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WO2014003192A1 - Structure à fibres fines - Google Patents

Structure à fibres fines Download PDF

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Publication number
WO2014003192A1
WO2014003192A1 PCT/JP2013/067960 JP2013067960W WO2014003192A1 WO 2014003192 A1 WO2014003192 A1 WO 2014003192A1 JP 2013067960 W JP2013067960 W JP 2013067960W WO 2014003192 A1 WO2014003192 A1 WO 2014003192A1
Authority
WO
WIPO (PCT)
Prior art keywords
fine fiber
fiber structure
battery
separator
fine
Prior art date
Application number
PCT/JP2013/067960
Other languages
English (en)
Japanese (ja)
Inventor
丈也 出井
航治 岩崎
恭介 高野
Original Assignee
帝人株式会社
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
Application filed by 帝人株式会社 filed Critical 帝人株式会社
Publication of WO2014003192A1 publication Critical patent/WO2014003192A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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 fine fiber structure comprising a fine fiber layer composed of polymer fine fibers, and more specifically to a battery such as a lithium battery or an alkaline battery, a separator such as an electric double layer capacitor or a capacitor, or an insulating material.
  • the present invention relates to a fine fiber structure that can be suitably used.
  • the battery includes a separator positioned between the anode and cathode to prevent electrical connection or short circuit between the anode and cathode.
  • a short circuit occurs when the conductive particles bridge the separator, or when the separator is degraded to allow electrode contact. In rare cases, battery shorts may occur all at once, but rather due to the accumulation of very small conductive paths called “soft shorts” over time.
  • “Dendrite short” is, for example, formed on one electrode of a battery with a dendrite containing a precipitate such as zincate in the case of an alkaline battery, or lithium metal in the case of a lithium battery, and through a separator. The other electrode is grown to provide an electrical connection between the anode and the cathode.
  • Primary alkaline batteries generally have a cathode, an anode, a separator disposed between the cathode and anode, and an alkaline electrolyte solution.
  • the cathode is typically formed from MnO 2 , carbon particles and a binder.
  • the anode can be formed from a gel containing zinc particles.
  • the electrolyte solution dispersed throughout the battery is most commonly an aqueous solution containing 30-40% potassium hydroxide.
  • Battery separators used in alkaline batteries have certain performance requirements. For example, such a separator needs to be stable in the presence of a strong alkaline electrolyte (for example, 30 to 40% KOH).
  • the lack of alkali chemical resistance can lead to internal shorts between the electrodes due to a loss of mechanical integrity.
  • Good electrolyte absorption is also necessary, meaning that the separator is fully impregnated with the electrolyte solution needed for the electrochemical reaction of the cell.
  • Another requirement of the separator is a barrier to the growing dendrites of conductive zinc oxide formed by electrochemical reactions in the cell that can cause a short circuit through the separator.
  • the separator must also allow the movement of ions between the electrodes, in other words, the separator should exhibit a low resistance to ion flow.
  • Secondary alkaline zinc-MnO 2 batteries have similar anode, cathode and electrolyte as primary alkaline batteries.
  • Certain additives eg, Bi 2 O 3 , BaSO 4 , organic inhibitors, etc.
  • additives eg, Bi 2 O 3 , BaSO 4 , organic inhibitors, etc.
  • Some of the additives can dissolve in the electrolyte and move to other electrodes.
  • the use of a separator with good dendrite barrier properties will help extend the cycle life of the zinc-MnO 2 secondary battery.
  • Battery separators for alkaline batteries conventionally have large pores with good (low) ionic resistance, but with a relatively poor barrier to growing dendrites (hereinafter sometimes referred to as “dendritic barriers”).
  • U.S. Patent No. 6,057,031 discloses a composite battery separator that includes at least one nonwoven layer and a layer that reduces dendritic shorts, which can be a microporous layer made of cellophane, polyvinyl alcohol, polysulfone, grafted polypropylene or polyamide. The thickness of the composite separator is about 8.3 mil.
  • the battery separator has an ionic resistance of less than 90 milliohm-cm 2 when measured in a 40% potassium hydroxide (KOH) electrolyte solution at 1 KHz.
