WO2014123268A1 - 역구조를 갖는 하이브리드 난워븐 세퍼레이터 - Google Patents
역구조를 갖는 하이브리드 난워븐 세퍼레이터 Download PDFInfo
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- WO2014123268A1 WO2014123268A1 PCT/KR2013/001247 KR2013001247W WO2014123268A1 WO 2014123268 A1 WO2014123268 A1 WO 2014123268A1 KR 2013001247 W KR2013001247 W KR 2013001247W WO 2014123268 A1 WO2014123268 A1 WO 2014123268A1
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- layer
- separator
- pet
- nanofiber layer
- nanofiber
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a separator used in a secondary battery, and more particularly, to a separator interposed between a positive electrode plate and a negative electrode plate of a secondary battery to selectively pass only ions during charge and discharge.
- Secondary batteries such as lithium ion secondary batteries, lithium polymer secondary batteries, and supercapacitors (electric double layer capacitors and similar capacitors) are required to have high energy density, large capacity, and thermal stability due to high performance, light weight, and large size trends for automotive power supplies. .
- the basic structure of the secondary battery which is widely used at present, interposes a separator between a positive electrode plate coated with a positive electrode active material and a negative electrode plate coated with a negative electrode active material, winds it up, inserts it into a battery case, and then fills an electrolyte and seals the case.
- the separator is a polyvinylidene fluoride (hereinafter referred to as PVDF) on one or both sides of a nonwoven fabric layer made of polyethylene terephthalate (hereinafter referred to as 'PET') or the like as a strength support layer to retain the required strength.
- PVDF polyvinylidene fluoride
- 'PET' polyethylene terephthalate
- Structures in which the same polymer material is electrospun with nanofibers are known.
- the separator described in the prior patent is on one side or both sides of the PET substrate layer
- the nanofibrous layer has a laminated structure. Since the specific surface area of the nanofibrous layer is much larger than that of the base layer, the frictional force with the heterogeneous material is also very large. Typically, the friction coefficient of the PVDF nanofiber layer is known to be three to four times higher than that of the PET base layer.
- secondary batteries generate by-products due to repeated electrical oxidation and reduction processes during continuous charging and discharging processes.
- the by-products significantly reduce the charge and discharge efficiency by blocking the micro-pores of the nanofibrous layer, and the life of the secondary battery is rapidly decreased, while overheating is caused by the phenomenon that ions are directed toward the larger pores to avoid the blocked pores. As a result, a fatal problem may occur in which a short circuit may occur due to melting of the separator.
- the nanofiber layer is relatively low in strength compared to the base layer, there is a problem in that it is not vulnerable to external impact or scratches and thus cannot guarantee uniform quality of the separator.
- the present invention is to solve the problem caused by the high friction of the nanofiber layer laminated or bonded to the secondary battery separator and to provide a separator that can ensure the structure and quality of a uniform secondary battery
- Another object of the present invention is to provide a separator capable of pre-filtering to prevent the performance degradation of the separator due to by-products and foreign substances generated during charging and discharging of the secondary battery in advance.
- the present invention has been made to solve the above technical problem, the secondary battery separator having a reverse structure of the present invention, the nanofiber layer; Characterized in that consisting of; non-woven substrate layer bonded to the nanofiber layer is interposed to form the outermost layer.
- the nanofibers forming the nanofiber layer is polyimide (PI), aramid, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFC), polyvinylidene Fluoride-hexafluoropropylene (PVDF-HFP) and mixtures thereof.
- PI polyimide
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PCTFC polychlorotrifluoroethylene
- PVDF-HFP polyvinylidene Fluoride-hexafluoropropylene
- the raw material of the said base material layer is polyethylene terephthalate (PET).
- an interface between the nanofiber layer and the base layer may be provided with a hot melt layer in which a separate bonding nanofibers are melted, and in particular, the nanofiber layer is composed of a plurality of layers, and is also separate from each interface of the nanofiber layer. Hot melt layer of the nanofibers for bonding may be provided.
- the substrate layer employed in the present invention the first PET fibers having a melting point of 0.6 ⁇ m or more and less than 3.0 ⁇ m and a melting point of 240 °C or more, and a binder function at 100 °C to 150 °C with a diameter of 1.2 ⁇ m or more and less than 6.0 ⁇ m It may include a second PET fiber having.
