WO2014142450A1 - Procédé de préparation de membrane de séparation poreuse pour batterie secondaire et membrane de séparation poreuse pour batterie secondaire préparée ainsi - Google Patents

Procédé de préparation de membrane de séparation poreuse pour batterie secondaire et membrane de séparation poreuse pour batterie secondaire préparée ainsi Download PDF

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WO2014142450A1
WO2014142450A1 PCT/KR2014/001566 KR2014001566W WO2014142450A1 WO 2014142450 A1 WO2014142450 A1 WO 2014142450A1 KR 2014001566 W KR2014001566 W KR 2014001566W WO 2014142450 A1 WO2014142450 A1 WO 2014142450A1
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polymer
porous separator
inorganic
separator
electrospinning
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Korean (ko)
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박종철
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Lime Co Ltd
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Finetex Ene Inc
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Priority claimed from KR1020130026999A external-priority patent/KR101447565B1/ko
Priority claimed from KR1020130027003A external-priority patent/KR101402976B1/ko
Priority claimed from KR20130027002A external-priority patent/KR101479749B1/ko
Priority claimed from KR1020130026998A external-priority patent/KR101447564B1/ko
Priority claimed from KR1020130027005A external-priority patent/KR101402981B1/ko
Priority claimed from KR1020130027004A external-priority patent/KR101402979B1/ko
Application filed by Finetex Ene Inc filed Critical Finetex Ene Inc
Publication of WO2014142450A1 publication Critical patent/WO2014142450A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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 method for manufacturing a porous separator for secondary batteries using electrospinning and to a porous separator for secondary batteries prepared according to the above, and more particularly, to a method for manufacturing a porous separator for secondary batteries using a bottom-up electrospinning and thus prepared It relates to a porous separator for secondary batteries.
  • a lithium secondary battery which includes a positive electrode, a negative electrode, an electrolyte, and a separator.
  • the positive electrode active material used for the positive electrode is a material capable of occluding and releasing lithium, and a composite of lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium nickel cobalt oxide, lithium iron phosphate oxide, and the like. Metal oxides are mainly used.
  • the negative electrode active material in the negative electrode is lithium alloy, carbon (carbon), cokes (activated carbon), graphite (graphite), silicon (Si), tin (Sn), etc. that can occlude and release lithium Metals and / or alloys and the like are mainly used.
  • the electrolyte is a non-aqueous electrolyte containing a lithium salt and an organic solvent
  • the lithium salt is LiClO 4 , LiCF 3 SO 3 , LiAsF 6 , LiBF 4 , LiPF 6 , LiSCN, LiC (CF 3 SO 2 ) 3 , LiBOB Ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), dimethoxyethane (DME), diethoxyethane (DEE), 2-methyltetrahydrofuran (2-MeTHF) are used as the organic solvent.
  • Dimethyl sulfoxide (DMSO) and the like are used individually or in combination.
  • the separator is one of the four core materials constituting the battery, which is located between the positive and negative electrodes of the battery to increase the stability of the battery by separating the lithium oxide, a highly active positive electrode material reacts directly with the negative electrode to prevent explosion Since it plays a role and is located between two electrodes, it has a structure in which pores are developed to smoothly move lithium ions between electrodes.
  • the thinner the separator the smaller the volume in the battery, and the greater the amount of electricity produced per unit volume. Therefore, the priority item for manufacturing the separator is thickness.
  • the strength of the separator is weakened. Therefore, the mechanical and thermal strength and durability of the separator must be focused. High temperature storage and overcharging of batteries are related to the thermal stability of the separator, and the safety problems caused by nail penetration and foreign matter are related to mechanical properties.
  • secondary batteries including high energy density and large capacity lithium ion secondary batteries, lithium ion polymer batteries, and supercapacitors (electric double layer capacitors and similar capacitors) must have a relatively high operating temperature range and continuously maintain high rate charge and discharge conditions. Since the temperature rises when used, the separators used in these batteries are required to have higher heat resistance and thermal stability than those required for ordinary separators. In addition, it should have excellent battery characteristics such as high ion conductivity that can cope with rapid charging and discharging and low temperature.
  • the separator is positioned between the anode and the cathode of the battery to insulate it, maintains the electrolyte to provide a path for ion conduction, and when the temperature of the battery becomes too high, a part of the separator melts to block pores in order to block the current.
  • the membrane should have a low shut-down temperature and a higher short-circuit temperature.
  • a contraction occurs at 150 ° C. or higher to expose an electrode part, thereby causing a short circuit. Therefore, it is very important to have both the closing function and the heat resistance for high energy density and large sized secondary battery.
  • Porous nanofibers can be used in various applications because of their wide surface area and excellent porosity.
  • the porous nanofibers can be used for water purification filters, air purification filters, composite materials, and battery separators.
  • such porous nanofibers can be usefully applied to the separator of a fuel cell for automobiles.
  • nanofiber refers to ultra-fine fibers having a diameter of only tens to hundreds of nanometers.
  • Products such as nonwoven fabrics, membranes, and braids composed of nanofibers are used for household goods, agriculture, and clothing. Widely used in the industrial and industrial applications.
  • Such nanofibers are produced by an electric field. That is, the nanofibers generate an electric repulsive force inside a polymer material as a raw material by applying an electric field of high voltage to the polymer material as a raw material, and thus, the molecules are agglomerated into nano-sized yarns to manufacture and produce the nanofibers.
  • the stronger the electric field, the thinner the polymer material is separated from the raw material can be obtained a nanofiber having a diameter of 10 to 1000nm.
  • the electrospinning apparatus for manufacturing and producing nanofibers having such diameters includes a spinning liquid main tank in which spinning solution is filled, a metering pump for quantitatively supplying spinning solution, and a plurality of nozzles for ejecting spinning solution. It is configured to include a nozzle block to be installed, a collector that is located at the bottom of the nozzle to aggregate the fibers to be emitted and a voltage generator for generating a voltage.
  • the spinning solution in the spinning solution main tank is continuously metered into a plurality of nozzles to which a high voltage is applied through a metering pump, and is supplied to the nozzle.
  • the working liquid is spun and concentrated through a nozzle on a collector to which high voltage is applied to form a short fiber web, and the short fiber web is embossed or needle punched to produce nanofibers.
  • the electrospinning device is divided into a bottom-up electrospinning device, a top-down electrospinning device and a horizontal electrospinning device according to the direction in which the collector is located.
  • the electrospinning device is a bottom-up electrospinning device having a configuration in which the collector is located at the top of the nozzle, a top-down electrospinning device having a configuration in which the collector is located at the bottom of the nozzle, and a horizontal electric in which the collector and the nozzle are arranged in the horizontal direction. It is divided into a radiator.
  • the production of nanofibers using a top-down electrospinning device has a problem in that the spinning liquid falls as it is in the form of water droplets (hereinafter referred to as "droplet") when spinning, the quality of the product is reduced.
  • droplet water droplets
  • the polymers used in the manufacture of nanofibers can be broadly divided into organic polymers and inorganic polymers.
  • organic polymers are inexpensive, light, and do not oxidize well. It acts as an insulator.
  • organic polymers have some fatal disadvantages despite these advantages.
  • Special functionalities (metallic) of inorganic polymers that are not present in dots and organic polymers are emerging as problems.
  • the polyacrylonitrile-based polymer has been widely used as an industrial fiber because of its excellent physicochemical stability and excellent chemical resistance and mechanical properties.
  • it is relatively hydrophobic than polymers such as nylon and polyvinyl alcohol, so it is known as a very suitable material as a filter material because it has excellent electrostatic retention capability when producing ultra-fine fibers through electrospinning and electrostatic processing.
  • nanofibers can be widely used as a sanitary agent, agricultural horticulture, food distribution, civil construction, toiletries, medicines, and electrical and electronic materials.
  • PVDF polyvinylidene fluoride
  • Polyvinylidene fluoride is prepared by the same process as the above scheme, and has a lower melting point (177 ° C) and density (1.78 g / cm 3 ), lower unit cost, and is highly chemically stable than other fluoro resins. It is often used as a high-quality paint for the insulation of buildings and the exterior walls of buildings.
  • polyvinylidene fluoride is a representative organic material exhibiting piezoelectricity and many studies have been conducted since the 1960s.