  • the microporous layer is desirably mixed with a very high level of barrier to air, but it is not desirable to have high ionic resistance, poor electrolyte wettability, and poor electrolyte absorption properties.
  • Lithium batteries belong to three general categories: lithium primary batteries, lithium ion secondary batteries and lithium ion gel polymer batteries.
  • Lithium primary batteries use many different types of battery chemistries, each using lithium as the anode, but with different cathode materials and electrolytes.
  • lithium manganese oxide or Li-MnO 2 cells lithium is used as the anode and MnO 2 is used as the cathode material; the electrolyte contains a lithium salt in a mixed organic solvent such as propylene carbonate and 1,2-dimethoxyethane. contains.
  • Lithium iron sulfide or Li / FeS 2 batteries use lithium as the anode, iron disulfide as the cathode, and lithium iodide in the organic solvent blend as the electrolyte.
  • Lithium ion secondary batteries use lithium-inserted carbon as an anode, lithium metal oxide (eg, LiCoO 2 ) as a cathode and an organic solvent blend with 1M lithium hexafluorophosphate (LiPF 6 ) as an electrolyte.
  • Lithium ion gel polymer batteries use similar anode and cathode materials as lithium ion secondary batteries. The liquid organic electrolyte forms a gel with the polymer separator, which helps provide a good bond between the separator and the electrode.
  • Patent Document 3 discloses an ultrafine fibrous porous polymer separator film for use as a battery separator in a lithium secondary battery, and the separator film has a thickness of 1 to 100 ⁇ m.
  • the separator film is formed from fine fibers formed by electrospinning a polymer melt or polymer solution having a diameter of 1 to 3000 nm.
  • Nonwoven materials that are easily used as separators in alkaline batteries have large diameter fibers and therefore it is difficult to achieve thin separators.
  • Such nonwoven fabric also has large pores, for example between 15 and 35 ⁇ m.
  • the anode and cathode particles can move to each other through large pores, creating an internal short circuit.
  • thicker separators are formed using multiple layers.
  • such a thick separator is not preferable from the viewpoint of battery performance because it provides higher ionic resistance, and when used in coin cells and other small batteries that are useful in electronic devices, the separator is thick, and thus is not designed. The usage is limited.
  • the present invention has been made in view of the above-described background art, and its purpose is to cause breakage or bending even when a roller or guide having a small diameter is passed or wound on a winding bobbin in the manufacturing or processing step.
  • a fine fiber structure made of fine fibers
  • a roller or guide having a small diameter is passed or wound on a take-up bobbin in a manufacturing or processing step, it is caused by bending or bending.
  • wrinkles, deformation of the shape and the like are likely to occur, and that the cause is due to the hardness of the fine fiber structure, and that the above problem can be solved by the following configuration.
  • a fine fiber structure comprising a fine fiber layer composed of polymer fine fibers having an average diameter of 50 to 3000 nm, wherein the fine fiber structure has a bending resistance by 45 ° cantilever method.
  • a fine fiber structure characterized by an air permeability of less than 46 m 3 / min / m 2 and a Macmillan number of 2 to 15.
  • a battery, an electric double layer capacitor, or a capacitor including the fiber structure as a separator or an insulating material is provided.
  • the fine fiber structure of the present invention is wrinkled or deformed due to bending or bending even when passing through a roller or guide with a small diameter or winding it on a winding bobbin in the manufacturing and processing steps. In addition, it has excellent ion permeability and short circuit resistance at the same time. For this reason, the fine fiber structure can be used as a separator or an insulating material, and can be fully utilized without being affected by wrinkles, deformation of the shape, etc., and high performance batteries, electric double layer capacitors, capacitors, etc. Can be manufactured.
  • the fine fiber structure of the present invention is excellent in thin, low ionic resistance and good dendrite barrier properties, soft short barrier properties, short circuit resistance, etc., and separators and insulating materials for batteries, electric double layer capacitors, capacitors, etc. Used for demonstrating excellent performance. That is, the fine fiber structure of the present invention has a high capacity for absorbing the electrolyte when used as a separator or insulating material for a battery, while the separator and the like are saturated even when saturated with an electrolyte solution. In order not to lose the dendrite barrier properties, it has excellent structure maintenance, chemical stability and dimensional stability in practical use.
