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WO2012128471A2 - Séparateur, procédé pour fabriquer un séparateur, et appareil pour fabriquer un séparateur - Google Patents

Séparateur, procédé pour fabriquer un séparateur, et appareil pour fabriquer un séparateur Download PDF

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Publication number
WO2012128471A2
WO2012128471A2 PCT/KR2012/000849 KR2012000849W WO2012128471A2 WO 2012128471 A2 WO2012128471 A2 WO 2012128471A2 KR 2012000849 W KR2012000849 W KR 2012000849W WO 2012128471 A2 WO2012128471 A2 WO 2012128471A2
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WO
WIPO (PCT)
Prior art keywords
separator
cellulose fiber
fiber layer
manufacturing apparatus
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2012/000849
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English (en)
Korean (ko)
Other versions
WO2012128471A3 (fr
Inventor
김익수
김병석
와타나베케이
기무라나오타카
김규오
이재환
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shinshu University NUC
Toptec Co Ltd
Original Assignee
Shinshu University NUC
Toptec Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2011061736A external-priority patent/JP5860603B2/ja
Application filed by Shinshu University NUC, Toptec Co Ltd filed Critical Shinshu University NUC
Publication of WO2012128471A2 publication Critical patent/WO2012128471A2/fr
Publication of WO2012128471A3 publication Critical patent/WO2012128471A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator, a separator manufacturing method, and a separator manufacturing apparatus.
  • the separator using the paper which fixed the cellulose fiber is known (for example, refer patent document 1). Since the separator described in patent document 1 uses the paper which beat
  • the present invention has been made to solve the above problems, and an object thereof is to provide a separator having high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity. Moreover, it aims at providing the manufacturing method and manufacturing apparatus of the separator which can manufacture such a separator.
  • the separator of the present invention includes at least one cellulose fiber layer and at least one nanofiber layer.
  • the fiber since the fiber is provided with a nanofiber layer having thin, fine voids and uniform characteristics, it has high insulation and high dendrite resistance.
  • the nanofiber layer since the nanofiber layer also has a large porosity, it has high electrolyte solution retention characteristics and high ion conductivity.
  • the separator of this invention since it is provided with a cellulose fiber layer, it has high mechanical strength.
  • the separator of the present invention becomes a separator having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity.
  • the cellulose fiber layer preferably has a thickness of 1 ⁇ m to 40 ⁇ m and an average fiber diameter of 0.1 ⁇ m to 10 ⁇ m.
  • the separator of the present invention since the thickness of the cellulose fiber layer is 40 ⁇ m or less, a thin separator can be manufactured, and a secondary battery or a capacitor having a large capacitance can be manufactured. Moreover, since the thickness of a cellulose fiber layer is 1 micrometer or more, mechanical strength does not fall.
  • the separator of the present invention since the cellulose fiber layer is made of cellulose fibers having an average fiber diameter of 0.1 ⁇ m or more, it is easy to maintain the strength of the cellulose fiber itself, and can form a cellulose fiber layer having sufficient mechanical strength without being too thick. have. On the other hand, since the cellulose fiber layer is made of cellulose fibers having an average fiber diameter of 10 ⁇ m or less, it is possible to manufacture a thin separator and to manufacture a non-aqueous battery having a large electric capacity.
  • the cellulose fiber layer is preferably made of cellulose fibers having an average fiber diameter of 2.0 mm or more.
  • the nanofiber layer has a porosity. ) Is in the range of 20% to 80%, and the average pore size is preferably in the range of 0.02 ⁇ m to 2 ⁇ m.
  • the porosity of a nanofiber layer exists in the range of 20%-80%, it has high electrolyte solution holding characteristic and it becomes possible to obtain high ion conductivity. Moreover, since the average pore size exists in the range of 0.02 micrometer-2 micrometers, and a dendrite does not easily invade a separator, it has high dendrite tolerance.
  • the separator of the present invention preferably has a structure in which the nanofiber layer is provided on both surfaces of the cellulose fiber layer.
  • the separator of the present invention preferably has a structure in which the cellulose fiber layer is provided on both surfaces of the nanofiber layer.
  • the method for producing a separator according to the present invention is a method for producing a separator for producing the separator according to the present invention, the process for preparing a long sheet made of the cellulose fiber layer and the nanosheet on one side of the long sheet being conveyed. It is characterized by including a step of forming a fiber layer.
  • the manufacturing method of the separator of this invention it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.
  • a cellulose fiber layer in which the nanofiber layer was formed can be commercialized as it is. For this reason, the process of isolate
  • the method further includes a step of forming the nanofiber layer on the other side of the long sheet being conveyed.
  • the method for producing a separator according to the present invention is a method for producing a separator for producing the separator according to the present invention, in which a separator is produced by sequentially forming the nanofiber layer and the cellulose fiber layer on one side of a long sheet being conveyed. It is preferable.