  • Four crystals are mixed in the polyvinylidene fluoride polymer, which can be classified into at least four types of ⁇ , ⁇ , ⁇ , and ⁇ , depending on the crystal form.
  • the ⁇ -type crystals of polyvinylidene fluoride are filled with trans-type molecular chains in parallel, and all of the permanent dipoles of the monomers are arranged in one direction, thereby showing large spontaneous polarization.
  • the polyvinylidene fluoride molecules can be regularly arranged through stretching to impart anisotropy to the aggregated state so that they can have piezoelectricity.
  • melt spinning systems have been applied to produce polyvinylidene fluoride fibers.
  • the high cost of building melt spinning equipment is expensive, and the size of the fiber produced by melt spinning is also limited.
  • the fiber produced by wet spinning has a significantly higher ⁇ -crystal ratio in the fiber at the initial stage of spinning than ⁇ -crystal ratio and a slower spinning speed than melt spinning, but increases the number of spinnerets. It also has the advantage of reducing fiber size.
  • Wet spinning also has the advantage of improving physical properties through a continuous post-treatment process (stretching, crimping, etc.).
  • the polymer is dissolved in a solvent to form a spinning solution (Dope), and the spinning solution is discharged into a coagulation bath containing an aqueous solution containing a solvent through a gear pump and a spinning nozzle.
  • a spinning solution Dope
  • the precipitant penetrates into the spinning liquid phase, and the filament solidifies as the phase separation and precipitation occur in the three-component system of polymer-solvent-precipitant. Is obtained.
  • Such a wet spinning system has the advantage that the mechanical properties of the fibers can also be improved by giving the stretching and tension in the spinning bath to orient the chain-shaped polymer in the fiber direction.
  • polyimide (PI) is a representative of high heat-resistant engineering plastics synthesized from aromatic diamine and aromatic tetracarboxylic dianhydride, and has excellent rigidity and dimensional stability.
  • polyimide whose molecular structure is relatively symmetrical, exhibits the highest heat resistance among engineering plastics.
  • the continuous use temperature is 288 ° C and the intermittent use temperature is 480 ° C.
  • polyimide has excellent electrical insulation, and the insulation breakdown voltage is 22 kV / mm in the wholly aromatic type.
  • the membrane using the polyimide is excellent in mechanical strength and heat resistance to high temperature, it is chemically stable and has a high permeability.
  • Aramid fibers are defined as 'fibers of molecular structure in which at least 85% of amide bonds (-NHCO-) are bonded between aromatic rings'. Are distinguished.
  • Aramid is divided into para-aramid and meta-aramid according to the bond form of benzene ring. Since para-aramid has high strength properties, it is mainly used as a material for body armor, and meta-aramid is not easily melted even at a high temperature of 400 ° C or higher than general fibers. Due to its outstanding characteristics, it is used for protective clothing including firefighting suits, battery insulating paper, industrial filters, industrial materials and construction.
  • Meta aramid refers to poly-meta-phenylene terephthalamide in which the amide bond is bonded to the meta position of the benzene ring, and has a structure represented by the following formula (1).
  • Metaaramid is the first high heat-resistant aramid fiber and can be used at 350 °C for a short time and 210 °C for continuous use, and when exposed to higher temperatures, it does not melt or burn like other fibers. . Above all, unlike other products that have been flame retardant or fireproof, it does not emit toxic gases or harmful substances even when carbonized and has excellent properties as an environmentally friendly fiber.
  • the meta-aramid has a very rigid molecular structure of the molecules constituting the fiber, not only the inherent strength is strong, but also the molecules are easily oriented in the fiber axial direction in the spinning step, thereby increasing the crystallinity. Can improve.
  • the inorganic polymer refers to a polymer containing an inorganic element in the polymer main chain or side chain.
  • Inorganic elements are narrowly divided into various metals (aluminum filling the s and p orbits, typical metals such as magnesium, titanium, zirconium, tungsten filling, transition metals such as tungsten, and internal transitions such as the lanthanide-actinium filling the f orbit. Metal), but broadly includes a skeleton formed of elements such as Si, Ge, P, and B, which are nonmetallic inorganic elements.
  • Inorganic polymers are divided into four types:
  • SiC silicon carbide
  • NICALON polycarbosilane
  • the application method of the composite of the inorganic polymer to the polymer is polymer impregnation and pyrolysis (PIP) method, which is made by mixing organic compounds such as PCS with silicon carbide powder to make a slurry, and then turning the slurry into silicon carbide It is a method of obtaining a silicon carbide matrix by penetrating into a fiber preform and pyrolyzing. Recently, attention has been paid to the development of fibers having excellent heat resistance. Therefore, by developing a new organic compound having excellent properties and improving the PIP method, it is possible to produce a silicon carbide matrix with an excellent crystallinity and stoichiometric ratio by increasing the thermal decomposition temperature.
  • PIP polymer impregnation and pyrolysis
  • silicon carbide (SiC) and silicon nitride (Si 3 N 4 ) ceramics are thermally and chemically stable at high temperatures, and have strong strengths. It is widely used in industry, nuclear reactor business, shelf-building machine, sports product manufacturing, etc., and various industrial uses such as manufacturing these ceramics in the form of film or fiber for special use. Silicon polymers are economical due to the low cost of raw materials and high polymerization yields, and can freely adjust the ratio of Si and C or N in the molecule, and can be formed by high meltability and solubility, thereby increasing the residual yield of ceramics. In order to achieve this, crosslinking may be performed by various chemical reactions. Depending on the thermal decomposition conditions can be easily selected, such as silicon carbide (SiC) and silicon nitride (Si 3 N 4 ), it can also be prepared by mixing with metal and pyrolysis.
  • SiC silicon carbide
  • Si 3 N 4 silicon nitride
  • a lithium ion secondary battery using a conventional polyolefin separator and a liquid electrolyte solution, or a conventional lithium ion polymer battery using a polymer electrolyte coated with a gel polymer electrolyte membrane or a polyolefin separator is used for high energy density and high capacity batteries in terms of heat resistance. It is very lacking. Therefore, it does not satisfy the heat resistance and safety required for high capacity, large area batteries such as automotive.
  • polyolefin-based films such as polyethylene (PE) and polypropylene (Polyprophylene, PP) are mainly used as separators used in lithium ion batteries.
  • Polyolefins suffer from the disadvantages of high heat shrinkage and physical weakness at high temperatures. Have.
  • US Patent Publication No. 2006-0019154 impregnated a polyolefin-based separator in a solution of polyamide, polyimide, polyamideimide having a melting point of 180 ° C. or higher, and then immersed in a coagulating solution to extract a solvent to obtain porous heat resistance.
  • a heat-resistant polyolefin separator in which a thin resin layer is bonded is proposed, and the heat shrinkage is small, and the heat resistance and excellent cycle performance are claimed.
  • the heat-resistant thin layer imparts porosity
  • the polyolefin separator used is also limited to using an air permeability of less than 200 seconds / minute.
  • heat-resistant resins such as aromatic polyamides, polyimides, polyethersulfones, polyetherketones, and polyetherimides having a melting point of 200 ° C. or higher in order to ensure sufficient safety at high energy density and size increase
  • the solution was applied to both sides of the polyolefin separator and immersed in a coagulating solution, washed with water and dried to give a polyolefin separator to which a heat resistant resin was adhered.
  • a phase separator for imparting porosity was contained in the heat resistant resin solution and the heat resistant resin layer was also limited to 0.5-6.0 g / m 2 .
  • the immersion of the heat resistant resin prevents the movement of lithium ions by blocking the pores of the polyolefin separation membrane, so that the charge and discharge characteristics are lowered, so that even if the heat resistance is secured, it is less than the capacity required for a large capacity battery such as an automobile.
  • the porosity of the commonly used polyolefin separator is about 40% and the pore size is also several tens of nm in size, so there is a limit in ion conductivity for large capacity batteries. .
  • US Pat. No. 6,447,958B1 discloses a slurry obtained by dissolving and dispersing a ceramic powder and a heat-resistant nitrogen-containing aromatic polymer in an organic solvent.
  • a porous woven fabric such as polyolefin, rayon, vinylon, polyester, acrylic, polystyrene, and nylon as a support, nonwoven fabric, paper, porous
  • the heat resistant polymer layer is introduced in the process of introducing a heat resistant polymer layer, and a process of preparing a porous heat resistant resin layer including application of the heat resistant resin and immersion in a coagulating solution, washing with water, and drying. This is a very complicated and costly problem.