  • the separator or the like when used as a separator or an insulating material for an electric double layer capacitor or capacitor, the separator or the like has a high capacity for absorbing the electrolyte, and when the separator is saturated with the electrolyte solution, the soft short barrier In order not to lose the characteristics, it has excellent structure maintainability, chemical stability, and dimensional stability in practical use.
  • electric double layer capacitor, capacitor separator and insulating material are all thinner, the materials used in the battery, electric double layer capacitor and capacitor (ie, anode, separator, insulating material, and cathode) Since the total thickness is reduced, a high electrochemically active material can be contained in a specific volume, and a large-capacity battery, an electric double layer capacitor, and a capacitor can be manufactured.
  • the separator or the like has a low ionic resistance, and ions easily flow between the anode and the cathode.
  • the fine fiber structure of the present invention includes at least one fine fiber layer composed of polymer fine fibers having an average diameter of 50 to 3000 nm, preferably 50 to 1000 nm, and more preferably 100 to 800 nm.
  • Such fine fibers can achieve good electrolyte absorbability and retention when used as separators or insulating materials for the above-mentioned batteries having a high surface area.
  • the crystallinity of the fine fibers is preferably 37% or more, more preferably 40% or more, still more preferably 45% or more, and particularly preferably 50% or more. If the degree of crystallinity is less than 37%, when the fine fiber structure including the fine fiber layer is used as a separator or the like and the electrolyte is infiltrated, the fiber tends to expand greatly and the pore diameter tends to be narrowed. In some cases, the battery becomes large, and sufficient performance cannot be obtained with a battery, capacitor, capacitor, or the like.
  • the average pore diameter of the fine fiber layer is 0.01 to 15 ⁇ m, preferably 0.01 to 5 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • the porosity of the fine fiber layer is 20 to 90%, preferably 40 to 80%, more preferably 50 to 80%. By increasing the porosity, it is possible to achieve good electrolyte absorption and retention in a battery or the like as described above.
  • the thickness of the fine fiber layer is 0.0025 to 0.3 mm, preferably 0.0127 to 0.127 mm.
  • the thickness should be sufficient to prevent dendrite-induced shorts between the anode and cathode, while allowing ions to flow well between the cathode and anode. It is preferable that When the fine fiber structure including the thin fine fiber layer as described above is used as a separator or an insulating material, it can create a further space in the electrode in the cell, improve the performance as a battery, and extend the life. be able to.
  • the basis weight of the fine fiber layer is 1 to 90 g / m 2 , preferably 5 to 30 g / m 2 .
  • the separator may not be able to reduce the dendrite short and soft short barrier characteristics between the anode and the cathode.
  • the fragile air permeability of the fine fiber layer is less than 46 m 3 / min / m 2 , preferably less than 8 m 3 / min / m 2 , more preferably less than 1.5 m 3 / min / m 2 .
  • the bending resistance of the fine fiber structure is 100 mm or less, preferably 90 mm or less, more preferably 80 mm or less.
  • the bending resistance exceeds 100 mm, in the process of manufacturing and processing a fine fiber structure, if it is passed through a roller or guide having a small diameter or wound on a winding bobbin, it will be wrinkled by bending or bending.
  • separators or insulating materials such as batteries, electric double layer capacitors and capacitors cannot be obtained.
  • the handleability deteriorates, so that it is preferably 10 mm or more, more preferably 20 mm or more, still more preferably 30 mm or more, still more preferably 38 mm, and particularly preferably 40 mm or more. desirable. That is, according to the present invention, in the fine fiber structure as described above, wrinkles due to bending and bending in the manufacturing and processing steps, deformation of the shape, and the like greatly affect the performance of the battery, and JIS L1096 (2010). 8.21 A method (45 ° cantilever method) allows the above-mentioned problem to be improved by setting the bending resistance to 100 mm or less.
  • the surface of the fine fiber structure and the internal hot-pressure treatment state are processed differently.
  • the fiber having the above-mentioned bending resistance by improving the strength of the surface fiber and maintaining the softness of the inner fiber by the method and the method of carrying out calendering with a gap between the heat rolls of the calender device It has been found that a structure can be obtained, and has reached the fine fiber structure of the present invention.