  • a separator having a structure in which a nanofiber layer is provided on one side of the cellulose fiber layer a separator having a structure in which the nanofiber layer is provided on both sides of the cellulose fiber layer, and a cellulose fiber layer on both sides of the nanofiber layer It becomes possible to manufacture any separator of the separator of the installed structure.
  • the separator manufacturing apparatus of the present invention is a separator manufacturing apparatus for producing the separator of the present invention, and the nano-to-long sheet conveyed by the conveying apparatus for conveying the long sheet composed of the cellulose fiber layer and the conveying apparatus is nano. It is characterized by including the field emission device for forming a fiber layer.
  • the separator manufacturing apparatus of this invention it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.
  • a cellulose fiber layer in which the nanofiber layer was formed can be used as a product as it is. For this reason, the process of isolate
  • the separator manufacturing apparatus of the present invention is a separator manufacturing apparatus for manufacturing the separator of the present invention, and includes a conveying apparatus for conveying a long sheet and an electric field for forming a nanofiber layer in the long sheet being conveyed by the conveying apparatus.
  • a cellulose fiber layer manufacturing apparatus which forms a cellulose fiber layer in the said elongate sheet
  • the separator having a structure in which a nanofiber layer is provided on one side of the cellulose fiber layer, the separator having a structure in which the nanofiber layer is provided on both sides of the cellulose fiber layer, and both sides of the nanofiber layer. It is possible to manufacture any of the separators having a structure in which a cellulose fiber layer is provided.
  • the cellulose fiber layer production apparatus is preferably a melt blow spinning device.
  • the cellulose fiber layer production apparatus is preferably an electric field emission device.
  • the present invention provides a separator having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity, and also provides a method and apparatus for manufacturing a separator capable of manufacturing such a separator.
  • FIG. 1 is a cross-sectional view of the separator 100 according to the first embodiment.
  • FIG. 2 is a cross-sectional view of the separator manufacturing apparatus 1 according to the first embodiment.
  • FIG 3 is a diagram showing that the separator 100 is manufactured by the method for manufacturing a separator according to the first embodiment.
  • FIG. 4 is a cross-sectional view of the separator manufacturing apparatus 2 according to the second embodiment.
  • FIG 5 is a cross-sectional view of the separator 102 according to the third embodiment.
  • FIG. 6 is a cross-sectional view of the separator manufacturing apparatus 3 according to the third embodiment.
  • FIG. 7 is a diagram showing that the separator 102 is manufactured by the method for manufacturing a separator according to the third embodiment.
  • FIG. 8 is a cross-sectional view of the separator manufacturing apparatus 4 according to the fourth embodiment.
  • FIG 9 is a cross-sectional view of the separator manufacturing apparatus 5 according to the fifth embodiment.
  • FIG. 1 is a cross-sectional view of the separator 100 according to the first embodiment.
  • the separator 100 includes one cellulose fiber layer 110 and two nanofiber layers 120 and 130, and a nanofiber layer (on both sides of the cellulose fiber layer 110). 120 and 130 are provided.
  • the cellulose fiber layer 110 is made of cellulose fibers having a thickness of 1 ⁇ m to 40 ⁇ m and an average fiber diameter of 0.1 ⁇ m to 10 ⁇ m.
  • the nanofiber layers 120 and 130 have a porosity in the range of 20% to 80%, and an average pore size in the range of 0.02 m to 2 m.
  • the separator 100 is obtained by the manufacturing method of the separator which concerns on Embodiment 1 using the separator manufacturing apparatus 1 which concerns on Embodiment 1 mentioned later.
  • FIG. 3 is a diagram showing that the separator 100 is manufactured by the method for manufacturing a separator according to the first embodiment.
  • 3 (a) to 3 (c) are respective process diagrams.
  • the separator manufacturing apparatus 1 which concerns on Embodiment 1 is conveyed by the conveying apparatus 10 and the conveying apparatus 10 which convey the long sheet which consists of the elongate cellulose fiber layer 110, as shown in FIG.
  • the field emission device 20a which forms the nanofiber layer 120 (refer to FIG. 3 (b)) on one side of the thin cellulose fiber layer 110, and the nanofiber layer 130 (FIG. 3 (c) on the other side).
  • Field emission device 20b The field radiating device 20a and the field radiating device 20b are both top direction field radiating devices provided with top direction nozzles.
  • the conveying apparatus 10 is comprised so that the cellulose fiber layer 110 used as a base material layer may be conveyed from the field radiating apparatus 20a toward the field radiating apparatus 20b.
  • the conveying apparatus 10 moves the cellulose fiber layer 110 in the first direction (the A1 direction in FIG. 2) when the field radiating device 20a forms the nanofiber layer 120 (see FIG. 3B).