- the porosity of the base layer is 45% to 85%
- the average pore diameter is preferably 0.5 to 7.0 ⁇ m.
- the punching strength of the substrate layer is 200 to 900gf
- the tensile strength is preferably 250 to 1500kgf / cm2.
- the first PET fibers and the second PET fibers are particularly effective to contain in a weight ratio of 30:70 to 70:30.
- the base layer is disposed on the outermost side of the separator, it is possible to solve the manufacturing problem due to high friction that may occur in the manufacturing process of the secondary battery. have.
- the shrinkage or wrinkle of the separator may be significantly reduced in the battery assembly process, and the membrane separation phenomenon due to the difference in melting temperature between the base layer and the nanofiber layer may be prevented. It can be effective.
- FIG. 1 is a side cross-sectional view of a separator according to an embodiment of the present invention
- FIG. 2 is a side cross-sectional view of a separator according to another embodiment of the present invention.
- Figure 3 is a side cross-sectional view of a separator according to another embodiment of the present invention.
- the term "about” means 30, 25, 20, 25, 10, 9, 8, 7, 6, 5, by reference quantity, level, value, number, frequency, percentage, dimension, size, amount, weight, or length. By amount, level, value, number, frequency, percentage, dimension, size, amount, weight or length, varying by 4, 3, 2 or 1%.
- FIG. 1 is a block diagram illustrating a basic structure of a hybrid Nanwarven separator having an inverse structure according to an embodiment of the present invention.
- the separator of FIG. 1 has a structure in which a substrate layer is bonded to both surfaces of a nanofiber layer, and the substrate layer forms the outermost layer of the separator.
- the nanofibers forming the nanofiber layer is polyimide (PI), aramid, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFC), polyvinylidene fluor Ride-hexafluoropropylene (PVDF-HFP) and a mixture thereof are selected from the group consisting of a nonwoven fabric material of the base material is PET.
- PI polyimide
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PCTFC polychlorotrifluoroethylene
- PVDF-HFP polyvinylidene fluor Ride-hexafluoropropylene
- materials used as secondary battery separators include polyethylene (PE), polypropylene (PP), and the like, but the base material layer of the present invention uses a PET material having high heat resistance and excellent affinity for chemicals and chemical resistance.
- the separator according to the present invention is the outermost layer is a PET base layer, and the PET base layer is interposed between the separator and the positive electrode plate and the negative electrode plate because the friction coefficient is about 1/3 to 1/4 compared to the nanofiber layer.
- the interfacial friction with the separator is small, so that the phenomenon that the separator comes with the manrail can be greatly reduced, so that structural deformation can be minimized when manufacturing the secondary battery.
- the PET base layer forms the outermost layer of the separator, the electrochemical by-products or foreign substances generated during charging and discharging of the secondary battery can be filtered in advance in the base layer. If the nanofiber layer is formed on both sides of the base layer as in the prior art, it is impossible to perform the function of moving passages of lithium ions as a separator by blocking the pores of the nanofiber layer, but in the state in which the nanofiber layer is interposed as in the present invention.
- the base layer which has several or several tens of voids than the fibrous layer, forms the outermost layer
- electrochemical by-products generated during charging and discharging, or foreign matter is first filtered by the base layer (even when the foreign material blocks the pores of the base layer).
- the substrate layer is very large and can be transferred to the nanofiber layer through other pores), and only the material that has passed through the substrate layer Since the oil layer so as to be capable of moving it is possible to prevent life shortening or ion displacement phenomenon of the secondary battery due to the pores of the nano-fiber clogging from occurring.
- FIG. 2 illustrates a structure in which a hot melt layer is included at an interface between a nanofiber layer and a base layer in the basic structure of the separator of FIG. 1.
- the hot melt layer is a structure in which the nanofiber layer serving as a separator and the base layer as the strength support layer are bonded to each other, and are formed by electrospinning.
- the hot melt layer is another nanofibrous layer and has a lower melting point than the above functional nanofibers and PET substrates.
