of 5.0 mm containing diethylene glycol was used as a binder PET fiber a17.
- ⁇ PET fiber a18 for binder> As a copolymer component, a core-sheath type heat-fusible PET fiber (sheath part melting point: 110 ° C., core part: 250 ° C.) having an average fiber diameter of 10.1 ⁇ m and a fiber length of 5.0 mm containing diethylene glycol is used as a binder PET. It was set as fiber a18.
- a papermaking slurry was prepared according to the fiber raw materials and fiber blending ratio shown in Table 6.
- “B11” in Table 6 is a crystallized PET fiber having an average fiber diameter of 0.7 ⁇ m and a fiber length of 1.7 mm containing diethylene glycol as a copolymer component
- “B12” is diethylene glycol as a copolymer component.
- Examples 30 to 44 Slurries 17 to 31 were wet paper-made at a speed of 18 m / min using a circular net / tilted combination paper machine to prepare nonwoven fabric substrates of Examples 30 to 44 shown in Table 7.
- the thickness was determined by using a heat calender device having a configuration of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
- Comparative Example 6 The slurry 32 was subjected to wet papermaking at a speed of 18 m / min using a circular mesh / tilted combination paper machine to prepare a nonwoven fabric substrate of Comparative Example 6 shown in Table 7.
- the thickness was determined by using a heat calender device having a configuration of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
- Comparative Example 7 The slurry 33 was subjected to wet papermaking at a speed of 18 m / min using a circular mesh / tilted combination paper machine to produce a nonwoven fabric substrate of Comparative Example 7 shown in Table 7.
- Comparative Example 8 The non-woven fabric substrate of Comparative Example 7 was subjected to a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and a 1 nip using a heat calender device having a metal roll-resin roll (Shore hardness D92). Thermal calendar treatment was performed under the conditions of (nip), and a nonwoven fabric substrate of Comparative Example 8 shown in Table 7 was produced.
- the liquid retention rate is measured twice or more for one sample, and the average value of the measured values is “A” if it is 300% or more, “B” if it is 270% or more and less than 300%, and if it is less than 270%. Represented by “C”.
- a 100% part by weight boehmite having a volume average particle size of 0.9 ⁇ m and a BET specific surface area of 5.5 m 2 / g is dispersed in 150 parts by weight of water. 75 parts by mass of a 2% by weight aqueous solution of methylcellulose sodium salt was added and mixed with stirring.
- the coating liquid A is 47 g / m 2 as a liquid at a line speed of 30 m / min.
- One side of the coating was applied.
- the coated substrate was dried by blowing hot air at 90 ° C. with a floating air dryer directly connected to a reverse gravure coater to obtain a separator.
- the nonwoven fabric substrates produced in Examples 30 to 44 contain PET fibers for binders mainly composed of PET and containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component.
- the nonwoven fabric base material produced in Comparative Example 6 does not contain PET fibers for binders containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component.
- the liquid retention was deteriorated.
- the resistance of the separator was increased.
- Comparative Example 7 since the nonwoven fabric base materials produced in Comparative Examples 7 and 8 do not contain a binder-use PET fiber containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component, Comparative Example 7 before thermal calendering treatment was used. The strength of the nonwoven fabric base material was weak, and the nonwoven fabric base material of Comparative Example 8 after the thermal calendering treatment had poor liquid retention and increased separator resistance.
- the nonwoven fabric substrate produced in Example 30 is a nonwoven fabric substrate because the fiber diameter of the PET fiber for binder containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component is slightly thin and the fiber length is slightly short. Some of the fibers dropped out from the fabric, and the tensile strength was slightly weaker than the nonwoven fabric substrates of Examples 31 to 34 and 37 to 44.
- the nonwoven fabric substrate produced in Example 35 has a slightly smaller number of fibers in the thickness direction because the fiber diameter of the PET fiber for binder containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component is slightly thick. Thus, the tensile strength was slightly weaker than the nonwoven fabric substrates of Examples 31 to 34 and 37 to 44.
- the nonwoven fabric substrate produced in Example 36 has a slightly lower content of PET fiber for binder containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component, and the basis weight is slightly lower. Compared to 31-34 and 37-44 nonwoven fabric substrates, the tensile strength was slightly weaker.
- the nonwoven fabric substrate produced in Example 41 has a slightly higher content of the PET fiber for the binder containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component, so that the voids of the nonwoven substrate are blocked.