  • the cellulosic fiber layer 110 from the height position of the field radiating device 20a to the height position of the field radiating device 20b in the second direction (A2 direction) substantially perpendicular to the first direction,
  • the cellulose fiber layer 110 is conveyed in the third direction (A3 direction) opposite to the first direction.
  • the conveying apparatus 10 includes an feeding roller 11 for feeding the cellulose fiber layer 110, a winding roller 12 for winding the cellulose fiber layer 110, and a tension roller 13 for adjusting the pulling of the cellulose fiber layer 110. 18, the plurality of drive rollers 14 for conveying the cellulose fiber layer 110, the first reverse roller 16a for directing the conveyance direction of the cellulose fiber layer 110 from the field radiating device 20a, and And a second reverse roller 16b for directing the conveyance direction of the cellulose fiber layer 110 from the first reverse roller 16a toward the field radiating device 20b.
  • the feed roller 11, the winding roller 12, the tension rollers 13 and 18, and the some drive roller 14 comprise the conveyance mechanism (not shown) which conveys the cellulose fiber layer 110. do.
  • the plurality of drive rollers 14 are drive devices for transporting the cellulose fiber layer 110.
  • the first reversing roller 16a and the second reversing roller 16b are formed such that the cellulose fiber layer 110 is reversed so that the direction of one side of the cellulose fiber layer 110 and the direction of the other side are reversed while the cellulose fiber layer 110 is being conveyed.
  • the cellulose fiber layer inversion mechanism 15 which inverts this is comprised.
  • the cellulose fiber layer inversion mechanism 15 inverts the cellulose fiber layer 110 from the field emission device 20a in accordance with the height position of the field emission device 20b.
  • the field radiating apparatuses 20a and 20b are mounted on the housing body 21 via an insulating member 25, and the collector 24 located on the other side of the cellulose fiber 110 and one of the cellulose fiber layers 110 are provided.
  • a nozzle unit 22 located at a position opposite to the collector 24 on the surface side and having a plurality of nozzles 23 for discharging the polymer solution supplied from a polymer solution supply unit (not shown) toward the cellulose fiber layer 110; Between the collector 24 and the nozzle unit 22, a power supply 29 for applying a high voltage (for example, 10 kV to 80 kV), and an auxiliary belt device 26 to assist the cellulose fiber layer 110 to be conveyed. Equipped.
  • a high voltage for example, 10 kV to 80 kV
  • the nozzle unit 22 of the electric field radiating apparatus 20a, 20b is equipped with the some upward direction nozzle 23 which discharges a polymer solution from a discharge port to an upward direction as a some nozzle.
  • the field radiating device 20a is configured to discharge the polymer solution from the discharge ports of the plurality of top direction nozzles 23 to electrospin the nanofibers.
  • the plurality of upward direction nozzles 23 are arranged at a pitch of, for example, 1.5 cm to 6.0 cm.
  • the number of the some upward direction nozzles 23 is 36 pieces (6 * 6 pieces when it arranges in vertical or horizontal same number)-21904 pieces (148 * 148 pieces when it is arranged in vertical and horizontal same number), for example.
  • the nozzle unit 22 is a rectangle (square being 0.5m-3m in one side, for example from an upper surface). Inclusive).
  • the collector 24 is attached to the conductive housing body 21 via an insulating member.
  • the positive electrode of the power supply device 29 is connected to the collector 24, and the negative electrode of the power supply device 29 is connected to the housing body 21 and the nozzle unit 22.
  • the auxiliary belt device 26 includes an auxiliary belt 27 that rotates in synchronization with the conveyance speed of the cellulose fiber layer 110, and five auxiliary belt rollers 28 that assist the rotation of the auxiliary belt 27.
  • One of the five auxiliary belt rollers 28, or two or more rollers for the auxiliary belt, is a drive roller, and the remaining auxiliary belt rollers are driven rollers. Since the auxiliary belt 27 is provided between the collector 24 and the cellulose fiber layer 110, the cellulose fiber layer 110 is smoothly conveyed without being pulled by the collector 24 to which a positive high voltage is applied.
  • a polymer solution is prepared, and the polymer solution is supplied to the nozzle unit 22.
  • the elongate cellulose fiber layer 110 (refer to FIG. 3 (a)) is set in the conveying apparatus 10, and the cellulose fiber layer 110 is then moved from the feeding roller 11 toward the winding roller 12. It conveys at a predetermined conveyance speed.
  • the nanofiber layer 120 is formed on one side of the cellulose fiber layer 110 being conveyed by the field emission device 20a (see FIG. 3B).
  • the nanofiber layer 130 is formed in the other surface of the cellulose fiber layer 110 conveyed by the field emission apparatus 20b (refer FIG.3 (c)).
  • the separator 100 having the structure in which the nanofiber layers 120 and 130 are provided on both surfaces of the cellulose fiber layer 110 is completed.