- two substrate layers are prepared, electrospun nanofibers forming a hot melt layer on one side of each substrate layer, and then bonded to both sides of the functional nanofibrous layer, hot melt by applying heat and pressure
- the bonding is completed by selectively melting only the layer, the above process sequence is not necessarily limited thereto, and the order of specific processes for forming the above structure may be changed.
- the functional nanofiber layer or the base layer is an adhesive material, or when heat and pressure are applied to melt a portion of the nanofiber layer or the base layer, but the nanofiber layer or the base layer itself is an adhesive material.
- the minimum adhesion strength required after the battery assembly process or assembly is not exhibited, so that the separation between the base layer and the nanofiber layer occurs, and when the nanofiber layer or a part of the base layer is melted and attached, the nanofiber layer and the base layer Melting may occur not only at the interface but also at the inside of the nanofiber layer and the base layer. This may prevent the movement of lithium ions by blocking the pores of the nanofiber layer or the base layer itself, thereby significantly reducing the function of the separator.
- FIG. 3 shows a structure in which the functional nanofiber layer is bonded to two layers in the structure of the separator of FIG. 1.
- a hot melt layer is formed at the interface between the nanofiber layer and the base layer and the nanofiber layer.
- the nanofiber layer and the base layer which perform their respective functions are preserved without melting and only a hot melt layer is formed for bonding, the nanofiber layer and the base layer do not cause entanglement due to melting. The resulting blockage of voids does not occur.
- the nanofibrous layer is formed of a plurality of layers, it is possible to compensate for defects that may exist in the nanofibrous layer as compared to a single layer, thereby ensuring the uniformity of the dispersion.
- PET nonwoven fabric constituting the substrate layer of the present invention is not only excellent in mechanical strength, such as tensile strength, punching strength, high breathability, and excellent in affinity with the electrolyte solution.
- the wettability of the separator may be improved and the time for filling the electrolyte may be saved, and the separator may be uniformly filled with the electrolyte.
- 'PET nonwoven fabric' or 'PET base layer' is used as an equivalent meaning.
- the PET nonwoven fabric in the present invention means a nonwoven fabric made of PET resin, but may include a PET copolymer or other additives as well as a nonwoven fabric made of only PET resin.
- Condensation polymerization of terephthalic acid or dimethyl terephthalate and ethylene glycol is a repeating unit of the PET resin
- butylene terephthalate is condensation polymerization of terephthalic acid or dimethyl terephthalate and tetramethylene glycol
- ethylene naphthalate is 2,6-naphthalene.
- butylenenaphthalate is 2,6-naphthalenedicarboxylic acid or dimethyl-2,6-naphthalenedicarboxylate and tetra It may be formed by condensation polymerization of methylene glycol.
- the PET resin may include a third copolymerization component in less than 30% by weight of the repeating unit.
- Monomers that can be used to form the copolymerization component are isophthalic acid, dimethyl-2,5-naphthalenedicarboxylate, 2,5-naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, diphenoxyethanedicar Acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, anthracenedicarboxylic acid or ⁇ , ⁇ -bis (2-chlorophenoxy) ethane-4,4-dicarboxylic acid, adipic acid Dibasic or polybasic acids such as 5-sodium sulfoisophthalic acid, trimellitic acid and pyromellitic acid, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, hexylene glycol, neopentylene glycol, polyethylene glycol
- the PET nonwoven fabric includes two kinds of PET having different melting points. That is, the first PET fibers made of PET having a melting point of 240 ° C. or more, and the second PET fibers made of PET having a binder function at 100 ° C. to 150 ° C.
- the first PET fiber has excellent thermal stability as a high melting point PET fiber having excellent heat resistance. Accordingly, the PET nonwoven fabric of the present invention has excellent dimensional stability and durability and has a high short circuit temperature, thereby greatly improving the stability of the secondary battery. Therefore, there is a great effect when applied to large capacity batteries, such as ESS, electric vehicles.
- the first PET fiber may be referred to as 'heat resistant fiber' as necessary.
- the second PET fiber serves as a binding fiber as a relatively low melting PET fiber, and serves to bond the first PET fibers and the first PET fibers and the second PET fibers to each other during the hot press during the manufacturing of the nonwoven fabric.
