WO2011030807A1 - リチウムイオン二次電池用基材およびリチウムイオン二次電池用セパレータ - Google Patents
リチウムイオン二次電池用基材およびリチウムイオン二次電池用セパレータ Download PDFInfo
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- WO2011030807A1 WO2011030807A1 PCT/JP2010/065460 JP2010065460W WO2011030807A1 WO 2011030807 A1 WO2011030807 A1 WO 2011030807A1 JP 2010065460 W JP2010065460 W JP 2010065460W WO 2011030807 A1 WO2011030807 A1 WO 2011030807A1
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- secondary battery
- lithium ion
- ion secondary
- base material
- pet
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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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- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/443—Particulate material
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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
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a base material for a lithium ion secondary battery that can be suitably used for a lithium ion secondary battery such as a lithium ion secondary battery or a lithium ion polymer secondary battery, and a separator for a lithium ion secondary battery using the base material.
- a lithium ion secondary battery such as a lithium ion secondary battery or a lithium ion polymer secondary battery
- separator for a lithium ion secondary battery using the base material is about.
- a lithium ion secondary battery using an organic electrolyte has attracted attention.
- This lithium ion secondary battery has an energy density of about 3.7 V, which is about three times that of an alkaline secondary battery, which is a conventional secondary battery, and thus has a high energy density.
- a water-based electrolyte cannot be used, a non-aqueous electrolyte having sufficient oxidation-reduction resistance is used.
- non-aqueous electrolytes are flammable, there is a risk of ignition and the like, and careful attention is paid to safety in their use. There are several possible cases of exposure to fire and other hazards, but overcharging is particularly dangerous.
- the current non-aqueous secondary battery has a safety circuit / PTC element equipped and a separator with a thermal fuse function for the purpose of destroying the battery safely when overcharged. Has been made. However, even if equipped with the above-mentioned means, depending on the overcharge conditions, the safety during overcharge is not guaranteed, and in fact, non-aqueous secondary battery ignition accidents Is still happening.
- a film-like porous film made of a polyolefin such as polyethylene is often used.
- a polyolefin such as polyethylene
- shutdown function a thermal fuse function that cuts off the current and shuts off the current
- non-woven fabrics composed of polyester fibers, and non-woven fabrics in which aramid fibers that are heat-resistant fibers are blended with polyester fibers.
- References 1-3 On the other hand, for example, by laminating a nonwoven fabric composed of polyester fibers on a film-like porous film made of polyolefin, and for compounding by inclusion of filler particles in a nonwoven fabric or woven fabric, or by resin surface coating Examples of imparting heat resistance have been reported (see, for example, Patent Documents 4 to 6).
- the non-woven fabric used as the base material has large pores and low surface smoothness, so the surface variation when combined by surface coating is large, and composites such as filler particles and resins There was a quality problem such as being likely to drop off.
- JP 2003-123728 A (no overseas family) JP 2007-317675 A (Pamphlet of International Publication No. 2001/67536, US Patent Application Publication No. 2003/0003363) JP 2006-19191 A (no overseas family) JP 2005-293891 A (no overseas family) JP 2005-536857 A (Pamphlet of International Publication No. 2004/021476, US Patent Application Publication No. 2006/0024569) JP 2007-157723 A (International Publication No. 2006/062153, US Patent Application Publication No. 2007/0264577)
- An object of the present invention is to provide a lithium ion secondary battery base material that is highly safe during overcharge and suitable for composite use, and a lithium ion secondary battery separator using the base material.
- polyester-based ultrashort fibers having an average fiber diameter of 5.0 ⁇ m or less and a fiber length of 2 mm or less are essential components.
- a base material for a lithium ion secondary battery comprising: (2) The base material for a lithium ion secondary battery according to the above (1), wherein the polyester ultrashort fiber has an aspect ratio (fiber length / fiber diameter) of 20 to 800, (3) The base material for a lithium ion secondary battery according to the above (1) or (2), wherein the content of the polyester ultrashort fiber relative to the nonwoven fabric is 1 to 30% by mass, (4) A treatment for impregnating or coating a slurry containing inorganic or organic filler particles on a substrate for a lithium ion secondary battery according to any one of claims 1 to 3, or impregnating a slurry containing a resin.