  • Japanese Patent Laid-Open Nos. 2001-222988 and 2006-59717 disclose gel electrolytes of polymers such as polyethylene oxide, polypropylene oxide, polyether, and polyvinylidene in polyaramid, polyimide woven fabric, nonwoven fabric, cloth, and porous film having a melting point of 150 ° C. or higher. It is impregnated or apply
  • the required heat resistance may be satisfied, but in terms of ion conduction, ion transport in the support or the heat-resistant aromatic polymer layer is still limited similarly to the case of the separator or gel electrolyte of a conventional lithium ion battery.
  • Nafion resins perfluorosulfonic acid resins
  • fluorine resins fluorine resins
  • Nafion resins have a weak mechanical strength, so that when used for a long time, pinholes are generated, thereby lowering energy conversion efficiency.
  • Attempts have been made to increase the film thickness of Nafion resin in order to reinforce mechanical strength.
  • the resistance loss is increased, and there is a problem in that the economy is inferior due to the use of expensive materials.
  • the conventional patent technology still does not satisfy the heat resistance and ion conductivity at the same time, there is no mention of the shut-down function (SHUTDOWN FUNCTION) of the membrane, the vehicle that requires excellent performance under harsh conditions such as heat resistance and rapid charge and discharge It is not yet satisfactory for high energy density and high capacity batteries such as solvent.
  • SHUTDOWN FUNCTION shut-down function
  • the nonwoven fabric when used as a membrane material as another method to increase the thermal stability of the membrane, it has a high porosity of about 60 to 80% because of the fibrous mat shape formed by chemical, physical or mechanical connection of natural or synthetic fibers. Porosity and a large melting point (melting point).
  • These non-woven fabrics have been used in nickel-cadmium batteries, but they are not applied to lithium secondary batteries because they have excellent mechanical strength and are difficult to prevent short circuits due to their relatively large open structure and rough surface. .
  • polyester nonwoven membranes have been studied to improve safety and lifespan, and high-temperature safety and uniform pore structure have been reported to improve lifespan using high melting point of polyester.
  • Electrospinning is a technology that can produce ultra-fine fibers and porous webs, ie, nonwoven fabrics, from several nm to several micrometers in diameter by using electrostatic spraying of high-viscosity fluids such as polymers. It is a device that can spin fine fibers by pulling.
  • the polymer solution at the end of the capillary tube located vertically in the electrospinning device equilibrates between gravity and surface tension to form hemispherical droplets.
  • This phenomenon is caused by the charge or dipole orientation at the surface of the hemispherical droplets when the electric field is applied. Force or dipole repulsion, thus creating a force opposite to the surface tension.
  • the hemispherical surface of the solution suspended at the end of the capillary stretches into a conical shape known as the Taylor cone, which at certain critical field strengths (Vc) overcomes the surface tension as the jet of charged polymer solution (Jet) ) Is released from the end of the Taylor cone.
  • the jet collapses into microdroplets, indicating a spray phenomenon.
  • the jet does not collapse and the solvent evaporates as it flows into the air toward the current collector plate, and the charged polymer continuous phase fibers accumulate on the current collector plate. This phenomenon is called electrospinning. .
  • the reason why very thin fibers are produced by the electrospinning is that the jet is thinned by the elongation and spray phenomenon of the jet as it flows toward the current collector plate. Because of this small diameter, the electrospun fibers have a larger surface area and volume, and can absorb more moisture than other large diameter fibers.
  • the ultra-fine fibrous web prepared as described above is ultra thin and ultra light, and has a very high surface area to volume ratio and high porosity as compared to conventional fibers. Therefore, it is structurally respirable and windproof to discharge sweat, and it is also possible to manufacture the liquid from entering the outside of the membrane. Therefore, research is being conducted to apply the electrospinning phenomena of polymers to various fields such as the manufacture of ultra-high performance filters, porous supports for tissue engineering, and chemical sensors.
  • the inorganic composite separator or the ceramic separator is manufactured by connecting inorganic particles of very fine size to each other with a small amount of binder.
  • Their high hydrophilicity and large specific surface area result in excellent wettability in the electrolyte, and excellent wettability in electrolytes such as EC and PC improve battery life and performance.
  • These ceramic separators have very good thermal stability and hardly shrink at high temperatures.
  • Such a ceramic separator shows excellent electrolyte wetting and thermal stability, but has a disadvantage in that it does not show a level of mechanical properties, particularly flexibility, suitable for a battery assembly process including winding.
  • the present invention is to provide a method for producing a secondary battery separator using a bottom-up electrospinning porous porous membrane for secondary batteries made of a high quality nanofiber without the droplet (Droplet) using a bottom-up electrospinning. The purpose.
  • the present invention includes a polymer nanofiber, in order to improve the low thermal stability of the polyolefin substrate and the low degree of clarity of the electrolyte, an inorganic layer that can improve the electrolyte wettability by coating the inorganic particles on the polymer nanofiber It is also an object to provide a porous separator for secondary batteries with improved battery stability and output characteristics by being firmly coupled.
  • the present invention comprises the steps of preparing a polymer solution by dissolving the polymer in a solvent; And it provides a method for producing a porous separator for secondary batteries comprising the step of electrospinning the polymer solution to produce nanofibers.
  • the polymer is preferably a heat resistant polymer or an inorganic polymer.
  • the heat resistant polymer is preferably at least one selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, metaaramid and polyimide.
  • the inorganic polymer is a single polymer containing a silane group or a siloxane group, or monomethacrylate, vinyl, hydride, distearate, bis (12-hydroxy-stearate), methoxy to the silane group or siloxane group.
  • Ethoxylate, propoxylate diglycidyl ether, monoglycidyl ether, monohydroxy, bis (hydroxyalkyl), chlorine, bis (3-aminopropyl) and bis ((aminoethyl-aminopropyl
  • it is a copolymer polymer containing a bonding group selected from the group consisting of a) dimethoxysilyl) ether.
  • the polymer solution may be electrospun on a polyolefin substrate or a polyolefin substrate coated with an inorganic material.
  • the electrospinning is preferably performed by a bottom-up electrospinning method.
  • the method may further include forming an inorganic coating layer by coating an inorganic slurry including an inorganic material and a binder on the nanofibers.
  • the inorganic slurry is preferably a weight ratio of the inorganic material and the binder is 95: 5 to 50:50.
  • the inorganic material is SiO 2 , Al 2 O 3 , TiO 2 , Li 3 PO 4 , zeolite, MgO, CaO, BaTiO 3 , Li 2 O, LiF, LiOH, Li 3 N, BaO, Na 2 O, Li 2 CO 3 , CaCO 3 , LiAlO 2 , SiO, SnO, SnO 2 , PbO 2 , ZnO, P 2 O 5 , CuO, MoO, V 2 O 5 , B 2 O 3 , Si 3 N 4 , CeO 2 , Mn 3 It is preferably one kind selected from the group consisting of O 4 , Sn 2 P 2 O 7 , Sn 2 B 2 O 5 , Sn 2 BPO 6, and mixtures thereof.
  • the binder is preferably one selected from the group consisting of polyacrylonitrile, polyvinylidene fluoride, polyimide, metaaramid, polymethyl methacrylate, carboxymethyl cellulose, polyvinyl alcohol, and styrene butadiene rubber. .
  • the present invention comprises the steps of dissolving the polymer in a solvent to prepare a polymer solution; And dividing at least two or more spinning sections in a progressing direction of the bottom-up electrospinning apparatus, and spinning the polymer solution in each of the divided spinning sections.
  • the present invention also provides a porous separator for secondary batteries comprising a polyolefin substrate and a polymer nanofiber layer formed on one surface of the polyolefin substrate by an electrospinning method.
  • the secondary battery porous separator may further include an inorganic coating layer formed by coating an inorganic material on one surface of the polymer nanofiber layer.
  • the porous separator for secondary batteries according to the present invention is composed of nanofibers prepared by electrospinning, and is in a porous form, and exhibits excellent thermal stability as compared to a conventional polyolefin-based film separator, and inorganic particles on the porous separator. By coating a thin thickness can improve the thermal stability of the separator.