  • polylactic acid polypropylene
  • PVAc polyvinyl acetate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PA polyamide
  • PUR polyurethane
  • PAN polyacrylonitrile
  • PAN polyetherimide
  • PCL polycaprolactone
  • PLA polylactic acid glycolic acid
  • PLGA silk, cellulose, chitosan and the like.
  • a solvent used for a polymer solution dichloromethane, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, chloroform, acetone, water, formic acid, acetic acid, cyclohexane, THF, etc. can be used, for example. You may mix and use multiple types of solvent.
  • the polymer solution may contain additives such as conductivity enhancers.
  • a plant fiber used as a raw material of a cellulose fiber coniferous, manila hemp, cedar, a white, etc. can be used, for example. You may mix and use multiple types of fiber.
  • a conveyance speed can be set, for example at 0.2 m / min-100 m / min.
  • the voltage applied between the collector 24 and the nozzle unit 22 can be set between 10 kV and 80 kV, and preferably around 50 kV.
  • the temperature of a spinning zone can be set to 10 to 40 degreeC, for example.
  • the humidity of a radiation zone can be set to 20%-60%, for example.
  • the nanofiber layers 120 and 130 are characterized by thin fibers and fine pores, they have high insulation and high dendrite resistance.
  • the nanofiber layer also has a large porosity, it has high electrolyte solution retention characteristics and high ion conductivity.
  • the separator 100 which concerns on Embodiment 1, since the cellulose fiber layer 110 is provided, it has high mechanical strength.
  • the separator 100 according to Embodiment 1 becomes a separator having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity.
  • the separator 100 which concerns on Embodiment 1, since the thickness of the cellulose fiber layer 110 is 40 micrometers or less, it becomes possible to manufacture a thin separator and to manufacture a non-aqueous battery with a large electric capacity. In addition, since the thickness of the cellulose fiber layer 110 is 1 ⁇ m or more, the mechanical strength does not decrease.
  • the separator 100 which concerns on Embodiment 1
  • the cellulose fiber layer 110 consists of cellulose fiber of 0.1 micrometer or more of average fiber diameters
  • the cellulose fiber layer 110 consists of cellulose fiber of 10 micrometers or less of average fiber diameters, it becomes possible to manufacture a thin separator and to manufacture a non-aqueous battery with a large electric capacity.
  • the separator 100 which concerns on Embodiment 1, since the part which cellulose fibers intertwine increases, it becomes possible to comprise the separator which has sufficient mechanical strength, without making it thick.
  • the separator 100 which concerns on Embodiment 1, since the porosity of the nanofiber layers 120 and 130 exists in the range of 20%-80%, it has high electrolyte solution holding property and can obtain high ion conductivity. Moreover, since the average pore size exists in the range of 0.02 micrometer-2 micrometers, and a dendrite does not easily invade a separator, it has high dendrite tolerance.
  • the separator 100 which concerns on Embodiment 1, it becomes possible to prevent growth of dendrites on both surfaces of the cellulose fiber layer 110, and it becomes possible to comprise the separator with higher dendrite tolerance.
  • the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity can be continuously manufactured with high productivity.
  • the cellulose fiber layer 110 in which the nanofiber layers 120 and 130 were formed can be used as a product as it is. For this reason, the process of isolate
  • the separator manufacturing apparatus 1 which concerns on Embodiment 1, it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.
  • the separator manufacturing apparatus 1 which concerns on Embodiment 1, the cellulose fiber layer 110 in which the nanofiber layers 120 and 130 were formed can be used as a product as it is. For this reason, the process of isolate
  • FIG. 4 is a cross-sectional view of the separator manufacturing apparatus 2 according to the second embodiment.
  • the separator manufacturing apparatus 2 according to the second embodiment has the same configuration as that of the separator manufacturing apparatus 1 according to the first embodiment, but the configuration of the electric field radiating apparatus is the first embodiment. It differs from the case of the separator manufacturing apparatus 1 which concerns. That is, in the separator manufacturing apparatus 2 which concerns on Embodiment 2, as shown in FIG. 4, the field emission apparatus 20a which forms the nanofiber layer 120 in one surface of the cellulose fiber layer 110 to be conveyed, and The field emission device 20c which forms the nanofiber layer 130 on the other side is provided.
  • the field emission device 20c is a downward direction field emission device having a downward direction nozzle.
  • the field radiating apparatus 20a and the field radiating apparatus 20c are the same straight line along the conveyance direction of the cellulose fiber layer 110 in this order. It is arrange
  • the field radiating device 20c is mounted on the support 35 through an insulating member, and is disposed on one side of the cellulose fiber 110 and the collector 34 on the other side of the cellulose fiber layer 110. It is provided with the nozzle unit 32 which has the several downward direction nozzle 33 located in the position which opposes, the power supply 29, and the auxiliary belt apparatus 36 which assists the cellulose fiber layer 110 to be conveyed. do.