- a lithium ion secondary battery comprising at least one process selected from a process for coating, a process for laminating and integrating porous films, and a process for impregnating or coating a solid electrolyte or a gel electrolyte Separator, I found.
- the base material (1) for a lithium ion secondary battery of the present invention comprises a polyester-based ultrashort fiber comprising a nonwoven fabric of polyester-based short fibers, having an average fiber diameter of 5.0 ⁇ m or less and a fiber length of 2 mm or less. It is characterized by being contained as an essential component, and is excellent in denseness and uniformity as compared with conventional base materials for lithium ion secondary batteries. As a result, the surface coating causes a small variation in the surface when composited, and it is difficult for the composite to fall off, thereby realizing good quality. Moreover, since it is comprised with the polyester-type short fiber, heat resistance is high and the safety
- the resulting lithium secondary battery substrate (3) is more excellent in denseness and uniformity required as a substrate.
- the separator for lithium ion secondary batteries of the present invention can be provided by using the base materials for lithium ion secondary batteries (1), (2) and (3) of the present invention.
- a base material for a lithium ion secondary battery according to the present invention comprises a polyester-based ultrashort fiber having an average fiber diameter of 5.0 ⁇ m or less and a fiber length of 2 mm or less as an essential component. This is a non-woven fabric of short fibers.
- an average fiber diameter means the arithmetic mean value of the fiber diameter of ten fibers measured by taking a 3000 times magnified photograph with a microscope.
- the base material for a lithium ion secondary battery of the present invention when the average fiber diameter of the polyester-based ultrashort fibers exceeds 5.0 ⁇ m, the number of fibers in the thickness direction is reduced, so the required denseness is ensured. become unable. On the other hand, if the fiber length exceeds 2 mm, the overlap between the fibers increases, and the number of fibers in the whole decreases, so that the required uniformity cannot be ensured.
- a more preferable average fiber diameter of the polyester-based ultrashort fibers is 0.5 to 5.0 ⁇ m, and a more preferable fiber length is 0.05 to 2 mm.
- the polyester ultrashort fiber has an aspect ratio (fiber length / fiber diameter) of preferably 20 to 800, more preferably 80 to 700.
- the content of the polyester ultrashort fiber is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. If it is less than 1% by mass, the denseness and uniformity may not be improved. If it exceeds 30% by mass, the strength required for the substrate may not be exhibited.
- the average fiber diameter of the short fibers other than the polyester-based ultrashort fibers contained in the base material for the lithium ion secondary battery of the present invention is preferably 0.1 to 10.0 ⁇ m.
- the thickness exceeds 10.0 ⁇ m, the number of fibers in the thickness direction decreases, so that the required denseness may not be ensured.
- the thickness is less than 0.1 ⁇ m, it is difficult to stably produce the fibers.
- a more preferable average fiber diameter is 0.5 to 5.0 ⁇ m.
- the basis weight of the base material for a lithium ion secondary battery of the present invention is preferably 6.0 to 30.0 g / m 2 . If it exceeds 30.0 g / m 2 , the base material alone will occupy the majority of the separator, making it difficult to obtain the effect of the composite, and if it is less than 6.0 g / m 2 , it will be difficult to obtain uniformity. This is because large variations tend to occur on the surface after the composite. More preferably, it is 8.0 to 20.0 g / m 2 .
- the basis weight means a basis weight based on a method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
- the polyester-based (extra) short fibers may be heat-bonded (extra) short fibers (binder (extra) short fibers) or non-heat-bonded (extra) short fibers.
- heat-bonded (extreme) short fibers core-sheath type, eccentric type, side-by-side type, sea-island type, orange type, multi-bimetallic type composite fiber, single component type, etc. can be mentioned.
- polyester series examples include polyethylene terephthalate series, polybutylene terephthalate series, polytrimethylene terephthalate series, polyethylene naphthalate series, polybutylene naphthalate series, and polyethylene isophthalate series. These may be used alone or in combination of two or more. Among these, when using for the base material for lithium ion secondary batteries, the polyethylene terephthalate type
- the composite of the base material for lithium ion secondary battery of the present invention is not particularly limited, but a slurry containing inorganic or organic filler particles is added to the base material for lithium ion secondary battery of the present invention.
- a slurry containing inorganic or organic filler particles is added to the base material for lithium ion secondary battery of the present invention.