  • the porous separator of the present invention when the porous separator of the present invention is applied to a secondary battery, by improving the hydrophilicity of the electrolyte by improving the surface of the non-polar polymer to improve the mobility of lithium ions, it is possible to improve the stability and output characteristics of the battery.
  • FIG. 1 is a view schematically showing an electrospinning device for manufacturing a porous separator for secondary batteries according to the present invention.
  • FIG. 2 is a view schematically showing an enlarged portion of an electrospinning apparatus for manufacturing a porous separator for secondary batteries according to the present invention.
  • FIG 3 is a view schematically showing a porous separator prepared according to the method of manufacturing a porous separator for secondary batteries according to an embodiment of the present invention.
  • FIG. 4 is a view schematically showing a porous separator manufactured according to a method of manufacturing a porous separator for a secondary battery according to another embodiment of the present invention.
  • the method of manufacturing a porous separator for a secondary battery according to the present invention includes dissolving a polymer in a solvent to prepare a polymer solution, and electrospinning the polymer solution to produce nanofibers.
  • FIG. 1 is a view schematically showing an electrospinning apparatus for manufacturing a porous separator for secondary batteries according to an embodiment of the present invention
  • Figure 2 is a part of the electrospinning apparatus for manufacturing a porous separator for secondary batteries according to the present invention It is a figure which expands and shows schematically.
  • the electrospinning pump is a metering pump for quantitative supply of the polymer spinning solution filled in the spinning solution main tank (1) and the spinning solution main tank (1) filled with the polymer spinning solution therein (2) and discharge the polymer spinning solution in the spinning solution main tank (1), located in the nozzle block (4) and the lower end of the nozzle (5) in which a plurality of nozzles (5) in the form of fins are arranged
  • the nozzle block 4 of the electrospinning device is partitioned into a spinning section 31 in the direction of travel (horizontal direction), and each nozzle 11 of the nozzle block 10 located in each of the spinning sections is It is connected to each supply device 51, respectively.
  • the nozzle block 10 of the electrospinning device is partitioned into the radiating section 31 in the traveling direction (horizontal direction), and each nozzle of the nozzle block 4 located in the radiating section 31 ( 5) each supply device 51 is installed.
  • the number of the nozzle and the spinneret is not particularly limited, but may be one, may be a plurality of two or more.
  • the supply device 51 is supplied with a polymer.
  • the nozzle block 4 of the electrospinning apparatus is partitioned into each spinning section, and each nozzle 5 of the nozzle block 4 located in each spinning section 31 has a respective supply device ( 51) by spinning the polymer to obtain a separation membrane consisting of a single layer or a multilayer of two or more layers.
  • the spinning solution main tank 1 is preferably composed of different main tanks, and the different main tanks are each supply device 51. Connected to feed the polymer.
  • each of the supply devices 51 is formed in a closed cylindrical shape as a whole, and the spinning solution continuously supplied from the different main tanks 1 to the nozzles 5 located in each spinning section 31. Supply.
  • the spinning solution main tank 1 is made of different main tanks, but the different main tanks are connected to respective supply devices 51 to supply polymers.
  • the spinning solution main tank 1 consists of one main tank, the inside of which can be partitioned into a plurality of spaces, each compartment is filled with polymer, and each space is supplied to each supply device 51. It is also possible to be connected individually to supply the polymer.
  • the polymer may be made of the same polymer component, but is not limited thereto.
  • each of the spinning section 31 partitioned on the nozzle block 4 is the same, each of the spinning section 31 partitioned on the nozzle block 4
  • the interval distance of is preferably made to be adjustable according to the thickness of each layer constituting the separator.
  • the polymer is supplied to the nozzle 5 of the nozzle block 4 from each supply device 51 of the electrospinning apparatus and is radiated onto the collector 7 located in the spin section 31. Will form the nanofibers (6).
  • the nanofibers 6 formed by electrospinning at each supply device 51 may be formed by stacking two or more multilayer separators.
  • the electrospinning device of the present invention may be any of bottom-up, top-down or complex type, but it is more preferable to develop the bottom-up.
  • the present invention provides a polymer solution in which at least two or more polymers are dissolved in a solvent, and the nozzle block 4 of the bottom-up electrospinning apparatus partitions at least two or more spinning sections 31 in the advancing direction, Each of the polymer solution may be discharged from each of the divided spinning sections 31 to manufacture two or more layers of porous separators, and the polymer solutions discharged from the spinning sections may be different from each other.
  • the spinning solution filled in the spinning solution main tank 1 is metered by the metering pump 2 to supply a fixed amount to each supply device.
  • the spinning solution means a polymer solution in which a polymer is dissolved in an organic solvent.
  • the organic solvent that can be used is not particularly limited as long as it can sufficiently dissolve the polymer and is a solvent applicable to the charge induction spinning method, and when the porous polymer separator is prepared by the charge induction spinning method, the organic solvent is almost removed. Therefore, it may be used to affect the characteristics of the battery.
  • Non-limiting examples of such organic solvents include dimethylformamide, tetrahydrofuran, methylene chloride, chloroform, cyclohexane, propylene carbonate, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, dimethyl carbonate, 1 , 2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, ethylene carbonate, ethylmethyl carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl -2-pyrrolidone, polyethylene sulfolane, tetraethylene glycol dimethyl ether, acetone, alcohol, water or a mixture of any one or more thereof may be selected and used, more preferably dimethylformamide (DMF) or Preference is given to using dimethylacetamide (DMAc).
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • the lower collector is subjected to a high voltage through the nozzle (5) of the nozzle block (4) connected to each supply device (51) 7) to discharge each spinning solution to produce a nanofiber.
  • each spinning solution supplied through the supply device 51 is discharged from the nozzle 5 located in each spinning section 31 partitioned in the nozzle block 4 of the electrospinning device, each spinning solution
  • the multilayer separator may be prepared by stacking.
  • the thickness of the polyolefin substrate is 5 to 50 ⁇ m
  • the average pore size is 0.005 ⁇ 3 ⁇ m physical properties and the electrical resistance is 130 ⁇ 185 °C more than 10,000 ⁇ / cm 2 It is particularly suitable for use for electrochemical devices.
  • the nanofibers 6 electrospun from the nozzles 5 are collected on the collector 7 while being widely spread by the air injected from the air supply nozzles, so that the collection area becomes wider and the integration density becomes uniform. Excess spinning solution that has not been fiberized in the nozzle is collected in the overflow removing nozzle and is moved back to the spinning solution supply device 51 through the temporary storage plate of the overflow solution.
  • the diameter of the nanofibers may be the same or different from each other, the thickness of the membrane, the diameter of the fiber, the shape of the fiber, the mechanical properties of the separator, etc., the intensity of the applied voltage, the type of polymer solution, the viscosity of the polymer solution, the discharge It can be arbitrarily adjusted by changing electrospinning process conditions such as flow rate.
  • the air velocity in the air supply nozzle is preferably 0.05m ⁇ 50m / sec, more preferably 1 ⁇ 30m / sec.
  • the air velocity is less than 0.05 m / sec, the nanofiber spreading property of the collector is low and the collection area is not greatly improved.
  • the air velocity exceeds 50 m / sec, the air velocity is too fast and the nanofibers are collected. The area of focus is rather reduced, and the more serious problem is not the nanofibers but rather the coarse skew attached to the collector, which significantly reduces the nanofiber performance.
  • the environmental conditions of temperature and humidity are different depending on the polymer material, but it is preferable to spin at an environmental condition of temperature of 30 to 40 °C, humidity of 40 to 70%.
  • a voltage of 1 kV or more in the voltage generator more preferably 20 kV or more.
  • the collector 7 is more advantageous in terms of productivity using an endless belt, the collector 7 is preferably reciprocating a predetermined distance from side to side to make the density of the separator uniform.
  • the nanofibers produced by continuously treating the separator formed on the collector 7 with an embossing roller are wound on the winding roller 13 to complete the porous membrane manufacturing process.
  • the prepared porous separator may be made of a polymer nanofiber layer 73, or may include a polyolefin substrate 71 and a polymer nanofiber layer 73 formed on one surface of the polyolefin substrate. .