- the liquid retention was slightly deteriorated and the resistance of the separator was slightly increased.
- the nonwoven fabric base material produced in Example 43 is a copolymer of PET fiber for binder containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component and 3,5-dicarbomethoxybenzenesulfonic acid as binder fibers.
- PET for binders not contained as a component is used in combination, since the content of PET for binders not containing 3,5-dicarbomethoxybenzenesulfonic acid as a copolymerization component is slightly high, voids in the nonwoven substrate A blocked portion was observed, and the liquid retention was slightly deteriorated and the resistance of the separator was slightly increased as compared with the nonwoven fabric substrates of Examples 30 to 40, 42 and 44.
- a nonwoven fabric base material for a lithium ion secondary battery separator is suitable.
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Abstract
Description
不織布基材(1)は、PET繊維を主体としてなり、バインダー用PET繊維と結晶化PET繊維を含有し、繊維長が2.5mm以下のバインダー用PET繊維を10~60質量%含有することを特徴としている。
不織布基材(2)は、不織布基材(1)において、平均繊維径が14.0μm以下であり、かつ、繊維長が0.5~2.5mmのバインダー用PET繊維(以下、「バインダー用PET繊維(I)」と略記する場合がある)を21~60質量%含有することを特徴としている。
不織布基材(3)は、不織布基材(1)において、平均繊維径が1.5~2.8μmで、かつ繊維長が1.0~2.5mmのバインダー用PET繊維(以下、「バインダー用PET繊維(II)」と略記する場合がある)を10~30質量%含有し、バインダー用PET繊維(II)と結晶化PET繊維の合計で80~100質量%含有し、結晶化PET繊維の平均繊維径が2.0~4.0μmであることを特徴とする。
本発明の不織布基材(1)~(4)は、無機顔料を含む塗液を不織布基材に塗工してなるセパレータの製造に好ましく用いられる。これに加え、本発明の不織布基材(1)~(4)は、不織布基材に有機粒子を含む塗液を塗工してなるセパレータ、ポリエチレン微多孔膜、ポリプロピレン微多孔膜等の樹脂微多孔膜と不織布基材を積層してなるセパレータ、不織布基材上に、静電紡糸法により微細繊維層を形成してなるセパレータ、固体電解質やゲル状電解質を塗工してなるセパレータ等に用いることもできる。このように、本発明の不織布基材(1)~(4)は、リチウムイオン二次電池セパレータの前駆体シートである。
<バインダー用PET繊維A1>
平均繊維径4.3μm、繊維長0.5mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A1とした。
平均繊維径4.3μm、繊維長1.5mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A2とした。
平均繊維径4.3μm、繊維長2.5mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A3とした。
平均繊維径14.0μm、繊維長2.5mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A4とした。
平均繊維径1.0μm、繊維長1.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A5とした。
平均繊維径7.2μm、繊維長2.0mmの芯鞘型熱融着性PET繊維(鞘部溶点:110℃、芯部:250℃)をバインダー用PET繊維A6とした。
平均繊維径4.3μm、繊維長0.3mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A7とした。
平均繊維径4.3μm、繊維長3.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A8とした。
平均繊維径15.0μm、繊維長2.5mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A9とした。
(実施例1~3、5~13)
スラリー1~3、5~12、14を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表2に示す実施例1~3、5~12、14の不織布基材を作製した。厚みは、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧200kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理を行うことで調整した。