  • the present invention also achieves the above-mentioned bending resistance while maintaining the porosity, thickness, basis weight, etc. of the fine fiber layer.
  • the measurement sample is cut out from the fine fiber structure at any angle, for example, MD direction, CD direction, etc.
  • the value obtained by dividing the tear strength of the fine fiber structure by the Elmendorf-type tear tester method by the basis weight is preferably 0.9 g / (g / m 2 ) or more.
  • the tear strength / basis weight is preferably 0.9 g / (g / m 2 ) or more.
  • it is 1.0 g / (g / m 2 ) or more, more preferably 1.5 g / (g / m 2 ) or more, particularly preferably 2.0 g / (g / m 2 ) or more.
  • the tear strength / basis weight is less than 0.9 g / (g / m 2 )
  • the fine fiber structure is wound between the electrodes, and the electrode burrs are used as the starting point for tearing and stable production. Tend to be difficult.
  • the tear strength and basis weight refer to the tear strength and basis weight of the fine fiber structure.
  • the measurement sample may be cut out from the fine fiber structure at any angle, for example, MD direction, CD direction, etc. It is sufficient if the tear strength / basis weight requirement is satisfied.
  • the shock absorption value according to Charpy impact testing method of the fine fibrous structure is preferably 290 kJ / m 2 or more, more preferably 300 kJ / m 2 or more, more preferably 400 kJ / m 2 or more, particularly preferably Is 450 kJ / m 2 or more. If the shock absorption value is smaller than 290 kJ / m 2 , when a vibration or impact is applied, the separator or insulating material cannot absorb the impact, and the internal members may be damaged or displaced. There is a tendency that performance degradation or failure of the battery including the separator or the insulating material is likely to be induced.
  • the fine fiber structure of the present invention has a low bending resistance of 100 mm or less, and at the same time has excellent tearing strength and impact absorption value, which are characteristics contrary to this, thereby producing a separator and an insulating material.
  • the separator or the like is not deformed or damaged during the processing step, the manufacturing process of the battery using the same, or the use thereof, and a higher performance battery, capacitor, capacitor, or the like can be provided.
  • the penetration rate of the fine fiber structure is preferably 20 cm 2 / min or more, more preferably 30 cm 2 / min or more.
  • the penetration rate of the electrolytic solution is less than 20 cm 2 / min, uniform penetration of the electrolytic solution into the interior of a battery, an electric double layer capacitor, a capacitor, or the like tends to be difficult. That is, in batteries, particularly lithium batteries, capacitors, capacitors, etc., the number of stacked electrodes and the area of the electrodes have increased due to the increase in capacity, and as a result, the penetration time of the electrolyte into the battery has increased and work efficiency has increased.
  • a separator or an insulating material that can cope with these problems can be obtained.
  • the residual solvent amount of the fine fiber structure is preferably less than 0.1% by weight, more preferably 0.05% by weight or less, and particularly preferably 0.03% by weight or less.
  • Suitable polymers that can be used in the fine fiber structure of the present invention include any thermoplastic and thermosetting that is substantially inert to the electrolyte solution used in batteries, electric double layer capacitors, capacitors, etc. Polymers.
  • Polymers suitable for use in forming the separator fibers include, but are not limited to, polyvinyl alcohol, aliphatic polyamide, semi-aromatic polyamide, aromatic polyamide, polysulfone, cellulose acetate, cellulose, polyethylene terephthalate, polypropylene terephthalate, poly Butylene terephthalate, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polymethylpentene, polyacrylonitrile polyphenylene sulfide, polyacetyl, polyurethane, polyacrylonitrile, polymethyl methacrylate, polystyrene and copolymers or derivative compounds thereof, and these The combination of is mentioned.
  • polymers such as polyvinyl alcohol (PVA), polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, swell or gel in the electrolyte, plugging the pores of the fine fiber structure There is a tendency. It will also soften or decompose in the electrolyte and provide structural integrity to the snare of the fine fiber structure.
  • PVA polyvinyl alcohol
  • PVD polyvinylidene fluoride
  • polyvinylidene fluoride-hexafluoropropylene polyethylene oxide
  • polyacrylonitrile polyacrylonitrile
  • polymethyl methacrylate polymethyl methacrylate
  • crosslinking agents and crosslinking conditions can be used. All of the above polymers can be crosslinked by known means such as chemical crosslinking, electron beam crosslinking or UV crosslinking.