  • the manufacturing process can increase the trapping area to uniform the integration density of the nanofibers, effectively prevent the droplet (Droplet) phenomenon to improve the quality of the nanofibers, and the fiber forming effect by the electric force is increased Nanofibers can be produced in large quantities.
  • the nozzles composed of the plurality of pins in a block form, the width and thickness of the nanofibers and filaments can be freely changed and adjusted.
  • the diameter of the nanofibers produced by the method of manufacturing a porous separator for secondary batteries according to the present invention as described above is preferably 30 to 2000nm, more preferably 50 to 1500nm.
  • the electrolyte membrane for the fuel cell must include an ion conductor to smoothly move the ions.
  • the ion conductor In order for these ions to move smoothly in the electrolyte membrane, the ion conductor must be evenly filled throughout the nanofibers. However, if the voids are too small or too large, a problem arises in that the ion conductivity is lowered because the ion conductors are filled with a bias.
  • the nanofibers may be impregnated with the ionic conductor smoothly only when there are many pores having a specific pore size. In other words, if the pore is too small, the ion conductor may not be impregnated smoothly, while if the pore is too large, the ion conductor may be excessively impregnated.
  • the size of the pore size of such an ion conductor may be smoothly impregnated into the pores of the nanofibers not exceeding the range of ⁇ 0.2 ⁇ m.
  • the porosity of the porous separator is preferably 40% or more, more preferably 40 to 80%, when the porosity is low, it is not suitable for use as a separator for high performance secondary batteries.
  • the total thickness of the porous membrane is preferably 5 to 70 ⁇ m, more preferably 10 to 30 ⁇ m. If the thickness of the porous separator is thinner than 5 ⁇ m may be a problem in the battery manufacturing process because the strength is weak, if the thickness of more than 70 ⁇ m may decrease the ion conductivity.
  • the inorganic slurry prepared by adding the inorganic material and the binder to the acetone using the nanofiber separator prepared by the electrospinning method as described above may be coated on the nanofiber separator by a casting method to form the inorganic coating layer 75.
  • the porous separator may include a polymer nanofiber layer 73 and an inorganic coating layer 75 formed on one surface of the polymer nanofiber layer.
  • the porous separator may include a polyolefin substrate 71, a polymer nanofiber layer 73 formed on one surface of the polyolefin 71 substrate, and an inorganic coating layer 75 formed on one surface of the polymer nanofiber layer.
  • the inorganic material is SiO 2 , Al 2 O 3 , TiO 2 , Li 3 PO 4 , zeolite, MgO, CaO, BaTiO 3 , Li 2 O, LiF, LiOH, Li 3 N, BaO, Na 2 O, Li 2 CO 3 , CaCO 3 , LiAlO 2 , SiO, SnO, SnO 2 , PbO 2 , ZnO, P 2 O 5 , CuO, MoO, V 2 O 5 , B 2 O 3 , Si 3 N 4 , CeO 2 , Mn 3 O 4 , Sn 2 P 2 O 7 , Sn 2 B 2 O 5 , Sn 2 It may be one selected from the group consisting of BPO 6 and mixtures thereof, the size may be 0.5 ⁇ m, but is not limited thereto.
  • the binder may be one selected from the group consisting of polyacrylonitrile, polyvinylidene fluoride, polyimide, metaaramid, polymethyl methacrylate, carboxymethyl cellulose, polyvinyl alcohol, and styrene butadiene rubber, It is used to coat the inorganic particles on nanofibers.
  • the weight ratio of the inorganic material and the binder is not particularly limited, but is preferably 95: 5 to 50:50.
  • the coating method may use various coating methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spray coating, dip coating, spin coating, and casting method. In particular, coating by a casting method is preferred.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • thermal spray coating dip coating
  • spin coating spin coating
  • casting method coating by a casting method is preferred.
  • the spinning solution means a solution in which each polymer is dissolved in an organic solvent.
  • the polymers may be the same or different from each other, and each of the polymers is preferably a heat resistant polymer or an inorganic polymer.
  • Non-limiting examples of the heat resistant polymer include polyvinylidene fluoride, polyvinylidene fluoride-hexafluoro propylene copolymer, or a composite composition thereof, polyamide, polyimide, polyamideimide, poly (meth-phenylene isopropyl) Deamid), metaaramid, polyethylenechlorotrifluoroethylene, polychlorotrifluoroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride-acrylonitrile copolymer, polyacrylamide, and the like. It is possible to use one or more selected from the group consisting of polyimide, polyacrylonitrile, metaarimid and polyvinylidene fluoride.
  • the polyimide which is one of the heat resistant polymers used in the present invention, may be prepared by a two step reaction.
  • the first step is to prepare a polyamic acid.
  • the polyamic acid proceeds by adding dianhydride to a reaction solution in which diamine is dissolved. Control of temperature, water content of the solvent, purity of the monomer, and the like are required.
  • organic polar solvents of dimethylacetamide (DMAc), dimethylformamide (DMF) and en-methyl-2-pyrrolidone (NMP) are mainly used.
  • the anhydrides include pyromellyrtic dianhydride (PMDA), benzophenonetetracarboxylicdianhydride (BTDA), 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride, ODPA), biphenyltetracarboxylic dianhydride (BPDA) and bis (3,4'-dicarboxyphenyl) dimethylsilanedihydride (bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA) It can be used to include one.
  • PMDA pyromellyrtic dianhydride
  • BTDA benzophenonetetracarboxylicdianhydride
  • ODPA 4,4'-oxydiphthalic anhydride
  • BPDA biphenyltetrac
  • the diamine may be 4,4'-oxydianiline (4,4'-oxydianiline, ODA), paraphenylenediamine (p-penylene diamine, p-PDA) and orthophenylenediamine (o-penylenediamine, o-PDA) may be used.
  • ODA 4,4'-oxydianiline
  • paraphenylenediamine p-penylene diamine, p-PDA
  • orthophenylenediamine o-penylenediamine, o-PDA
  • the weight average molecular weight (Mw) of the polyamic acid is preferably 10,000 to 500,000. If the molecular weight of the polyamic acid is less than 10,000, it is not possible to obtain sufficient physical properties to form a nonwoven fabric, and if it exceeds 500,000, handling of the solution may not be easy and processability may be reduced.
  • the reprecipitation method is a method of obtaining a solid polyamic acid by adding a polyamic acid solution to an excess Poor solvent.
  • Water is mainly used as a reprecipitation solvent, but toluene or ether may be used as a cosolvent. .
  • the chemical imidization method is a method of chemically imidizing a reaction using a dehydration catalyst such as acetic anhydride / pyridine, and is useful for producing a polyimide film.
  • the thermal imidization method is a method of thermally imidating a polyamic acid solution by heating it to 150 to 350 ° C.
  • the simplest process or crystallinity is high, and the polymer is decomposed because an amine exchange reaction occurs when an amine solvent is used. have.
  • Isocyanate method uses diisocyanate as a monomer instead of diamine, and polyimide is produced while CO 2 gas is generated when the monomer mixture is heated to a temperature of 120 ° C. or higher.
  • polyacrylonitrile which is one of the heat resistant polymers used in the present invention, is a copolymer made from a mixture of acrylonitrile and units constituting most of them.
  • Other monomers that frequently enter are butadiene styrene vinylidene chloride or other vinyl compounds.
  • the same acrylic fiber contains at least 85% acrylonitrile and modacryl contains 35-85% acrylonitrile.
  • the fiber is of a desired nature, such as an increase in affinity for the dye.
  • the degree of polymerization of the polyacrylonitrile is preferably 1,000 to 1,000,000, more preferably 2,000 to 1,000,000. If the degree of polymerization of the polyacrylonitrile is too low, it dissolves or swells in a carbonate-based electrolyte and causes desorption of the electrode from the current collector as the cycle progresses, thereby decreasing the efficiency of the battery. This increases the viscosity of the electrode mixture is difficult to handle.
  • the acrylonitrile monomer, a hydrophobic monomer, and a hydrophilic monomer within the range which satisfy
  • the weight percent of acrylonitrile monomer in the polymer polymerization is less than 60 when the total monomer subtracted less than 60 by using a weight ratio of the hydrophilic monomer and the hydrophobic monomer in a 3: 4 ratio, and the viscosity is too low for electrospinning. Even if a crosslinking agent is added thereto, it is difficult not only to cause nozzle contamination but also to form a stable jet during electrospinning.