- Examples of the impregnation or coating treatment the treatment of impregnating or applying a resin-containing slurry, the treatment of laminating and integrating a porous film, the treatment of impregnating or applying a solid electrolyte or a gel electrolyte, and the like.
- the base material for a lithium ion secondary battery of the present invention as a method for producing a nonwoven fabric, a method of forming a fiber web and bonding, fusing, and entanglement of fibers in the fiber web can be used.
- 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 and an air array method, a wet method such as a papermaking method, a spunbond method, and a melt blow method.
- the web obtained by a wet method is homogeneous and dense, and can be suitably used as a base material for a lithium ion secondary battery.
- the wet method is a method of obtaining a fiber web by dispersing fibers in water to form a uniform papermaking slurry, and using this papermaking slurry with a papermaking machine having at least one of a wire such as a circular net, a long net, and an inclined type. 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 heat-bonded (extreme) short fiber By performing a binder bonding method.
- a uniform nonwoven fabric is formed from a uniform web by the binder bonding method. It is preferable to adjust the thickness or make the thickness uniform by applying pressure to the wet nonwoven fabric produced in this way with a calendar or the like.
- the fiber length of fibers other than polyester-based ultrashort fibers is preferably more than 2 mm and not more than 7 mm, more preferably 3 to 5 mm. preferable. If the fiber length exceeds 7 mm, the wet method may make it difficult to disperse the fibers due to the balance with the average fiber diameter, resulting in problems such as poor formation and the formation of a good fiber web. Sometimes.
- fibers other than the polyester-based ultrashort fibers can be entangled with the polyester-based ultrashort fibers to improve the strength of the substrate, when the fiber length in the fibers other than the polyester-based ultrashort fibers is 2 mm or less, The strength required for the base material may not be exhibited.
- the strength required for the base material is a strength that can withstand a short circuit when the separator is finished and wound on a battery, and the puncture strength can be an index.
- the puncture strength is preferably 30 g or more. More preferably, it is 50 g or more.
- Example 1 40 parts of oriented and crystallized polyethylene terephthalate (PET) short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), and fiber length 10 parts of orientation-crystallized PET ultrashort fibers with an aspect ratio of 329 mm and 50 parts of PET short fibers for binder with a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm
- PET polyethylene terephthalate
- This papermaking slurry is made up by a wet method using a circular paper machine, and the PET short fibers for binder are bonded by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.2 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.2 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 2 49 parts of PET crystal short fibers oriented and crystallized with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), a fiber length of 1 mm, and an aspect ratio 1 part of 329 oriented crystallized PET short fibers and 50 parts of PET short fibers for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm are mixed together,
- the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- the papermaking slurry is made up by a wet method using a circular paper machine, and a PET-based short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.6 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.6 g / m 2 and a thickness of 18 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 3 49.3 parts of PET-based short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), a fiber length of 1 mm, Together 0.7 parts of oriented crystallized PET short fibers with an aspect ratio of 329 and 50 parts of PET short fibers for binder with a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm Were mixed in a pulper under water and stirred with an agitator to prepare a uniform papermaking slurry (1% concentration).
- This papermaking slurry is made up by a wet method using a circular paper machine, and a PET-based short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.5 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.5 g / m 2 and a thickness of 18 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 4 20 parts of oriented and crystallized PET short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), a fiber length of 1 mm, and an aspect ratio 30 parts of 329 oriented crystallized PET ultrashort fibers and 50 parts of PET short fibers for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm are mixed together,
- the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- the papermaking slurry is made up by a wet method using a circular paper machine, and the PET short fibers for binder are bonded to each other with a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 9.8 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.8 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 5 17 parts of orientation-crystallized PET short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), a fiber length of 1 mm, and an aspect ratio 33 parts of 329 oriented crystallized PET ultrashort fibers and 50 parts of PET short fibers for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm are mixed together,
- the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- the papermaking slurry is made up by a wet method using a circular paper machine, and the PET short fibers for the binder are adhered by a cylinder dryer at 120 ° C. to develop the nonwoven fabric strength.
- the basis weight is 9.6 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.6 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 6 40 parts of orientation-crystallized PET short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), a fiber length of 2 mm, and an aspect ratio 10 parts of 658 orientation-crystallized PET ultrashort fibers and 50 parts of a PET short fiber for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm are mixed together,
- the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- This papermaking slurry is made up by a wet method using a circular paper machine, and the PET short fibers for binder are bonded by a cylinder dryer at 120 ° C. to develop the nonwoven fabric strength.