  • the nozzle unit 32 is attached to the housing body 31 and has a some lower direction nozzle 33 which discharges a polymer solution from a discharge port to a downward direction as a some nozzle.
  • the collector 34 is mounted on the conductive support 35 via an insulating member.
  • the positive electrode of the power supply device 29 is connected to the collector 34, and the negative electrode of the power supply device 29 is the housing body 35. And the nozzle unit 32.
  • the auxiliary belt device 36 includes an auxiliary belt 37 that rotates in synchronization with the conveyance speed of the cellulose fiber layer 110, and five rollers 38 for assisting belts that assist the rotation of the auxiliary belt 37.
  • the separator manufacturing apparatus 2 according to the second embodiment is different from the case of the separator manufacturing apparatus 1 according to the first embodiment, although the configuration of the field radiating device is the same as that of the separator manufacturing apparatus 1 according to the first embodiment. It becomes possible to manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity continuously with high productivity.
  • the separator manufacturing apparatus 2 which concerns on Embodiment 2, the cellulose fiber layer 110 in which the nanofiber layer 120,130 was formed can be manufactured as it is. For this reason, the process of isolate
  • the separator manufacturing apparatus 2 which concerns on Embodiment 2, it becomes possible to manufacture the separator which has a structure in which the nanofiber layer was provided in both surfaces of a cellulose fiber layer, without making the installation height of a separator manufacturing apparatus very high.
  • the separator manufacturing apparatus 2 which concerns on Embodiment 2 has the structure similar to the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1 except the structure of the field emission apparatus, the separator manufacturing apparatus which concerns on Embodiment 1 ( It has one of the effects that 1) has.
  • FIG 5 is a cross-sectional view of the separator 102 according to the third embodiment.
  • the separator 102 according to the third embodiment basically has the same configuration as the separator 100 according to the first embodiment, but the structure of the cellulose fiber layer is the separator 100 according to the first embodiment. It is different from the case. That is, the separator 102 which concerns on Embodiment 3 is equipped with the cellulose fiber layer 112 manufactured by the cellulose fiber layer manufacturing apparatus 40 mentioned later as shown in FIG.
  • the separator 102 is obtained by the separator method which concerns on Embodiment 3 using the separator manufacturing apparatus 3 which concerns on Embodiment 3 mentioned later.
  • FIG. 6 is a cross-sectional view of the separator manufacturing apparatus 3 according to the third embodiment.
  • FIG. 7 is a diagram showing that the separator 102 is manufactured by the method for manufacturing a separator according to the third embodiment.
  • the separator manufacturing apparatus 3 which concerns on Embodiment 3 basically has the same structure as the separator manufacturing apparatus 1 which concerns on Embodiment 1, but Embodiment 1 is the point which further comprises the structure of a conveying apparatus, and a cellulose fiber layer manufacturing apparatus. It differs from the case of the separator manufacturing apparatus 1 which concerns on this. That is, the separator manufacturing apparatus 3 which concerns on Embodiment 3 has the conveying apparatus 60 which conveys the long sheet W, the field emission apparatus 20a, 20b, and the cellulose fiber layer (as shown in FIG. 6). The cellulose fiber layer manufacturing apparatus 40 which forms 112 is provided.
  • the field emission apparatus 20a the elongate sheet inversion mechanism 65a mentioned later, the cellulose fiber layer manufacturing apparatus 40, and later mentioned
  • the long sheet reversing mechanism 65b and the electric field radiating device 20b are arranged along the conveyance direction of the long sheet W in this order.
  • the long sheet conveying apparatus 60 is provided as a conveying apparatus.
  • the long sheet conveying device 60 includes an feeding roller 61 for feeding the long sheet W, a winding roller 62 for winding the long sheet W, and a tension roller for adjusting the pulling of the long sheet W ( 63, 68, the some drive roller 64 which conveys the long sheet W, the 1st reverse roller 66a, 66c, and the 2nd reverse roller 66b, 66d.
  • the feed roller 61, the winding roller 62, the tension rollers 63 and 68, and the some drive roller 64 comprise the conveyance mechanism 60 which conveys the long sheet W.
  • the some drive roller 64 is a drive apparatus which conveys the long sheet W. As shown in FIG.
  • the 1st reversing roller 66a and the 2nd reversing roller 66b have the long sheet W so that the direction of the one surface of the long sheet W and the other surface may be reversed while the long sheet W is conveyed.
  • a long sheet reversing mechanism 65a for reversing the structure is formed.
  • the 1st reversing roller 66c and the 2nd reversing roller 66d are a long sheet
  • the long sheet inversion mechanism 65b which inverts (W) is constituted.
  • the field emission devices 20a and 20b have the same configuration as the field emission devices 20a and 20b used in the first embodiment.
  • the cellulose fiber layer manufacturing apparatus 40 forms the cellulose fiber layer 112 in the long sheet W conveyed by the long sheet conveying apparatus 60, as shown in FIG.