  • PVA can be crosslinked either by chemical crosslinking, electron beam crosslinking or UV crosslinking.
  • Chemical cross-linking of the PVA fine fiber layer can be done by treating the PVA layer with dialdehyde and acid, then neutralizing the acid with NaHCO 3 and washing the layer with water.
  • Cross-linking of PVA makes it water-insoluble and increases its mechanical strength and its oxidation and chemical resistance.
  • a polyvinylidene fluoride-hexafluoropropylene separator is crosslinked by adding a crosslinking agent (PEGDMA oligomer) and a crosslinking initiator (2,2-azobisisobutyronitrile) and heating the separator at 80 ° C. for 12 hours. It is possible. Polyacrylonitrile separators can be crosslinked by adding a crosslinking agent (eg, ethylene glycol dimethacrylate or triethylene glycol dimethacrylate) and an initiator (eg, benzoyl peroxide) and heating at 60 ° C. .
  • a crosslinking agent eg, ethylene glycol dimethacrylate or triethylene glycol dimethacrylate
  • an initiator eg, benzoyl peroxide
  • the battery can be, for example, a zinc-manganese oxide or Zn-MnO 2 battery in which the anode is zinc and the cathode is manganese oxide (MnO 2 ), or a zinc-air battery in which the anode is zinc and the cathode is air.
  • a zinc-manganese oxide or Zn-MnO 2 battery in which the anode is zinc and the cathode is manganese oxide (MnO 2 )
  • MnO 2 manganese oxide
  • NiOOH nickel oxy-hydroxide
  • H 2 nickel metal hydride
  • alkaline batteries include zinc / mercury oxide where the anode is zinc and the cathode is mercury oxide (HgO), the anode is cadmium and the cadmium / mercury oxide where the cathode is mercury oxide, the anode is Zinc / silver oxide, which is zinc and the cathode is silver oxide (AgO), cadmium / silver oxide where the anode is cadmium and the cathode is silver oxide. All these battery types use 30-40% potassium hydroxide as the electrolyte. Another embodiment of the invention relates to a lithium battery.
  • the lithium battery of the present invention can be a lithium primary battery, such as a Li—MnO 2 or Li—FeS 2 lithium primary battery, a lithium ion secondary battery, or a lithium ion gel polymer battery.
  • Lithium primary batteries utilize many different types of battery chemistry, each using lithium as the anode, but different cathode materials (SO 2 , SOCl 2 , SO 2 Cl 2 , CFn, CuO, FeS 2 , MnO 2, etc. ) And an electrolyte.
  • lithium manganese oxide or Li-MnO 2 cells lithium is used as the anode and MnO 2 as the cathode material; the electrolyte contains a lithium salt in a mixed organic solvent such as propylene carbonate and 1,2-dimethoxyethane.
  • Lithium iron sulfide or Li / FeS 2 batteries use lithium as the anode, iron disulfide as the cathode, and lithium iodide in an organic solvent blend (eg, propylene carbonate, ethylene carbonate, dimethoxyethane, etc.) as the electrolyte.
  • Lithium ion secondary batteries use lithium-inserted carbon as an anode, lithium metal oxides (eg, LiCoO 2 , LiNiO 2 , LiMn 2 O 4, etc.) as cathodes and blends of organic solvents (eg, propylene carbonate, ethylene carbonate, Diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, etc.) are used as an electrolyte together with 1M lithium hexafluorophosphoric acid (LiPF 6 ).
  • Lithium ion gel polymer batteries use anodes and cathodes similar to lithium ion secondary batteries.
  • the liquid organic electrolyte forms a gel with a polymeric separator (eg, PVdF, PVdF-HFP, PMMA, PAN, PEO, etc.), which helps to obtain a good bond between the separator and the electrode.
  • Gel electrolytes have higher ionic resistance than liquid electrolytes, but offer additional advantages in terms of safety and formation requirements.
  • Another embodiment of the present invention is an electric double layer capacitor, wherein the carbon-based electrode is organic or non-aqueous such as, for example, a solution of acetonitrile or propylene carbonate and a 1.2 molar quaternary tetrafluoroammonium borate.