  • the spin viscosity is too high, it is difficult to spin, even if the additive to lower the viscosity is added to the diameter of the ultrafine fibers and the productivity of the electrospinning is too low to achieve the object of the present invention.
  • the amount of the comonomer in the acrylic polymer is increased, the amount of the crosslinking agent should be added to ensure the stability of electrospinning and to prevent the mechanical properties of the nanofibers from deteriorating.
  • the hydrophobic monomer is an ethylene compound such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinylpyrrolidone, vinylidene chloride, vinyl chloride and the like Preference is given to using any one or more selected from derivatives.
  • the hydrophilic monomer is acrylic acid, allyl alcohol, metaallyl alcohol, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, butanediol monoacrylate, dimethylaminoethyl acrylate, butene tricarboxylic acid It is preferable to use any one or more selected from ethylene-based compounds such as vinylsulfonic acid, allylsulfonic acid, metalylsulfonic acid, parastyrenesulfonic acid, and polyhydric acids or derivatives thereof.
  • an initiator used to prepare the acrylonitrile-based polymer even if an azo compound or a sulfate compound is used, there is no big problem, but in general, it is preferable to use a radical initiator used for a redox reaction.
  • meta-aramid which is one of the heat resistant polymers used in the present invention, preferably has a weight average molecular weight of 3,000 to 500,000. If the weight average molecular weight of the metaaramid is less than 3,000, the physical properties of the fiber is inferior, and if the weight average molecular weight exceeds 500,000, the processability may be lowered.
  • the metaaramids include meta-oriented synthetic aromatic polyamides.
  • Metaaramid polymers must have a fiber-forming molecular weight and can include polyamide homopolymers, copolymers, and mixtures thereof that are primarily aromatic, wherein at least 85% of the amide (-CONH-) bonds are directly directed to the two aromatic rings. Attached. The ring may be unsubstituted or substituted.
  • the polymer becomes meta-aramid when two rings or radicals are meta-oriented relative to each other along the molecular chain.
  • the copolymer has up to 10% other diamines substituted with the primary diamine used to form the polymer, or up to 10% other substituted with the primary diacid chloride used to form the polymer. Have diacid chloride.
  • metaaramids are poly (meth-phenylene isophthalamide) (MPD-I) and copolymers thereof.
  • MPD-I poly (meth-phenylene isophthalamide)
  • One such metaaramid fiber is Lee. Wilmington, Delaware, USA. Child. Nomex® aramid fibers available from EI du Pont de Nemours and Company, while metaaramid fibers are available from Teijin Ltd., Tokyo, Japan. Trade name Tejinconex (registered trademark); New Star® meta-aramid, available from Yantai Spandex Co. Ltd, Shandong, China; And Chinfunex® Aramid 1313, available from Guangdong Charming Chemical Co. Ltd., Xinhui, Guangdong, China.
  • This meta-aramid is the first high heat-resistant aramid fiber, it can be used at 350 °C in a short time, 210 °C in continuous use, and when exposed to a temperature higher than this does not melt or burn like other fibers, it is carbonized . Above all, unlike other products that have been flame retardant or fireproof, it does not emit toxic gases or harmful substances even when carbonized and has excellent properties as an eco-friendly fiber.
  • meta-aramid since meta-aramid has a very strong molecular structure, the molecules constituting the fiber are not only strong in nature but also easily oriented in the fiber axial direction in the spinning step, thereby improving crystallinity and improving the strength of the fiber. There is an advantage to increase.
  • PVDF polyvinylidene fluoride
  • the organic electrolyte solution which has excellent compatibility with the organic electrolyte, has the advantage of being able to be used as a safe electrolyte without being leaked. Since the organic solvent electrolyte is injected later, the polymer matrix can be produced in the air.
  • the polyvinylidene fluoride includes a homopolymer of vinylidene fluoride or a copolymer polymer containing 50% or more of vinylidene fluoride in a molar ratio, and the homopolymer from the viewpoint of excellent strength of the polyvinylidene fluoride resin
  • the polyvinylidene fluoride resin is a copolymerized polymer, and as other copolymerized monomer copolymerized with vinylidene fluoride monomer, a known one can be appropriately selected and used, but is not particularly limited. Chlorine monomers and the like can be suitably used.
  • the weight average molecular weight (Mw) of the polyvinylidene fluoride resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 500,000.
  • Mw weight average molecular weight of the polyvinylidene fluoride resin
  • the nanofibers constituting the nanofibers may not obtain sufficient strength, and when the polyvinylidene fluoride resin exceeds 500,000, the solution may not be easily handled and the processability may be poor. It becomes difficult to obtain.
  • the inorganic polymer that can be used in the present invention is a homopolymer containing a silane group or a siloxane group, or a silane group or a siloxane group and a monomethacrylate, vinyl, hydride, distearate, bis (12-hydroxy-stearate).
  • Methoxy, ethoxylate, propoxylate, diglycidyl ether, monoglycidyl ether, monohydroxy, bis (hydroxyalkyl), chlorine, bis (3-aminopropyl) and bis ((amino A copolymer polymer including a linking group selected from ethyl-aminopropyl) dimethoxysilyl) ether may be used, but is not limited thereto.
  • the number average molecular weight (Mn) of the inorganic polymer is more preferably in the range of 10,000 to 100,000.
  • Mn number average molecular weight of the inorganic polymer
  • the number average molecular weight of the inorganic polymer is less than 10,000, physical properties for producing the nonwoven fabric may not be sufficiently obtained. If the number average molecular weight of the inorganic polymer is greater than 100,000, the handling may not be easy and the processability may be reduced.
  • a polyamic acid spinning solution was prepared by dissolving polyamic acid having a weight average molecular weight of 100,000 in dimethylacetamide (DMAc).
  • the polyamic acid spinning solution was put into a bottom-up electrospinning apparatus and supplied to a spinning nozzle to be electrospun upward on a collector to prepare a polyamic acid nanofiber having a thickness of 10 ⁇ m.
  • the discharge amount per spinning nozzle was 10ml / min
  • the distance between the electrode and the collector was 40cm
  • the applied voltage was 20kV.
  • the polyamic acid nanofibers prepared by electrospinning were subjected to heat treatment at 300 ° C. to imidize the polyamic acid nanofibers with polyimide nanofibers to prepare a porous separator for secondary batteries made of polyimide nanofibers.
  • Polyacrylonitrile (Hanil Synthetic Fiber) having a weight average molecular weight of 157,000 was dissolved in dimethylformamide (DMF) to prepare a polyacrylonitrile spinning solution.
  • DMF dimethylformamide
  • the polyacrylonitrile spinning solution was added to a bottom-up electrospinning apparatus and supplied to a spinning nozzle to be electrospun upward on a collector to prepare a porous separator for secondary batteries made of polyacrylonitrile nanofibers having a thickness of 5 ⁇ m.
  • the discharge amount per spinning nozzle was 10ml / min
  • the distance between the electrode and the collector was 40cm
  • the applied voltage was 20kV.
  • Polyvinylidene fluoride (KYNAR741) was dissolved in dimethylacetamide (DMAc) to prepare a polyvinylidene fluoride spinning solution. It was dissolved in (DMF) to prepare a metaaramid spinning solution.
  • DMAc dimethylacetamide
  • DMF metaaramid spinning solution
  • the radiation zone of the bottom-up electrospinning device is divided into two sections, the polyvinylidene fluoride spinning solution is introduced into a first supply device connected to the first radiation section, and the second supply device is connected to the second spinning section.
  • the metaaramid solution was added thereto, and the electrospinning was continuously performed in a bottom-up manner.
  • Polyvinylidene fluoride nanofibers are formed on a collector in a first section to which the first feeder is connected, and the polyvinylidene fluoride nanofibers are formed on a second section to which a second feeder is connected by moving the collector at a constant speed.
  • the meta-aramid solution was spun on the upper layer to form the meta-aramid nanofibers, thereby forming a porous separator for secondary batteries formed of two layers.
  • the discharge amount per spinning nozzle was 10ml / min
  • the distance between the electrode and the collector was 40cm
  • the applied voltage was 20kV
  • the thickness of each nanofiber layer was 5
  • the total thickness of the prepared porous separator for secondary battery is 10 ⁇ m Prepared.