スラリー4を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表2に示す実施例4のセパレータを作製した。厚みは、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧100kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理を行うことで調整した。
スラリー13、16を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表2に示す比較例1~2のセパレータを作製した。厚みは、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧200kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理を行うことで調整した。
スラリー15を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表2に示す比較例2のセパレータを作製した。厚みは、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧100kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理を行うことで調整した。
実施例及び比較例の不織布基材を流れ方向に長辺がくるように50mm巾、200mm長に切り取り、試験片を卓上型材料試験機(商品名:STA-1150、(株)オリエンテック製)を用いて、つかみ間隔100mm、引張速度300mm/分の条件で伸長し、切断時の荷重値を引張強度とした。1試料について5ヶ所以上引張強度を測定し、全測定値の平均値を表3に示した。
実施例及び比較例の不織布基材を100mm×100mmに切り取り、その質量(W1)を計測した後、試験片をプロピレンカーボネートに1分間浸し、1分間干した後の質量(W2)を計測し、保液率を下記(式1)により求めた。
体積平均粒子径0.9μm、BET比表面積5.5m2/gのベーマイト100質量部を、水150質量部に分散したものに、その1質量%水溶液の25℃における粘度が200mPa・sのカルボキシメチルセルロースナトリウム塩2質量%水溶液75質量部を添加・攪拌混合し、ガラス転移点-18℃、体積平均粒子径0.2μmのカルボキシ変性スチレン-ブタジエン共重合樹脂エマルション(固形分濃度50質量%)10質量部を添加・攪拌混合し、最後に調整水を加えて固形分濃度を25質量%に調整し、塗液Aを作製した。
△:塗工時のシワの発生が少ない。
×:塗工時のシワの発生が多い。
<バインダー用PET繊維(平均繊維径1.3μm)>
平均繊維径1.3μmのバインダー繊維は、海島繊維から海成分を溶出することで製造されたフィラメントを、所定の長さに切断することにより製造した。
平均繊維径1.6μmのバインダー繊維は、海島繊維から海成分を溶出することで製造されたフィラメントを、所定の長さに切断することにより製造した。
平均繊維径2.8μmのバインダー繊維は、海島繊維から海成分を溶出することで製造されたフィラメントを、所定の長さに切断することにより製造した。
平均繊維径4.3μmのバインダー繊維は、溶融紡糸法で製造されたフィラメントを、所定の長さに切断することにより製造した。
溶融紡糸法で製造された、平均繊維径2.4μmのフィラメントを、長さ3.0mmに切断した結晶化PETステープル(軟化点250℃)を延伸結晶化PET繊維24として用いた。
海島繊維から海成分を溶出することで製造された平均繊維径1.6μmのフィラメントを、長さ3.0mmに切断した結晶化PETステープル(軟化点250℃)を延伸結晶化PET繊維16として用いた。
溶融紡糸法で製造された、平均繊維径4.3μmのフィラメントを、長さ3.0mmに切断した結晶化PETステープル(軟化点250℃)を延伸結晶化PET繊維43として用いた。
ダブルディスクリファイナーを用いて、カナダ標準ろ水度50mLに叩解したリヨセル(溶剤紡糸セルロース)繊維を用いた。
ダブルディスクリファイナーを用いて、カナダ標準ろ水度250mLに叩解したパラアラミド繊維を用いた。
表4~5に示した繊維原料と含有量に従って、抄紙用スラリーを調製した。これらを、乾燥後の坪量が9.0g/m2となるように傾斜ワイヤー抄紙機を用いて8m/minの速度で抄造し、シリンダードライヤーによって乾燥し、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧100kN/m、加工速度5m/min、1ニップ(nip)の条件で熱カレンダー処理を行って、厚み13μmの不織布基材を得た。
実施例及び比較例の不織布基材を、流れ方向に長辺がくるように、50mm巾、200mm長に切り取り、試験片を卓上型材料試験機(商品名:STA-1150、(株)オリエンテック製)を用いて、つかみ間隔100mm、引張速度300mm/分の条件で伸長し、切断時の荷重値を引張強度とした。結果を表4~5に示す。
塗工時のシワを模擬するため、以下の試験を行った。すなわち、実施例及び比較例の不織布基材を、幅250mmにスリットし、巻き出し速度3m/min、巻き出し張力5Nで送り出し、鉛直上方2mに設けたロールで水平方向に方向転換後、巻き取った。20m巻き取る間のシワの発生程度により、次の3段階に分類した。
△:時々シワが発生するが、横方向の張力を加えると消失する
×:常時シワが発生し、横方向の張力を加えてもすぐに再発する
実施例及び比較例の不織布基材に、平均粒径1.0μmの水酸化マグネシウム100質量部、スチレン-ブタジエンラテックス1.5質量部、カルボキシメチルセルロースナトリウム1.0質量部を含む、不揮発分濃度40質量%の塗液を、乾燥後の塗工量が10g/m2になるように、ロッドコーターを用いて塗工した。このとき、台紙としては黒色の色画用紙を用いた。