  • the cellulose fiber layer manufacturing apparatus 40 has a nozzle unit 42 having a plurality of downward direction nozzles 43 for discharging the cellulose solution supplied from the cellulose solution supply unit (not shown) toward the long sheet W, and toward the cellulose solution.
  • the high temperature airflow supply part 44 which injects high temperature airflow, and the high temperature airflow suction apparatus 47 are provided.
  • the nozzle unit 42 is attached to the housing body 21 and described later in the direction along the cellulose solution discharge direction and the plurality of downward direction nozzles 43 for discharging the cellulose solution downward from the discharge port as a plurality of nozzles. It has a high temperature airflow path (not shown) which flows the high temperature airflow supplied from the high temperature airflow supply part 44. As shown in FIG.
  • the plurality of downward direction nozzles 43 are arranged at a pitch of, for example, 1.5 cm to 6.0 cm.
  • the nozzle unit 42 may use a nozzle unit having various sizes and various shapes.
  • the hot airflow supply 44 includes a suction pump 45 and a heater 46.
  • the high temperature airflow supply 44 forms the high temperature airflow by heating the air blown in from the outside by the suction pump 84 with the heater 46.
  • the hot air flow is led to a hot air flow path (not shown) of the nozzle unit 42.
  • the heater 46 can adjust the output so that a high temperature airflow may be a predetermined temperature within a range of 120 ° C to 500 ° C.
  • the high temperature airflow suction device 47 is disposed on the inner surface side of the long sheet W as viewed from the nozzle unit 42, and the mesh member 48, the high temperature airflow suction unit 50, and the discharge pump 51 are disposed. Equipped.
  • the high temperature airflow flowing from the high temperature airflow path (not shown) is sucked by the high temperature airflow suction unit 50 through the mesh member 44 in which a plurality of holes for airflow passage are formed, and is discharged to the discharge pump 51. Is discharged to the outside.
  • FIG. 7 is a diagram showing that the separator 102 is manufactured by the method for manufacturing a separator according to the third embodiment.
  • 7A to 7E are respective process diagrams.
  • the cellulose solution is prepared in one cellulose fiber layer manufacturing apparatus 40, and the cellulose solution is supplied to the nozzle unit 42.
  • a polymer solution is prepared, and the polymer solution is supplied to each nozzle unit 22.
  • the long sheet W is set to the long sheet conveying apparatus 60, and the long sheet W is conveyed from the input roller 61 toward the winding roller 62 at a predetermined conveyance speed after that (FIG. See (a) of 7).
  • the cellulose solution is obtained by melting cellulose, which is a material of the cellulose fiber layer 112, or dissolving it in a solvent.
  • the nanofiber layer 120 is formed on one surface of the long sheet W by the field emission device 20a while conveying the long sheet 110 (see FIG. 7B).
  • the direction of one side of the long sheet W and the direction of the other side are reversed by the long sheet reversing mechanism 65a (inverting rollers 66a, 66b) so that one side becomes the upper side.
  • the cellulose fiber layer 112 is formed on one surface of the long sheet W by the cellulose fiber manufacturing apparatus 40 while conveying the long sheet W in which the nanofiber layer 120 was formed (FIG. 7 ( c)).
  • the nanofiber layer 120 and the nanofiber layer 130 are laminated
  • the long sheet reversing mechanism 65b (reversing rollers 66c, 66d) reverses the direction of the one surface of the long sheet W and the direction of the other surface such that one surface becomes the lower side.
  • the nanofiber layer 130 is formed on one side of the long sheet W by the field emission device 20b while conveying the long sheet W on which the nanofiber layer 120 and the cellulose fiber layer 112 are laminated. (See FIG. 7D). Thereby, the laminated sheet by which the nanofiber layer 120, the cellulose fiber layer 112, and the nanofiber layer 130 were laminated
  • the separator 102 and the long sheet are separated while the laminated sheet is introduced to manufacture the separator 102 (see FIG. 5E).
  • the separator 102 can be manufactured.
  • nonwoven fabric, woven fabric, knitted fabric, film, paper, etc. made of various materials can be used.
  • the thickness of a long sheet the thing of 5 micrometers-500 micrometers can be used, for example.
  • the thing of 10m-10km can be used, for example.
  • the separator manufacturing apparatus 3 which concerns on Embodiment 3 differs from the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1 in that the structure of a conveying apparatus and the cellulose fiber layer manufacturing apparatus differ from the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1, Like (1), it becomes possible to continuously manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity with high productivity.
  • the separator manufacturing apparatus 3 which concerns on Embodiment 3, it becomes possible to adjust the thickness of a cellulose fiber layer, the fiber length of a cellulose fiber, the porosity and the pore size of a cellulose fiber layer, and form the cellulose fiber layer which has a desired characteristic. It becomes possible. It is suitable for forming a cellulose fiber layer made of cellulose fibers having a relatively large average fiber diameter.