  • the electric double layer capacitor can be used together with an electrolyte or an aqueous electrolyte such as a 30 to 40% KOH solution. Moreover, in this invention, it can be set as the electric double layer capacitor depending on the reduction-oxidation chemical reaction which provides a capacitance.
  • Such electric double layer capacitors are referred to as “pseudocapacitors” or “redox capacitors”. Pseudocapacitors can use carbon, noble metal hydrated oxides, modified transition metal oxides and conductive polymer based electrodes, as well as aqueous and organic electrolytes.
  • Another embodiment of the present invention is an aluminum electrolytic capacitor that includes an etched aluminum foil anode, an aluminum foil or film cathode, and a separator interposed therebetween.
  • the separator and insulating material comprising the fine fiber structure of the present invention are impregnated with a liquid electrolytic solution or a conductive polymer.
  • the liquid electrolyte solution contains a polar solvent and at least one salt selected from an inorganic acid, an organic acid, an inorganic acid salt, and an organic acid salt.
  • the capacitor of the present invention includes two conductive aluminum foils and a separator immersed in an electrolyte, and one of the conductive aluminum foils may be coated with an insulating oxide layer.
  • the aluminum foil coated with the oxide layer is the anode, while the liquid electrolyte and the second foil function as the cathode.
  • the multilayer assembly is rolled up, secured with a pin connector, and placed in a cylindrical aluminum case.
  • the foil is high purity aluminum and billions of fine tunnels are chemically etched to increase the surface area in contact with the electrolyte.
  • the anode foil supports the capacitor dielectric, which is a thin layer of aluminum oxide (Al 2 O 3 ) chemically grown on the anode foil.
  • the electrolyte is a blend of components of different formulations according to voltage and operating temperature range. The main components are a solvent and a conductive salt as a solute that conducts electricity. Common solvents are ethylene glycol (EG), dimethylformamide (DMF) and gammabutyllactone (GBL). Common solutes are ammonium borate and other ammonium salts. A small amount of water is added to the electrolyte to maintain the integrity of the aluminum oxide dielectric.
  • the separator can prevent the foil electrolytes from contacting each other or from being short-circuited, and can hold the electrolyte container.
  • the fine fiber structure layer of the present invention and the formation process of the fine fiber layer constituting the fine fiber structure layer may be a known electrospinning process, or WO 2003/080905 (US Patent Application No. 10 / 822,325).
  • the electroblowing process disclosed in (1) can be employed.
  • a single fine fiber layer (fiber web) is formed by passing once through the transport and collection means passing through the above process (that is, once through the transport and collection means under the spin pack).
  • the fibrous web can also be multi-layered by passing under one or more spin packs arranged on the same conveying means.
  • the collected fine fiber layer can improve the tensile strength by bonding fibers, for example.
  • the bonding method between the fine fibers is not particularly limited, but a known method such as thermal calendering between heated and smooth nip rolls, ultrasonic bonding, point bonding, and bonding that can pass through a high-temperature atmosphere should be adopted. Can do.
  • the fine fiber layer Due to the bonding between the fibers, the fine fiber layer is improved in handleability, and the strength of the fine fiber layer can be imparted to form a separator for a battery, an electric double layer capacitor, a capacitor, or an insulating material.
  • physical properties such as thickness, density, hole diameter, and shape can be adjusted depending on the bonding method.
  • thermal calendering it is necessary that the fine fibers are melted and fused excessively until individual fiber forms are lost, so as not to form a complete film.
  • a fine fiber layer fine fiber web obtained by electrospinning, electroblowing or the like or a multilayer fine fiber layer obtained by laminating the same is applied to a metal roll heated to 250 to 350 ° C.
  • a fine fiber structure satisfying the bending resistance by the method can be produced.
  • the above processing is not limited to polymers and the like, but it has been found that the processing is particularly effective in adjusting the bending resistance of fine fiber structures made of polyimide, aromatic polyamide, semi-aromatic polyamide, and the like.
  • the fine fiber structure of the present invention may be a single layer or a multilayer of fine fiber layers made of polymer fine fibers.
  • the fiber structure When the fiber structure is composed of multiple layers, it may be composed of a fine fiber layer composed of the same polymer fine fiber, or may be composed of a fine fiber layer of different polymer fine fibers.