前記のセパレータ作製において、台紙として用いた黒画用紙に、不織布基材を抜けて付着した塗液の量に応じて、次の4段階に分類した結果を表4~5に示す。
B 台紙に斑点状に塗液が付着した(付着面積10%未満)。
C 台紙に裏抜けした塗液が付着した(付着面積10%以上30%以下)。
D 台紙に裏抜けした塗液が大量に付着した(付着面積30%超)。
作製した各セパレータを用い、容量30mAhの評価用リチウムイオン二次電池(電極面積:15cm2、正極:マンガン酸リチウム、負極:ハードカーボン、電解液:1M六フッ化リン酸リチウム(LiPF6)の炭酸エチレン(EC)/炭酸ジエチル(DEC)=3/7(容量比)混合溶媒溶液、パウチ型電池)を作製した。この電池の満充電後の端子間電圧E0と、150mAで10秒間放電した直後の端子間電圧E1とより、下記(式2)によって求めた内部抵抗を表4~5に示す。
<バインダー用PET繊維A11>
共重合成分として、3,5-ジカルボメトキシベンゼンスルホン酸とジエチレングリコールを含有する平均繊維径0.5μm、繊維長0.5mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A11とした。
共重合成分として、3,5-ジカルボメトキシベンゼンスルホン酸とジエチレングリコールを含有する平均繊維径1.0μm、繊維長1.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A12とした。
共重合成分として、3,5-ジカルボメトキシベンゼンスルホン酸とジエチレングリコールを含有する平均繊維径2.0μm、繊維長2.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A13とした。
共重合成分として、3,5-ジカルボメトキシベンゼンスルホン酸とジエチレングリコールを含有する平均繊維径4.3μm、繊維長3.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A14とした。
共重合成分として、3,5-ジカルボメトキシベンゼンスルホン酸とジエチレングリコールを含有する平均繊維径10.0μm、繊維長4.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A15とした。
共重合成分として、3,5-ジカルボメトキシベンゼンスルホン酸とジエチレングリコールを含有する平均繊維径14.0μm、繊維長5.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維A16とした。
共重合成分として、ジエチレングリコールを含有する平均繊維径10.5μm、繊維長5.0mmの単一成分型未延伸PET繊維(軟化点120℃、融点230℃)をバインダー用PET繊維a17とした。
共重合成分として、ジエチレングリコールを含有する平均繊維径10.1μm、繊維長5.0mmの芯鞘型熱融着性PET繊維(鞘部溶点:110℃、芯部:250℃)をバインダー用PET繊維a18とした。
(実施例30~44)
スラリー17~31を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表7に示す実施例30~44の不織布基材を作製した。厚みは、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧200kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理を行うことで調整した。
スラリー32を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表7に示す比較例6の不織布基材を作製した。厚みは、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧200kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理を行うことで調整した。
スラリー33を円網・傾斜コンビネーション抄紙機を用いて、18m/minの速度で湿式抄紙し、表7に示す比較例7の不織布基材を作製した。
比較例7の不織布基材を、金属ロール-樹脂ロール(ショア硬度D92)の構成の熱カレンダー装置を使用して、金属ロール温度195℃、線圧200kN/m、加工速度10m/min、1ニップ(nip)の条件で熱カレンダー処理し、表7に示す比較例8の不織布基材を作製した。
実施例及び比較例の不織布基材を流れ方向に長辺がくるように50mm巾、200mm長に切り取り、試験片を卓上型材料試験機(商品名:STA-1150、(株)オリエンテック製)を用いて、つかみ間隔100mm、引張速度300mm/分の条件で伸長し、切断時の荷重値を引張強度とした。1試料について5ヶ所以上引張強度を測定し、全測定値の平均値を求めた。引張強度が、700N/m以上であれば「A」、600N/m以上700N/m未満であれば「B」、600N/m未満であれば「C」で表し、表8に示した。
実施例及び比較例の不織布基材を100mm×100mmに切り取り、その質量(W1)を計測した後、試験片をプロピレンカーボネートに1分間浸し、1分間干した後の質量(W2)を計測し、保液率を下記(式1)により求めた。