- the basis weight is 10.0 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- calendar treatment was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.0 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 7 40 parts of PET-based short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), a fiber length of 0.6 mm, 10 parts of oriented and crystallized PET short fibers with an aspect ratio of 197 were mixed together with 50 parts of PET short fibers for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm. Then, the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- a uniform papermaking slurry 1% concentration
- This papermaking slurry is made up by a wet method using a circular paper machine, and a PET short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength, and the basis weight is 9.9 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- calendering was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.9 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 8 40 parts of oriented PET crystal short fibers with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, and oriented crystals with a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m) and a fiber length of 3 mm 10 parts of a PET short fiber, 20 parts of a PET ultrashort fiber for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m), a fiber length of 1 mm, and an aspect ratio of 232, and a fineness of 0.2 dtex ( 30 parts of a PET short fiber for binder having an average fiber diameter of 4.3 ⁇ m and a fiber length of 3 mm is mixed together, disaggregated in pulper water, and stirred uniformly with an agitator to make a uniform papermaking slurry (1% Concentration) was prepared.
- This slurry for paper making is made up using a wet method using a circular paper machine, and a non-woven fabric strength is expressed by bonding a PET ultrashort fiber for a binder and a PET short fiber for a binder by a cylinder dryer at 120 ° C.
- a nonwoven fabric having a basis weight of 10.1 g / m 2 and a width of 50 cm was produced.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.1 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 9 10 parts of PET ultrashort fibers oriented and crystallized with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), a fiber length of 1 mm, and an aspect ratio of 424, and a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and fibers 30 parts of oriented PET crystal short fibers having a length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), 10 parts of oriented PET crystal short fibers having a fiber length of 3 mm, and a fineness of 0 .20 dtex (average fiber diameter: 4.3 ⁇ m), fiber length: 1 mm, aspect ratio of 232 PET ultrashort fibers for binders, fineness: 0.2 dtex (average fiber diameter: 4.3 ⁇ m), fiber length: 3 mm 30 parts of PET short fibers were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an
- This slurry for paper making is made up using a wet method using a circular paper machine, and a non-woven fabric strength is expressed by bonding a PET ultrashort fiber for a binder and a PET short fiber for a binder by a cylinder dryer at 120 ° C.
- a nonwoven fabric having a basis weight of 10.3 g / m 2 and a width of 50 cm was produced.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.3 g / m 2 and a thickness of 18 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 10 10 parts of PET ultrashort fibers oriented and crystallized with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), a fiber length of 1 mm, and an aspect ratio of 424, and a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and fibers 30 parts of oriented PET crystal short fibers having a length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), 10 parts of oriented PET crystal short fibers having a fiber length of 3 mm, and a fineness of 0 .2 dtex (average fiber diameter 4.3 ⁇ m), fiber length 0.1 mm, 20 parts of PET ultrashort fiber for binder with an aspect ratio of 23, fineness 0.2 dtex (average fiber diameter 4.3 ⁇ m), fiber length 3 mm 30 parts of PET short fibers for binder were mixed together, disaggregated in water of a pulper, and a uniform papermaking slurry (1% concentration) was prepared under stirring
- This slurry for paper making is made up using a wet method using a circular paper machine, and a non-woven fabric strength is expressed by bonding a PET ultrashort fiber for a binder and a PET short fiber for a binder by a cylinder dryer at 120 ° C.
- a nonwoven fabric having a basis weight of 9.8 g / m 2 and a width of 50 cm was produced.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.8 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- This slurry for paper making is made up using a wet method using a circular paper machine, and a non-woven fabric strength is expressed by bonding a PET ultrashort fiber for a binder and a PET short fiber for a binder by a cylinder dryer at 120 ° C.
- a nonwoven fabric having a basis weight of 9.3 g / m 2 and a width of 50 cm was produced.
- calendar treatment was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.3 g / m 2 and a thickness of 16 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 12 20 parts of oriented and crystallized PET short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), fiber length of 0.6 mm, and aspect ratio of 254, and a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m) Mixing together 20 parts of oriented PET crystal short fibers with a fiber length of 3 mm and 60 parts of PET short fibers for binder with a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm. Then, the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- a uniform papermaking slurry 1% concentration
- This papermaking slurry is made up by a wet method using a circular paper machine, and the PET-based short fibers for binder are bonded to each other by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.1 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.1 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 13 20 parts PET oriented ultrashort fibers with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), fiber length of 2 mm and aspect ratio of 849, fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m), fiber 20 parts of PET short fibers having an orientation crystallized length of 3 mm and 60 parts of PET short fibers for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm are mixed together.