  • the separator manufacturing apparatus 3 which concerns on Embodiment 3 has the structure similar to the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1 except having the structure of a conveying apparatus and the cellulose fiber layer manufacturing apparatus further, it implements. It has a corresponding effect among the effects which the separator manufacturing apparatus 1 which concerns on the form 1 has.
  • the order in which the field radiating device and the cellulose fiber layer manufacturing device are disposed is appropriately changed in the separator manufacturing apparatus 3 according to the third embodiment, so that both sides of the separator and the cellulose fiber layer having a structure in which the nanofiber layer is provided on one side of the cellulose fiber layer. It is possible to manufacture either the separator of the structure in which the nanofiber layer was provided, and the separator of the structure in which the cellulose fiber layer was provided on both surfaces of the nanofiber layer.
  • FIG. 8 is a cross-sectional view of the separator manufacturing apparatus 4 according to the fourth embodiment.
  • the separator manufacturing apparatus 4 which concerns on Embodiment 4 has the structure similarly to the separator manufacturing apparatus 3 which concerns on Embodiment 3, the structure of the separator manufacturing apparatus 3 which concerns on Embodiment 3 is a structure of the field emission apparatus. ) Is different. That is, in the separator manufacturing apparatus 4 which concerns on Embodiment 4, as shown in FIG. 8, 20 d of lower direction electric field emission apparatuses which form the nanofiber layer 120 in the elongate sheet W to be conveyed, The downward direction field emission device 20c which forms the nanofiber layer 130 in the elongate sheet W conveyed is provided.
  • the field radiating apparatus 20d, the cellulose fiber layer manufacturing apparatus 40, and the field radiating apparatus 20c are long sheets (in this order). It is arrange
  • the separator manufacturing apparatus 4 according to the fourth embodiment is different from the case of the separator manufacturing apparatus 3 according to the third embodiment, although the configuration of the field emission device is the same as that of the separator manufacturing apparatus 3 according to the third embodiment. It becomes possible to manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity continuously with high productivity.
  • the separator manufacturing apparatus 4 which concerns on Embodiment 4
  • the separator manufacturing apparatus 4 which concerns on Embodiment 4, it becomes possible to manufacture the separator which has a structure in which the nanofiber layer was provided in both surfaces of a cellulose fiber layer, without making the installation height of a separator manufacturing apparatus very high.
  • the separator manufacturing apparatus 4 which concerns on Embodiment 4 has the structure similar to the case of the separator manufacturing apparatus 3 which concerns on Embodiment 3 except the structure of the field emission apparatus, the separator manufacturing apparatus which concerns on Embodiment 3 ( It has a corresponding effect among the effects that 3) has.
  • FIG 9 is a cross-sectional view of the separator manufacturing apparatus 5 according to the fifth embodiment.
  • the separator manufacturing apparatus 5 according to the fifth embodiment basically has the same configuration as the separator manufacturing apparatus 4 according to the fourth embodiment, but the structure of the cellulose fiber layer manufacturing apparatus according to the fourth exemplary embodiment is the separator manufacturing apparatus 4 according to the fourth exemplary embodiment. It is different from the case. That is, in the separator manufacturing apparatus 5 which concerns on Embodiment 5, as shown in FIG. 9, the field emission apparatus 20e is provided as a cellulose fiber layer manufacturing apparatus.
  • the field radiator 20e is a top direction field radiator having a top direction nozzle.
  • the separator manufacturing apparatus 5 which concerns on Embodiment 5 differs from the separator manufacturing apparatus 4 which concerns on Embodiment 4,
  • the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity can be continuously manufactured with high productivity.
  • positions an electric field radiating device and a cellulose fiber layer manufacturing apparatus suitably. It is possible to manufacture either the separator of the structure in which the nanofiber layer was provided, and the separator of the structure in which the cellulose fiber layer was provided on both surfaces of the nanofiber layer.
  • the separator manufacturing apparatus 5 which concerns on Embodiment 5, it becomes possible to adjust the thickness of a cellulose fiber layer, the fiber length of a cellulose fiber, the porosity and the pore size of a cellulose fiber layer, and form the cellulose fiber layer which has a desired characteristic. It becomes possible. It is suitable for forming a cellulose fiber layer composed of cellulose fibers having a relatively small average fiber diameter.
  • the separator manufacturing apparatus 5 which concerns on Embodiment 5, it becomes possible to manufacture the separator which has a structure in which the nanofiber layer was provided in both surfaces of a cellulose fiber layer, without making the installation height of a separator manufacturing apparatus very high.
  • the separator manufacturing apparatus 5 which concerns on Embodiment 5 has the structure similar to the case of the separator manufacturing apparatus 4 which concerns on Embodiment 4 except the structure of a cellulose fiber layer manufacturing apparatus, the separator manufacturing apparatus which concerns on Embodiment 4 It has a corresponding effect among the effects of (4).