体積平均粒子径0.9μm、BET比表面積5.5m2/gのベーマイト100質量部を、水150質量部に分散したものに、その1質量%水溶液の25℃における粘度が200mPa・sのカルボキシメチルセルロースナトリウム塩2質量%水溶液75質量部を添加・攪拌混合し、ガラス転移点-18℃、体積平均粒子径0.2μmのカルボキシ変性スチレン-ブタジエン共重合樹脂エマルション(固形分濃度50質量%)10部を添加・攪拌混合し、最後に調整水を加えて固形分濃度を25質量%に調整し、塗液Aを作製した。実施例及び比較例の不織布基材の樹脂ロール面に、塗工装置としてリバースグラビアコーターを用い、30m/minのライン速度にて、塗液Aを、液としての付着量が47g/m2となるように片面塗工した。塗工された基材は、リバースグラビアコーターに直結されたフローティングエアドライヤーで、90℃の熱風を吹き付けて乾燥させ、セパレータを得た。
前記の各セパレータを用い、正極にマンガン酸リチウム、負極にメソカーボンマイクロビーズ、電解液にヘキサフルオロリン酸リチウム(LiPF6)の1mol/L炭酸ジエチル(DEC)/炭酸エチレン(EC)(容量比7/3)混合溶媒溶液を用いた設計容量30mAhの評価用電池を作製した。
作製した各電池について、60mA定電流充電→4.2V定電圧充電(1時間)→60mAで定電流放電→2.8Vになったら次のサイクル のシーケンスにて、5サイクルの慣らし充放電を行った後、60mA定電流充電→4.2V定電圧充電(1時間)→6mAで30分間定電流放電(放電量3mAh)→放電終了直前の電圧を測定(電圧a)→60mA定電流充電→4.2V定電圧充電(1時間)→90mAで2分間定電流放電(放電量3mAh)→放電終了直前の電圧(電圧b)の測定を行い、内部抵抗を下記(式3)により求めた。結果を表8に記す。
B:内部抵抗4Ω以上5Ω未満
C:内部抵抗5Ω以上
Claims (5)
- ポリエチレンテレフタレート繊維を主体としてなるリチウムイオン二次電池セパレータ用不織布基材において、該不織布基材がバインダー用ポリエチレンテレフタレート繊維と結晶化ポリエチレンテレフタレート繊維を含有し、繊維長が2.5mm以下のバインダー用ポリエチレンテレフタレート繊維を10~60質量%含有することを特徴とするリチウムイオン二次電池セパレータ用不織布基材。
- 平均繊維径が14.0μm以下であり、かつ、繊維長が0.5~2.5mmのバインダー用ポリエチレンテレフタレート繊維を21~60質量%含有する請求項1記載のリチウムイオン二次電池セパレータ用不織布基材。
- 平均繊維径が1.5~2.8μmであり、かつ繊維長が1.0~2.5mmのバインダー用ポリエチレンテレフタレート繊維を10~30質量%含有し、該バインダー用ポリエチレンテレフタレート繊維と結晶化ポリエチレンテレフタレート繊維を合計で80~100質量%含有し、結晶化ポリエチレンテレフタレート繊維の平均繊維径が2.0~4.0μmである請求項1記載のリチウムイオン二次電池セパレータ用不織布基材。
- ポリエチレンテレフタレート繊維を主体としてなるリチウムイオン二次電池セパレータ用不織布基材において、3,5-ジカルボメトキシベンゼンスルホン酸を共重合成分として含有するバインダー用ポリエチレンテレフタレート繊維を含有することを特徴とするリチウムイオン二次電池セパレータ用不織布基材。
- 請求項1~4のいずれかに記載のリチウムイオン二次電池セパレータ用不織布基材に、無機顔料を含む塗液を塗工する処理、有機粒子を含む塗液を塗工してなる処理、樹脂微多孔膜を積層する処理、静電紡糸法により微細繊維層を形成してなる処理、固体電解質やゲル状電解質を塗工する処理から選ばれる少なくとも1つの処理を施してなるリチウムイオン二次電池セパレータ。
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CN201710524282.9A CN107248563B (zh) | 2013-02-05 | 2014-01-28 | 锂离子二次电池分隔件用无纺布基材和锂离子二次电池分隔件 |
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US14/763,967 US9768430B2 (en) | 2013-02-05 | 2014-01-28 | Non-woven fabric base material for lithium ion secondary battery separator and lithium ion secondary battery separator |
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US15/631,267 US10230087B2 (en) | 2013-02-05 | 2017-06-23 | Non-woven fabric base material for lithium ion secondary battery separator and lithium ion secondary battery separator |
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JPWO2019049510A1 (ja) * | 2017-09-11 | 2020-10-15 | 株式会社クラレ | 非水電解質電池セパレータ用塗工液、並びに、それを用いた非水電解質電池用セパレータ及び非水電解質電池 |
US11342578B2 (en) | 2017-05-15 | 2022-05-24 | Lg Energy Solution, Ltd. | Method for manufacturing solid electrolyte membrane for all solid type battery and solid electrolyte membrane manufactured by the method |
JP7323728B1 (ja) * | 2023-01-31 | 2023-08-08 | 大王製紙株式会社 | 湿式不織布を含む電磁波シールド用基材及び電磁波シールド材 |
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