- the pulper was disaggregated in water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- This papermaking slurry is made up by a wet method using a circular paper machine, and a PET-based short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.4 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- calendering was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.4 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 14 20 parts PET oriented ultrashort fibers with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), fiber length of 1 mm and aspect ratio of 424, fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), fiber 20 parts of PET crystal short fibers having an orientation crystallized length of 3 mm, a fineness of 0.3 dtex (average fiber diameter 5.3 ⁇ m), 10 parts of PET crystal short fibers having an orientation crystallization of 3 mm fiber length, and a fineness of 0 .2 dtex (average fiber diameter 4.3 ⁇ m), fiber length 3 mm PET short fiber for binder is mixed with 50 parts together, disaggregated in pulper water, and uniform slurry for paper making under stirring by agitator (1% concentration) was prepared.
- This papermaking slurry is made up by a wet method using a circular paper machine, and a PET short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength, and the basis weight is 9.9 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- calendering was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.9 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 15 10 parts of PET crystal ultrashort fibers having a fineness of 0.004 dtex (average fiber diameter of 0.70 ⁇ m), a fiber length of 0.5 mm, and an aspect ratio of 714, a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), 20 parts of oriented short crystallized PET fibers with a fiber length of 3 mm, fineness of 0.1 dtex (average fiber diameter 3.0 ⁇ m), 20 parts of oriented short crystallized PET fibers with a fiber length of 3 mm, fineness 50 parts PET binder short fiber for binder of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and fiber length 3 mm are mixed together, disaggregated in pulper water, and evenly made under agitator stirring.
- a fineness of 0.06 dtex average fiber diameter of 2.4 ⁇ m
- 20 parts of oriented short crystallized PET fibers with a fiber length of 3 mm fineness of 0.1 dtex (average fiber diameter 3.0 ⁇ m)
- a slurry (1% concentration) was prepared. This papermaking slurry is made up by a wet method using a circular paper machine, and a PET-based short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 9.7 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- calendering was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.7 g / m 2 and a thickness of 16 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Example 16 10 parts of oriented and crystallized PET short fibers having a fineness of 0.004 dtex (average fiber diameter of 0.70 ⁇ m) and a fiber length of 3 mm, fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m), fiber length of 1 mm, aspect ratio of 424 20 parts of orientation-crystallized PET ultrashort fibers, 20 parts of orientation-crystallized PET staple fibers having a fineness of 0.1 dtex (average fiber diameter of 3.0 ⁇ m) and a fiber length of 3 mm, and a fineness of 0.
- a uniform papermaking slurry 50 parts of 2 dtex (average fiber diameter 4.3 ⁇ m) and 3 mm fiber length PET-based short fibers for binder are mixed together, disaggregated in pulper water, and stirred uniformly with an agitator to form a uniform papermaking slurry ( 1% concentration) was prepared.
- the papermaking slurry is made up by a wet method using a circular paper machine, and the PET short fibers for binder are bonded to each other with a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 9.8 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 9.8 g / m 2 and a thickness of 16 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Comparative Example 1 50 parts of oriented and crystallized PET short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and a fiber length of 3 mm, and for binders having a fineness of 0.2 dtex (average fiber diameter of 4.3 ⁇ m) and a fiber length of 3 mm 50 parts of PET short fibers were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- This papermaking slurry is made up by a wet method using a circular paper machine, and the PET short fibers for binder are bonded by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.2 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.2 g / m 2 and a thickness of 17 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- Comparative Example 2 40 parts of oriented PET crystal short fibers with a fineness of 0.06 dtex (average fiber diameter of 2.4 ⁇ m) and fiber length of 3 mm, and an oriented crystal with a fineness of 0.3 dtex (average fiber diameter of 5.3 ⁇ m) and a fiber length of 2 mm 10 parts of the PET ultrashort fibers, 50 parts of the PET short fibers for binder having a fineness of 0.2 dtex (average fiber diameter 4.3 ⁇ m) and a fiber length of 3 mm are mixed together in the water of the pulper.