- the binding treatment is performed using the same PET material without using a separate adhesive resin, thereby obtaining a nonwoven fabric having excellent mutual adhesiveness and excellent electrolyte wettability.
- the second PET fiber may be referred to as a 'binding fiber' as necessary.
- the second PET fiber of the present invention is effective to combine with the first PET fiber during the drying process during the process of making the nonwoven fabric
- the second PET fiber generally serves as a binder fiber within the temperature in consideration of the dry temperature of 100 to 150 °C. It becomes important to do so.
- the content ratio of the heat resistant first PET fiber and the binding second PET fiber is not particularly limited, if the content of the heat resistant fiber is too high, the content of the binding fiber is relatively low, so that the bonding force between the fibers is insufficient, so that the fibers are detached from the battery manufacturing process. Symptoms may occur.
- the content of the first PET fiber and the second PET fiber is 30:70 to 70:30 when the total weight of one substrate layer is 100.
- the diameter of the heat resistant first PET fiber is not particularly limited, but as the diameter is thinner to a nano size, the pores become finer, which is advantageous for application to a secondary battery separator, but when the thickness is less than 0.6 ⁇ m, the manufacturing cost is increased and fine. There is a problem that entanglement between fibers occurs.
- 1PET fiber uses a fiber having a diameter of about 0.6 ⁇ m or more and less than 3.0 ⁇ m and micro level fibers.
- the second PET fiber which is the binder fiber
- the second PET fiber has an advantage of increasing air permeability as the cross-sectional diameter increases, but when the thickness exceeds 6.0 ⁇ m, there is a problem that the punching strength is lowered.
- the smaller the diameter has the advantage of increasing the strength, but less than 1.2 ⁇ m has a problem of too low air permeability, in addition to the above-described binding characteristics, fiber diameter is also an important factor.
- the aspect ratio of the first PET fiber and the second PET fiber is preferably about 500 to 2,000. If less than about 500, the fiber length is short, so that the mechanical strength of the fiber is much decreased, and if it is more than about 2000, the dispersibility of the fiber is greatly decreased, resulting in unevenness of the product and entanglement of the fiber. This reduces the quality of the product.
- the PET substrate according to the example of the present invention described above uses two kinds of PET fibers having different melting points, and each fiber also uses two kinds of fibers having different cross-sectional diameters, that is, different thicknesses.
- the thin film can be thinned as required by the industry, has an excellent porosity of 45% to 85%, a fine pore diameter of 0.5 ⁇ m to 7.0 ⁇ m, and a uniform porosity distribution.
- PET nonwoven fabric of the present invention is very excellent in mechanical strength, showing a tensile strength of 250 to 1500kgf / cm 2 and a punching strength of 200gf to 900gf.
- the PET base layer may have a single layer structure, or may have a multilayer structure of two or more layers.
- the total thickness is preferably about 10 to 50 ⁇ m.
- the first PET fiber (Graylay, Kolon) having a melting point of 240 ° C. or more and 1.5 ⁇ m in diameter and the second PET fiber (Graylay, Kolon) having a diameter of 1.5 ⁇ m having a binder function at 100-150 degrees are shown in Table 1 below.
- the final thickness of the sample was prepared with a difference of 8 ⁇ m.
- the prepared sample is placed in a beaker in a laboratory plant room.
- the above sample was carried out at the same concentration by varying the weight percent of the first fiber and the second fiber, select a concentration excellent in dispersibility among the concentration of 0.01 to 0.1% by weight compared to water.
- a high speed agitation is performed at 3600 RPM for 1 minute using a blade-type stirrer to disperse the PET fiber well. If the stirring time is too long, the PET fibers are entangled with each other to inhibit dispersion and deterioration in quality due to the foreign matter form after sample preparation.
- the first natural dehydrated sample is wrapped in a fine blanket and passed through a roll dryer at 115 ° C. to remove moisture in the second sample.
- the puncture strength measurement is made by unfolding the sample and then fixing it to the test frame.
- the immobilized sample is applied to the needle having a diameter of 1 mm while the sample is punctured while applying a force of 1 Kgf. Record the value at the time of drilling in gf unit.