  • a porous separator was prepared in the same manner as in Example 1.
  • a polysiloxane (DOW CORNING, MB50-010) having a number average molecular weight of 50,000 was dissolved in an acetone solvent to prepare a 20 mass% polysiloxane spinning solution, and the spinning solution was coated on an 10-micron-thick polyolefin substrate (Celgard 2400).
  • the distance between the collectors was 40 cm, an applied voltage of 15 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22, and a humidity of 20%.
  • a polysiloxane nanofiber was prepared in the same manner as in Example 4 except that 10 mass% of the polysiloxane spinning solution was prepared and used instead of 20 mass% of the polysiloxane spinning solution.
  • Separation membranes were prepared using a 13 ⁇ m thick polyolefin film (Celgard 2400) which was not treated separately.
  • a polyamic acid having a weight average molecular weight of 100,000 was dissolved in a THF / DMAc 8: 2 mixed solvent to prepare a spinning solution, and the spinning solution was applied to a polyolefin substrate (Celgard 2400) having a thickness of 10 cm and a distance of 40 cm was applied. Upward electrospinning was performed at a voltage of 15 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 ° C., and a humidity of 20% to form polyamic acid nanofibers having a thickness of 3 ⁇ m. Thereafter, the polyamic acid nanofibers were calcined at 300 ° C. and imidized into polyamide nanofibers.
  • a slurry was prepared by adding 0.5 ⁇ m size Al 2 O 3 inorganic particles and polyvinylidene fluoride (PVDF) having a weight average molecular weight of 50,000 to acetone in a 9: 1 weight ratio. Thereafter, the prepared slurry was coated on the polyamide nanofiber prepared in Step 1 by a casting method by 5 ° C. in thickness to form an inorganic coating layer.
  • PVDF polyvinylidene fluoride
  • Example 7 Preparation of a Porous Separator for a Secondary Battery Including an Inorganic Coating Layer
  • Example 6 except that 0.5 ⁇ m-sized Al 2 O 3 inorganic particles and polyvinylidene fluoride (PVDF) having a weight average molecular weight of 50,000 were added to acetone in an 8: 2 weight ratio instead of a 9: 1 weight ratio.
  • PVDF polyvinylidene fluoride
  • Separation membrane was prepared using a polyolefin film (Celgard 2400) of 18 ⁇ m thickness not treated separately.
  • PVDF polyvinylidene fluoride
  • porous separators prepared in Examples 6 and 7 and the separators prepared in Comparative Examples 3 and 4, respectively, were cut to a size of 5 cm ⁇ 5 cm, and then 1M LiPF 6 EC / DMC / DEC (1 / 1/1)
  • the excess electrolyte solution on the surface was removed by paper filter paper, and then measured by comparing the weight before and after immersion in the electrolyte solution, the electrolyte absorption rate was measured as follows. Table 2 shows.
  • porous membranes prepared in Examples 6 and 7 and the membranes prepared in Comparative Examples 3 and 4, respectively were prepared in a size of 5 cm ⁇ 2.5 cm, respectively, sandwiched between two slide glasses, and then tightened with clips, and then at 150 ° C. After preventing for 30 minutes, the shrinkage was calculated, and the results are shown in Table 2 below.
  • the porous membranes (Examples 6 and 7) to which the nanofibers and the inorganic coating layer are firmly attached by electrospinning, the inorganic material is added to the general polyolefin film (Comparative Example 3) and the polyolefin film. Compared with the directly coated separator (Comparative Example 4), the heat resistance and electrolyte wettability were significantly improved.
  • Example 8 Preparation of a Porous Separator for a Secondary Battery Including an Inorganic Coating Layer
  • a polyacrylonitrile (Hanil Synthetic Fiber) having a weight average molecular weight of 157,000 was dissolved in a DMF solvent to prepare a spinning solution, and the spinning solution was separated from the electrode on the polyolefin substrate (Celgard 2400) having a thickness of 10 ⁇ m by 40 cm, Upward electrospinning was performed at an applied voltage of 15 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 ° C., and a humidity of 20% to form polyacrylonitrile nanofibers having a thickness of 3 ⁇ m.
  • a slurry was prepared by adding 0.5 ⁇ m size Al 2 O 3 inorganic particles and polymethyl methacrylate (Poly (methyl methacrylate), PMMA) (LG IG840) to acetone in a 9: 1 weight ratio. Thereafter, the prepared slurry was coated on the polyacrylonitrile nanofiber prepared in Step 1 by a casting method with a thickness of 5 ⁇ m to form an inorganic coating layer.
  • Poly (methyl methacrylate), PMMA) LG IG840
  • Example 10 Preparation of a Porous Separator for a Secondary Battery Including an Inorganic Coating Layer
  • a polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 was dissolved in a DMAc solvent to prepare a spinning solution.
  • a 3 ⁇ m-thick polyvinylidene fluoride nanofiber was formed by upward electrospinning at an applied voltage of 15 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 ° C., and a humidity of 20%.
  • a slurry was prepared by adding 0.5 ⁇ m size Al 2 O 3 inorganic particles and polymethyl methacrylate (Poly (methyl methacrylate), PMMA) (LG IG840) to acetone in a 9: 1 weight ratio. Thereafter, the prepared slurry was coated on the polyvinylidene fluoride nanofiber prepared in Step 1 by a thickness of about 5 ⁇ m to form an inorganic coating layer.
  • Poly (methyl methacrylate), PMMA) LG IG840
  • Example 11 Preparation of a Porous Separator for Secondary Battery Including an Inorganic Coating Layer
  • Example 10 Except that 0.5 ⁇ m-sized Al 2 O 3 inorganic particles and polymethyl methacrylate (PMMA) (LG IG840) were added to acetone in an 8: 2 weight ratio instead of a 9: 1 weight ratio, By performing the same process as in Example 10 to prepare a porous separator for a secondary battery including an inorganic coating layer.
  • PMMA polymethyl methacrylate
  • Example 12 Preparation of a Porous Separator for Secondary Battery Including an Inorganic Coating Layer
  • Meta-aramid having a weight average molecular weight (Mw) of 50,000 was dissolved in a DMAc solvent to prepare a spinning solution.
  • the spinning solution was placed on a polyolefin substrate (Celgard 2400) having a thickness of 10 ⁇ m with a distance of 40 cm and an applied voltage of 15 kV.
  • a slurry was prepared by adding 0.5 ⁇ m size Al 2 O 3 inorganic particles and polymethyl methacrylate (Poly (methyl methacrylate), PMMA) (LG IG840) to acetone in a 9: 1 weight ratio. Thereafter, the prepared slurry was coated on the meta-aramid nanofiber prepared in step 1 by a casting method with a thickness of 5 ⁇ m to form an inorganic coating layer.
  • Poly (methyl methacrylate), PMMA) LG IG840
  • Example 13 Preparation of a Porous Separator for Secondary Battery Including an Inorganic Coating Layer
  • a separator was prepared.
  • porous membranes prepared in Examples 8 to 13 and the membranes prepared in Comparative Examples 3 and 5, respectively, were prepared in a size of 5 cm ⁇ 2.5 cm, respectively, sandwiched between two slide glasses, and then tightened with clips, and then, at 150 ° C. After preventing for 30 minutes, the shrinkage was calculated, and the results are shown in Table 3 below.
  • the porous separator (Examples 8 to 13) to which the nanofibers and the inorganic coating layer by electrospinning are firmly attached, the inorganic material is added to the general polyolefin film (Comparative Example 3) and the polyolefin film. Compared with the directly coated separator (Comparative Example 5), the heat resistance was much improved.

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Abstract

La présente invention concerne un procédé de préparation d'une membrane de séparation poreuse pour une batterie secondaire et une membrane de séparation poreuse pour une batterie secondaire préparée ainsi et, plus particulièrement, un procédé de préparation d'une membrane de séparation poreuse pour une batterie secondaire et une membrane de séparation poreuse pour une batterie secondaire préparée ainsi, la membrane de séparation poreuse étant préparée par utilisation d'un processus de filage électrostatique dirigé vers le haut de telle sorte que la membrane de séparation comprend des nanofibres préparées par filage électrostatique, et possède ainsi des propriétés poreuses, des gouttelettes générées durant un filage électrostatique vers le bas classique n'étant pas formées, et une stabilité thermique est améliorée comparativement à une membrane de séparation de type film à base de polyoléfine classique.