- the slurry was disaggregated and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
- This papermaking slurry is made up by a wet method using a circular paper machine, and a PET-based short fiber for a binder is adhered by a cylinder dryer at 120 ° C. to develop a nonwoven fabric strength.
- the basis weight is 10.5 g / m 2.
- a non-woven fabric having a width of 50 cm was prepared.
- a calendar process was performed at a roll temperature of 180 ° C. to produce a nonwoven fabric having a basis weight of 10.5 g / m 2 and a thickness of 19 ⁇ m, which was used as a base material for a lithium ion secondary battery.
- the nonwoven fabrics of Examples 1 to 16 and Comparative Examples 1 and 2 were passed, respectively, and after applying the slurry by pulling application, passed through a gap having a predetermined interval, and then dried, A separator having a porous film with a thickness of 3 ⁇ m was obtained.
- thickness means the value measured by the method prescribed
- the puncture strength was measured at five or more locations for one sample, and the smallest puncture strength among all the measured values was indicated as ⁇ if it was 50 g or more, ⁇ if it was 30 g or more and less than 50 g, and ⁇ if it was less than 30 g.
- the base material for a lithium ion secondary battery obtained in the examples is composed of a nonwoven fabric of PET short fibers, an average fiber diameter is 5 ⁇ m or less, and a PET ultrashort fiber having a fiber length of 2 mm or less is an essential component. It was characterized by containing, and it was excellent in denseness and uniformity compared with the conventional base material for lithium ion secondary batteries. Thereby, the favorable result that the variation of the surface at the time of compounding by surface coating was small was obtained. Further, since it is composed of PET fibers, almost no thermal shrinkage was observed at 150 ° C., and no substantial deformation occurred at the visual level. Therefore, heat resistance is high and safety at the time of overcharge is high.
- Example 3 in which the content of the system ultrashort fibers was less than 1% by mass, the variation in the surface when composited by surface coating was slightly large.
- Example 14 containing fibers having an average fiber diameter exceeding 5 ⁇ m as fibers other than polyester-based ultrashort fibers, there is a tendency that variations in the surface when combined by surface coating are increased. It was seen.
- the base material for a lithium ion secondary battery obtained in Comparative Example 1 has the PET short fibers used having an average fiber diameter of 2.4 ⁇ m, a fiber length of 3 mm, and an average fiber diameter of 5.0 ⁇ m. Since it does not contain a PET ultrashort fiber having a fiber length of 2 mm or less, the uniformity required for the base material for a lithium ion secondary battery does not satisfy a sufficient requirement. As a result, the surface was uneven when it was combined by surface coating.
- the base material for a lithium ion secondary battery obtained in Comparative Example 2 has an average fiber diameter of 5.3 ⁇ m of a PET ultrashort fiber having a fiber length of 2 mm or less, and exceeds 5.0 ⁇ m. It is dense and does not meet sufficient requirements. As a result, the surface was uneven when it was combined by surface coating.
- Comparative Example 3 corresponding to a conventional separator, the thermal shrinkage rate is large, and when this is used for a battery, the separator contracts during abnormal overcharging when the internal temperature reaches 150 ° C., and the positive electrode and the negative electrode are in contact with each other. May cause a short circuit due to safety problems.
- the base material for a lithium ion secondary battery of the present invention can be suitably used for a separator for a lithium ion secondary battery such as a lithium ion secondary battery or a lithium ion polymer secondary battery.