  • nanofiber layer forming apparatus for example, one, three or more field radiating apparatuses may be used.
  • one cellulose fiber layer production apparatus was used as the cellulose fiber layer production apparatus, but the present invention is not limited thereto.
  • two or more cellulose fiber layer production apparatuses may be used.
  • the melt blow spinning apparatus or the field spinning apparatus was used as a cellulose fiber layer manufacturing apparatus, this invention is not limited to this.
  • the separator of the structure which provided the nanofiber layer on both surfaces of the cellulose fiber layer was manufactured, this invention is not limited to this.
  • the separator which provided the nanofiber layer on one side of a cellulose fiber layer may be manufactured, and the separator which provided the cellulose fiber layer on both surfaces of a nanofiber layer may be manufactured.
  • the anode of the power supply device 29 is connected to the collector 24 and the cathode of the power supply device 29 is connected to the nozzle unit 22 in each said embodiment, this invention is not limited to this. .
  • the anode of the power supply device may be connected to the nozzle, and the cathode of the power supply device may be connected to the collector.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne un séparateur, un procédé pour fabriquer un séparateur, et un appareil pour fabriquer un séparateur, le séparateur (100) comprenant : une couche de fibre cellulosique (110) ; une couche de nano-fibre (120) qui est accouplée avec une surface de la couche de fibre cellulosique (110) ; et une autre couche de nano-fibre qui est accouplée avec l'autre surface de la couche de fibre cellulosique (110). La couche de fibre cellulosique (110) possède une largeur de 1 µm à 40 µm, est faite d'une fibre cellulosique qui possède un diamètre moyen de 0,1 µm à 10 µm, et la couche de fibre cellulosique (110) est faite de la fibre cellulosique qui possède une longueur moyenne d'au moins 2,0 mm, fournissant ainsi le séparateur qui possède une haute résistance à la conductivité, une conductivité élevée, une haute durabilité à la dendrite, et une haute conductivité ionique.
PCT/KR2012/000849 2011-03-18 2012-02-06 Séparateur, procédé pour fabriquer un séparateur, et appareil pour fabriquer un séparateur Ceased WO2012128471A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-061736 2011-03-18
JP2011061736A JP5860603B2 (ja) 2011-03-18 2011-03-18 セパレーター製造装置
KR10-2011-0125756 2011-11-29
KR1020110125756A KR20120109289A (ko) 2011-03-18 2011-11-29 세퍼레이터의 제조 방법 및 세퍼레이터 제조 장치

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WO2012128471A2 true WO2012128471A2 (fr) 2012-09-27
WO2012128471A3 WO2012128471A3 (fr) 2012-11-22

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Cited By (3)

* Cited by examiner, † Cited by third party
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WO2019126979A1 (fr) * 2017-12-26 2019-07-04 广州华创化工材料科技开发有限公司 Substrat de séparateur de batterie au lithium-ion ainsi que son procédé de préparation et son application
CN112332020A (zh) * 2020-10-31 2021-02-05 华南理工大学 一种跨尺度微纳纤维素锂离子电池隔膜及其制备方法
CN120165177A (zh) * 2025-04-01 2025-06-17 河南科高辐射化工科技有限公司 一种纤维素基电池隔膜及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100470314B1 (ko) * 2003-06-17 2005-02-07 (주)삼신크리에이션 전기화학소자용 복합막, 그 제조방법 및 이를 구비한전기화학소자
JP2008235047A (ja) * 2007-03-22 2008-10-02 Kuraray Co Ltd 電池用セパレータ及びその製造方法
JP5049092B2 (ja) * 2007-10-18 2012-10-17 株式会社クラレ キャパシタ用セパレータおよびキャパシタ
JP2011035373A (ja) * 2009-07-10 2011-02-17 Tomoegawa Paper Co Ltd 蓄電デバイス用セパレータ

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019126979A1 (fr) * 2017-12-26 2019-07-04 广州华创化工材料科技开发有限公司 Substrat de séparateur de batterie au lithium-ion ainsi que son procédé de préparation et son application
US11616272B2 (en) 2017-12-26 2023-03-28 Fibrway Material Science & Technology Development Co., Ltd. Battery separator substrate including dense layer formed on support layer, and method for preparing the same
CN112332020A (zh) * 2020-10-31 2021-02-05 华南理工大学 一种跨尺度微纳纤维素锂离子电池隔膜及其制备方法
CN112332020B (zh) * 2020-10-31 2022-06-14 华南理工大学 一种跨尺度微纳纤维素锂离子电池隔膜及其制备方法
CN120165177A (zh) * 2025-04-01 2025-06-17 河南科高辐射化工科技有限公司 一种纤维素基电池隔膜及其制备方法和应用

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