  • a fine fiber layer different in at least one of polymer, thickness, basis weight, pore diameter, fiber size, porosity, air permeability, ionic resistance, tensile strength, etc. is laminated. May be.
  • the fine fiber structure of the present invention only needs to include at least one fine fiber layer satisfying the requirements of the present invention, and does not satisfy the requirements of the present invention, for example, fibers, as long as the object of the present invention is not impaired.
  • a fiber structure such as a wet nonwoven fabric or a dry nonwoven fabric having a diameter exceeding 3000 nm, a porous resin film, or the like may be included.
  • each characteristic value in an Example was measured with the following method.
  • (1) Average diameter of fine fibers Arbitrary 50 fine fibers were sampled and measured with a scanning electron microscope JSM6330F (manufactured by JEOL) to obtain the average value of the fiber diameters. The measurement was performed at a magnification of 20,000 times.
  • Porosity (%) 100-basis weight / (polymer density ⁇ thickness) ⁇ 100 (8) Macmillan number
  • a fine fiber layer is cut into 20 mm ⁇ , sandwiched between two SUS electrodes, and calculated by dividing the ionic conductivity of the electrolyte by the conductivity calculated from the AC impedance at 10 kHz.
  • the electrolyte used was 0.5 molar lithium trifluoromethanesulfonate (LiTFS), propylene carbonate: ethylene carbonate: dimethoxyethane (22: 8: 70), and the measurement temperature was 25 ° C.
  • the sample measured the Macmillan number by said method using the sample before performing the process of the next winding cancellation
  • Thermal contraction rate (%) (sample length before heat exposure ⁇ sample length after heat exposure) / sample length before heat exposure ⁇ 100 [Example 1]
  • the target polymer was produced by the following interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863. 25.13 g (99 mol%) of isophthalic acid dichloride and 0.25 g (1 mol%) of terephthalic acid dichloride as a third component were dissolved in 125 ml of tetrahydrofuran having a water content of 2 mg / 100 ml and cooled to ⁇ 25 ° C.
  • both surfaces of the obtained fine fiber web are brought into contact with and passed through a metal roll heated to 300 ° C., and then calendering is performed at a roll surface temperature of 150 ° C.
  • the measurement was performed at a linear pressure of 75 kg / cm to obtain a fine fiber structure composed of one porous fine fiber layer.
  • Table 1 [Example 2]
  • both sides of the obtained fine fiber web are passed through a metal roll heated to 250 ° C., and then calendering is performed at a roll surface temperature of 100 ° C. and a linear pressure.
  • Example 3 In the process of hot-pressing the fine fiber web, both surfaces of the obtained fine fiber web are passed through a metal roll heated to 350 ° C., and then calendering is performed at a roll surface temperature of 200 ° C. and a linear pressure. A fine fiber structure shown in Table 1 was obtained in the same manner as in Example 1 except that the measurement was performed at 75 kg / cm. The results are shown in Table 1.
  • Example 3 In the process of hot-pressing the fine fiber web, both surfaces of the obtained fine fiber web are passed through a metal roll heated to 350 ° C., and then calendering is performed at a roll surface temperature of 200 ° C. and a linear pressure. A fine fiber structure shown in Table 1 was obtained in the same manner as in Example 1 except that the measurement was performed at 75 kg / cm. The results are shown in Table 1.
  • the calendering process is performed only on the roll surface temperature of 300 ° C.
  • Example 2 A fine fiber structure shown in Table 1 was obtained in the same manner as in Example 1 except that the measurement was performed at / cm. The results are shown in Table 1.
  • the evaluation was performed using a cellulose separator for an electricity storage device (manufactured by Nippon Advanced Paper Industries, polymer density 1.5 g / cm 3 ). The results are shown in Table 1.
  • the fine fiber structure of the present invention is wrinkled or deformed due to bending or bending even when a roller or guide having a small diameter is passed or wound on a winding bobbin in the manufacturing or processing steps.
  • it is excellent in ion permeability and short circuit resistance at the same time.