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Abstract
Description
(1)ポリエステル系短繊維の不織布からなるリチウムイオン二次電池用基材において、平均繊維径が5.0μm以下であり、かつ、繊維長が2mm以下であるポリエステル系極短繊維を必須成分として含有することを特徴とするリチウムイオン二次電池用基材、
(2)ポリエステル系極短繊維のアスペクト比(繊維長/繊維径)が20~800である上記(1)記載のリチウムイオン二次電池用基材、
(3)不織布に対するポリエステル系極短繊維の含有量が1~30質量%である上記(1)または(2)記載のリチウムイオン二次電池用基材、
(4)請求項1~3のいずれかに記載のリチウムイオン二次電池用基材に、無機又は有機のフィラー粒子を含有するスラリーを含浸又は塗工する処理、樹脂を含有するスラリーを含浸又は塗工する処理、多孔質フィルムを積層一体化する処理、固体電解質やゲル状電解質を含浸又は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ことを特徴とするリチウムイオン二次電池用セパレータ、
を見出した。
本発明のリチウムイオン二次電池用基材(1)、(2)及び(3)を用いることにより本発明のリチウムイオン二次電池用セパレータを提供することができる。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたポリエチレンテレフタレート(PET)系短繊維を40部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長1mm、アスペクト比329の配向結晶化させたPET系極短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.2g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.2g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を49部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長1mm、アスペクト比329の配向結晶化させたPET系極短繊維を1部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.6g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.6g/m2、厚さ18μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を49.3部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長1mm、アスペクト比329の配向結晶化させたPET系極短繊維を0.7部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.5g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.5g/m2、厚さ18μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長1mm、アスペクト比329の配向結晶化させたPET系極短繊維を30部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.8g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.8g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を17部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長1mm、アスペクト比329の配向結晶化させたPET系極短繊維を33部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.6g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.6g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を40部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長2mm、アスペクト比658の配向結晶化させたPET系極短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.0g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.0g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を40部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長0.6mm、アスペクト比197の配向結晶化させたPET系極短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.9g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.9g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を40部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長1mm、アスペクト比232のバインダー用PET系極短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を30部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系極短繊維とバインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.1g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.1g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長1mm、アスペクト比424の配向結晶化させたPET系極短繊維を10部と、繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を30部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長1mm、アスペクト比232のバインダー用PET系極短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を30部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系極短繊維とバインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.3g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.3g/m2、厚さ18μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長1mm、アスペクト比424の配向結晶化させたPET系極短繊維を10部と、繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を30部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長0.1mm、アスペクト比23のバインダー用PET系極短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を30部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系極短繊維とバインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.8g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.8g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長1mm、アスペクト比424の配向結晶化させたPET系極短繊維を10部と、繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を30部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長0.05mm、アスペクト比11のバインダー用PET系極短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を30部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系極短繊維とバインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.3g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.3g/m2、厚さ16μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長0.6mm、アスペクト比254の配向結晶化させたPET系極短繊維を20部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を60部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.1g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.1g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