PCT/KR2014/001566 2013-03-14 2014-02-26 Procédé de préparation de membrane de séparation poreuse pour batterie secondaire et membrane de séparation poreuse pour batterie secondaire préparée ainsi Ceased WO2014142450A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
KR10-2013-0026999 2013-03-14
KR10-2013-0026998 2013-03-14
KR10-2013-0027003 2013-03-14
KR1020130026999A KR101447565B1 (ko) 2013-03-14 2013-03-14 무기 코팅층을 포함하는 이차전지용 다공성 분리막 및 이의 제조방법
KR10-2013-0027004 2013-03-14
KR1020130027003A KR101402976B1 (ko) 2013-03-14 2013-03-14 폴리올레핀 기재 상 폴리이미드를 전기방사한 후 무기물을 코팅한 이차전지용 다공성 분리막 및 이의 제조방법
KR10-2013-0027002 2013-03-14
KR20130027002A KR101479749B1 (ko) 2013-03-14 2013-03-14 폴리올레핀에 폴리비닐리덴플루오라이드(pvdf)를 전기방사하고 무기물을 코팅한 이차전지용 다공성 분리막 및 이의 제조방법
KR10-2013-0027005 2013-03-14
KR1020130026998A KR101447564B1 (ko) 2013-03-14 2013-03-14 상향식 전기방사를 이용한 이차전지용 분리막의 제조방법 및 그에 따라 제조된 분리막
KR1020130027005A KR101402981B1 (ko) 2013-03-14 2013-03-14 폴리올레핀 기재 위에 무기고분자를 전기방사한 이차전지용 다공성 분리막 및 이의 제조방법
KR1020130027004A KR101402979B1 (ko) 2013-03-14 2013-03-14 폴리올레핀 기재 상 메타아라미드를 전기방사한 후 무기물을 코팅한 이차전지용 다공성 분리막 및 이의 제조방법

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105552279A (zh) * 2016-01-29 2016-05-04 常州达奥新材料科技有限公司 一种静电纺丝法制备高热稳定性防过充电池隔膜的方法
WO2016159720A1 (fr) * 2015-04-02 2016-10-06 에스케이이노베이션 주식회사 Membrane de séparation composite pour batterie secondaire au lithium et son procédé de fabrication
EP3490031A4 (fr) * 2016-08-29 2019-05-29 BYD Company Limited Séparateur de batterie au lithium-ion et son procédé de préparation , et batterie au lithium-ion
EP3493297A4 (fr) * 2016-08-29 2019-06-05 BYD Company Limited Film composite polymère et son procédé de préparation et batterie au lithium-ion comprenant le film composite polymère
EP3493298A4 (fr) * 2016-08-29 2019-06-05 BYD Company Limited Pellicule composite polymère et son procédé de préparation et batterie lithium-ion la comprenant
CN110808351A (zh) * 2019-11-07 2020-02-18 贵州梅岭电源有限公司 一种锂离子动力电池聚酰亚胺复合隔膜及其制备方法
CN111653821A (zh) * 2020-05-29 2020-09-11 东南大学 一种聚酰亚胺静电纺丝纤维改性硅氧烷复合型固态聚合物电解质及其制备和应用
US10985356B2 (en) 2015-04-02 2021-04-20 Sk Innovation Co., Ltd. Composite separation membrane for lithium secondary battery and manufacturing method therefor
WO2023021274A1 (fr) * 2021-08-16 2023-02-23 University Of Surrey Supercondensateur comprenant un séparateur à dipôle électrique permanent
CN116103837A (zh) * 2023-02-09 2023-05-12 湖州南木纳米科技有限公司 一种耐高温聚酰亚胺复合隔膜及其制备方法
CN116695290A (zh) * 2023-07-11 2023-09-05 陕西科技大学 一种间位芳纶纤维废丝的回收方法
CN118630422A (zh) * 2024-07-02 2024-09-10 青岛科技大学 一种电池纳米纤维阻隔膜及制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080017114A (ko) * 2006-08-21 2008-02-26 주식회사 엘지화학 전극과 분리막의 결합력 및 도전성이 우수한 전극조립체 및이를 포함하고 있는 전기화학 셀
KR20110026186A (ko) * 2009-09-07 2011-03-15 한국생산기술연구원 친수성 폴리올레핀계 분리막, 이의 제조방법 및 이를 이용한 이차전지
KR20110057079A (ko) * 2009-11-23 2011-05-31 주식회사 엘지화학 다공성 코팅층을 구비한 분리막의 제조방법, 이로부터 형성된 분리막 및 이를 구비한 전기화학소자
KR20110105365A (ko) * 2010-03-18 2011-09-26 주식회사 아모그린텍 셧다운 기능을 갖는 초극세 섬유상 다공성 분리막 및 그 제조방법과 제조장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080017114A (ko) * 2006-08-21 2008-02-26 주식회사 엘지화학 전극과 분리막의 결합력 및 도전성이 우수한 전극조립체 및이를 포함하고 있는 전기화학 셀
KR20110026186A (ko) * 2009-09-07 2011-03-15 한국생산기술연구원 친수성 폴리올레핀계 분리막, 이의 제조방법 및 이를 이용한 이차전지
KR20110057079A (ko) * 2009-11-23 2011-05-31 주식회사 엘지화학 다공성 코팅층을 구비한 분리막의 제조방법, 이로부터 형성된 분리막 및 이를 구비한 전기화학소자
KR20110105365A (ko) * 2010-03-18 2011-09-26 주식회사 아모그린텍 셧다운 기능을 갖는 초극세 섬유상 다공성 분리막 및 그 제조방법과 제조장치

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10985356B2 (en) 2015-04-02 2021-04-20 Sk Innovation Co., Ltd. Composite separation membrane for lithium secondary battery and manufacturing method therefor
WO2016159720A1 (fr) * 2015-04-02 2016-10-06 에스케이이노베이션 주식회사 Membrane de séparation composite pour batterie secondaire au lithium et son procédé de fabrication
CN105552279A (zh) * 2016-01-29 2016-05-04 常州达奥新材料科技有限公司 一种静电纺丝法制备高热稳定性防过充电池隔膜的方法
US11264674B2 (en) 2016-08-29 2022-03-01 Byd Company Limited Polymer composite membrane, preparation method for same, and lithium-ion battery including same
EP3493298A4 (fr) * 2016-08-29 2019-06-05 BYD Company Limited Pellicule composite polymère et son procédé de préparation et batterie lithium-ion la comprenant
EP3493297A4 (fr) * 2016-08-29 2019-06-05 BYD Company Limited Film composite polymère et son procédé de préparation et batterie au lithium-ion comprenant le film composite polymère
US11223090B2 (en) 2016-08-29 2022-01-11 Byd Company Limited Polymer composite membrane, preparation method thereof, and lithium-ion battery including the same
EP3490031A4 (fr) * 2016-08-29 2019-05-29 BYD Company Limited Séparateur de batterie au lithium-ion et son procédé de préparation , et batterie au lithium-ion
CN110808351A (zh) * 2019-11-07 2020-02-18 贵州梅岭电源有限公司 一种锂离子动力电池聚酰亚胺复合隔膜及其制备方法
CN111653821A (zh) * 2020-05-29 2020-09-11 东南大学 一种聚酰亚胺静电纺丝纤维改性硅氧烷复合型固态聚合物电解质及其制备和应用
CN111653821B (zh) * 2020-05-29 2022-06-07 东南大学 一种聚酰亚胺静电纺丝纤维改性硅氧烷复合型固态聚合物电解质及其制备和应用
WO2023021274A1 (fr) * 2021-08-16 2023-02-23 University Of Surrey Supercondensateur comprenant un séparateur à dipôle électrique permanent
CN116103837A (zh) * 2023-02-09 2023-05-12 湖州南木纳米科技有限公司 一种耐高温聚酰亚胺复合隔膜及其制备方法
CN116695290A (zh) * 2023-07-11 2023-09-05 陕西科技大学 一种间位芳纶纤维废丝的回收方法
CN118630422A (zh) * 2024-07-02 2024-09-10 青岛科技大学 一种电池纳米纤维阻隔膜及制备方法

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