  • the fine fiber structure can be used for a separator or an insulating material, and can be fully utilized without being affected by wrinkles, etc., and a high performance battery, electric double layer capacitor, capacitor, etc. can be manufactured. it can.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne une structure à fibres fines qui n'est pas affectée par des plissements ou des déformations de forme à cause d'une rupture ou d'une courbure même si elle est passée par un rouleau ou un guide de petit diamètre ou enroulée sur une bobine d'enroulement lors d'étapes de fabrication ou de traitement, et qui présente simultanément d'excellentes propriétés de perméabilité aux ions, de résistance aux courts-circuits et similaires, et qui est adaptée à être utilisée comme séparateur ou matériau isolant pour une batterie, un condensateur à double couche électrique, un condensateur électrique, ou un appareil similaire. L'invention concerne une structure à fibres fines comprenant une couche poreuse de fibres fines constituée de fibres fines polymériques avec un diamètre moyen entre 50 et 3000 nm, la structure à fibres fines étant caractérisée en ce que la résistance à la courbure de la structure à fibres fines selon une méthode en porte-à-faux à 45° est inférieure ou égale à 100 mm, et la taille moyenne des pores, l'épaisseur, la porosité, la masse surfacique, la perméabilité à l'air Frazier et le nombre de Macmillan dans la couche poreuse de fibres fines sont respectivement de 0,01 à 15 μm, 0,0025 à 0,3 mm, 20 à 90 %, 1 à 90 g/m2, moins de 46 m3/min/m2, et 2 à 15.
PCT/JP2013/067960 2012-06-25 2013-06-25 Structure à fibres fines WO2014003192A1 (fr)

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JP2012142153 2012-06-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023184182A1 (fr) * 2022-03-29 2023-10-05 宁德新能源科技有限公司 Dispositif électrochimique et dispositif électronique
WO2023184180A1 (fr) * 2022-03-29 2023-10-05 宁德新能源科技有限公司 Appareil électrochimique et appareil électronique

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JP2006089851A (ja) * 2003-10-09 2006-04-06 Kuraray Co Ltd 極細長繊維不織布とその製造方法およびその用途
JP2006188770A (ja) * 2004-12-10 2006-07-20 Japan Vilene Co Ltd 不織布及び不織布の製造方法、並びに不織布を用いた電気二重層キャパシタ用セパレータ、リチウムイオン二次電池用セパレータ、電気二重層キャパシタ又はリチウムイオン二次電池
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
JP2010504444A (ja) * 2006-09-20 2010-02-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 改良されたナノウェブ
WO2010044264A1 (fr) * 2008-10-15 2010-04-22 株式会社巴川製紙所 Séparateur de dispositif de stockage d’énergie
JP2011184815A (ja) * 2010-03-05 2011-09-22 Teijin Techno Products Ltd 芳香族ポリアミド極細繊維の製造方法及び芳香族ポリアミド極細繊維
JP2012069339A (ja) * 2010-09-22 2012-04-05 Teijin Techno Products Ltd 電池用セパレーター

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006089851A (ja) * 2003-10-09 2006-04-06 Kuraray Co Ltd 極細長繊維不織布とその製造方法およびその用途
JP2006188770A (ja) * 2004-12-10 2006-07-20 Japan Vilene Co Ltd 不織布及び不織布の製造方法、並びに不織布を用いた電気二重層キャパシタ用セパレータ、リチウムイオン二次電池用セパレータ、電気二重層キャパシタ又はリチウムイオン二次電池
JP2010504444A (ja) * 2006-09-20 2010-02-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 改良されたナノウェブ
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
WO2010044264A1 (fr) * 2008-10-15 2010-04-22 株式会社巴川製紙所 Séparateur de dispositif de stockage d’énergie
JP2011184815A (ja) * 2010-03-05 2011-09-22 Teijin Techno Products Ltd 芳香族ポリアミド極細繊維の製造方法及び芳香族ポリアミド極細繊維
JP2012069339A (ja) * 2010-09-22 2012-04-05 Teijin Techno Products Ltd 電池用セパレーター

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023184182A1 (fr) * 2022-03-29 2023-10-05 宁德新能源科技有限公司 Dispositif électrochimique et dispositif électronique
WO2023184180A1 (fr) * 2022-03-29 2023-10-05 宁德新能源科技有限公司 Appareil électrochimique et appareil électronique

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