長2mm、アスペクト比849の配向結晶化させたPET系極短繊維を20部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を60部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.4g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.4g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長1mm、アスペクト比424の配向結晶化させたPET系極短繊維を20部と、繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.3dtex(平均繊維径5.3μm)、繊維長3mmの配向結晶化させたPET系短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.9g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.9g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.004dtex(平均繊維径0.70μm)、繊維長0.5mm、アスペクト比714の配向結晶化させたPET系極短繊維を10部、繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.7g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.7g/m2、厚さ16μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.004dtex(平均繊維径0.70μm)、繊維長3mmの配向結晶化させたPET系短繊維を10部、繊度0.06dtex(平均繊維径2.4μm)、繊維長1mm、アスペクト比424の配向結晶化させたPET系極短繊維を20部と、繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化させたPET系短繊維を20部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量9.8g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量9.8g/m2、厚さ16μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を50部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.2g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.2g/m2、厚さ17μmの不織布を製造し、リチウムイオン二次電池用基材とした。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化させたPET系短繊維を40部と、繊度0.3dtex(平均繊維径5.3μm)、繊維長2mmの配向結晶化させたPET系極短繊維を10部と、繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmのバインダー用PET系短繊維を50部とを一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な抄造用スラリー(1%濃度)を調製した。この抄造用スラリーを円網抄紙機による湿式法を用いて抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、坪量10.5g/m2、幅50cmの不織布を作製した。次に、ロール温度180℃でカレンダー処理を行い、坪量10.5g/m2、厚さ19μmの不織布を製造し、リチウムイオン二次電池用基材とした。
実施例及び比較例で得られたリチウムイオン二次電池用基材について、下記の評価を行い、結果を表1に示した。
実施例1~16及び比較例1~2の基材並びに比較例3として従来公知のセパレータである20μmの厚さのポリエチレン(PE)製微多孔膜を、150℃の恒温槽内に30分間放置し、各基材の収縮率を測定して加熱特性を評価した。収縮率の測定は次のようにして行った。5cm×5cmに切り出した基材片を、クリップで固定した2枚のガラス板で挟みこみ、150℃の恒温槽内に30分放置した後に取り出し、各基材片の長さを測定し、試験前の長さと比較して長さの減少割合を収縮率とした。
板状ベーマイト(平均粒径:1μm、アスペクト比:10)1000g、水800g、イソプロピルアルコール200g、ポリビニルブチラール375gを容器に入れ、撹拌機(商品名:スリーワンモーター、新東化学社製)で1時間撹拌して分散させ、均一なスラリーとした。このスラリー中に、実施例1~16及び比較例1~2の不織布をそれぞれ通し、引き上げ塗布によりスラリーを塗布した後、所定の間隔を有するギャップの間を通し、その後乾燥して、片面あたりの厚さが3μmの多孔膜を有するセパレータを得た。
作製したセパレータについて、任意の10ヶ所の厚さ測定を実施し、その差が1μm以下であれば○、1μmを超えて2μm以下であれば△、2μmを超えていれば×で表した。なお、厚さはJIS B 7502に規定された方法により測定した値、つまり、5N荷重時の外側マイクロメーターにより測定された値を意味する。
実施例1~16及び比較例1~2の基材を、50mm幅の短冊状に切り揃えた。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)に据え付けた40mmφの固定枠に装着し、先端に丸み(曲率1.6)をつけた直径1.0mmの金属針((株)オリエンテック製)を試料面に対して直角に50mm/分の一定速度で貫通するまで降ろした。このときの最大荷重(g)を計測し、これを突刺強度とした。1試料について5ヶ所以上突刺強度を測定し、全測定値の中で最も小さい突刺強度について、50g以上であれば○、30g以上50g未満であれば△、30g未満であれば×で表した。
Claims (4)
- ポリエステル系短繊維の不織布からなるリチウムイオン二次電池用基材において、平均繊維径が5.0μm以下であり、かつ、繊維長が2mm以下であるポリエステル系極短繊維を必須成分として含有することを特徴とするリチウムイオン二次電池用基材。
- ポリエステル系極短繊維のアスペクト比(繊維長/繊維径)が20~800である請求項1記載のリチウムイオン二次電池用基材。
- 不織布に対するポリエステル系極短繊維の含有量が1~30質量%である請求項1または2記載のリチウムイオン二次電池用基材。
- 請求項1~3のいずれかに記載のリチウムイオン二次電池用基材に、無機又は有機のフィラー粒子を含有するスラリーを含浸又は塗工する処理、樹脂を含有するスラリーを含浸又は塗工する処理、多孔質フィルムを積層一体化する処理、固体電解質やゲル状電解質を含浸又は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ことを特徴とするリチウムイオン二次電池用セパレータ。
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JPH11126595A (ja) * | 1997-10-21 | 1999-05-11 | Nippon Glass Fiber Co Ltd | アルカリ電池セパレータおよびその製造方法 |
JP2000030687A (ja) * | 1998-07-08 | 2000-01-28 | Mitsubishi Paper Mills Ltd | 非水電解液電池用セパレーター |
JP2002124239A (ja) * | 2000-08-10 | 2002-04-26 | Japan Vilene Co Ltd | 電池用セパレータ |
JP2003142065A (ja) * | 2001-08-15 | 2003-05-16 | Mitsubishi Paper Mills Ltd | 電気化学素子用セパレーターおよびその製造方法 |
JP2003157897A (ja) * | 2001-11-22 | 2003-05-30 | Japan Vilene Co Ltd | 固体電解質用支持体 |
JP2005190778A (ja) * | 2003-12-25 | 2005-07-14 | Japan Vilene Co Ltd | 電池用セパレータ及びこれを用いた電池 |
JP2009230975A (ja) * | 2008-03-21 | 2009-10-08 | Mitsubishi Paper Mills Ltd | リチウムイオン二次電池用基材 |
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WO2013093229A1 (fr) | 2011-12-22 | 2013-06-27 | IFP Energies Nouvelles | Catalyseur utilisable en hydroconversion comprenant au moins une zéolithe et des metaux des groupes viii et vib et preparation du catalyseur |
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KR101606157B1 (ko) | 2016-03-24 |
KR20120068811A (ko) | 2012-06-27 |
CN102498591A (zh) | 2012-06-13 |
CN102498591B (zh) | 2015-05-20 |
JP5265636B2 (ja) | 2013-08-14 |
JP2011082148A (ja) | 2011-04-21 |
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