- the sample is measured 10 times and used as the average value.
- the pore size measurement is performed using a porometer. After cutting the sample to 30 mm x 30 mm, the sample is fixed to the pometer meter, the dry state and the standard solution are added to the sample, and the result in the wet state is used to calculate the derivative. The average pore size, max pore size, pore dispersion, etc. are measured.
- the electrolyte solution was impregnated for 5 minutes, the remaining electrolyte solution was removed from the surface, and weighed.
- the outermost layer was PET (8 ⁇ m X 2) 16 ⁇ m, and the structure of the PVDF nanofibers (1.5 ⁇ m X 2) 3 ⁇ m and hot melt layer 1 ⁇ m inside the PET nonwoven fabric
- the air permeability, puncture strength, tensile strength and thermal stability experiments were performed on a total membrane of 20 ⁇ m and a commercial membrane (Celgard ® 2320) manufactured by Celgard, USA, and the results are shown in Table 2 below.
- Preparation Example 1 was found to be relatively excellent air permeability and thermal stability compared to the conventional Celgard membrane, but mechanical strength such as puncture strength and tensile strength is not equivalent to the required value.
- the preparation examples 2 to 6 can be usefully used as a separator because the chemical and mechanical properties are very superior to the threshold compared to the rest of the comparative examples.
- the hot melt layer formed in the interface between a nanofiber layer and / or a base material layer is demonstrated.
- the material of the hot melt layer is not particularly limited as long as it has ionic conductivity and does not adversely affect battery performance. Synol, vinyl acetate, polyvinyl alcohol, vinyl chloride, polyvinyl acetal, acrylic, saturated polyester, polyamide, polyethylene, butadiene rubber, nitrile rubber, butyl rubber, silicone rubber, vinyl, Phenol-chromoprene rubber-based, polyamide-based, and rubber-epoxy watches, or mixtures of two or more thereof, copolymers, graft polymers, and compound materials through general chemical modification, and more preferably.
- it can be made of a material selected from the group consisting of polypropylene-based, ethylene vinyl acetate-based and butadiene rubber-based have.
- the hot melt layer preferably has a thin thickness and high porosity, for example, the thickness of the hot melt layer is about 0.2 to 30% of the thickness of the PET nonwoven fabric layer, specifically, about 0.1. To 3.0 ⁇ m, and may be a single layer or a multilayer.
- the hot melt layer of the present invention has a low electrical resistance when used in the secondary battery can prevent the degradation of the secondary battery. If the thickness is less than 0.1 ⁇ m outside the range of the adhesion strength is weak and the nanofiber layer and / or the base layer is easily separated, if exceeding 3.0 ⁇ m the air permeability and porosity is lowered due to the increase of the hot melt layer, rather it may lower the performance of the separator There is a problem.
- a hot melt layer made of nanofibers was formed on the PET substrate layer by electrospinning.
- the electrospinning process is not particularly limited and may be modified and applied to the present invention in a manner known in the art.
- electrospinning applies a voltage such that the spinning solution has a charge, manufacturing a nanofiber by discharging the spinning solution with the charge through a spinning nozzle, and a current collector having a charge opposite to the spinning solution. It may include the step of integrating the nanofibers.
- the electrospinning process has the advantage of being able to easily produce fibers having a nano size diameter.
- the hot melt layer is preferably made of nanofibers having an average diameter of about 50 to 1500nm.
- the average diameter of the nanofibers is less than about 50 nm, the air permeability of the separator may be reduced, and when the average diameter of the nanofibers exceeds about 1500 nm, it may not be easy to control the size and thickness of the pores of the separator.
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Abstract
Description
제1파이버 중량% | 제2파이버 중량% | 비 고 | |
제조예 1 | 20 | 80 | 두께 8㎛ |
제조예 2 | 30 | 70 | 두께 8㎛ |
제조예 3 | 40 | 60 | 두께 8㎛ |
제조예 4 | 50 | 50 | 두께 8㎛ |
제조예 5 | 60 | 40 | 두께 8㎛ |
제조예 6 | 70 | 30 | 두께 8㎛ |
제조예 7 | 80 | 20 | 두께 8㎛ |
공기투과도Cm3/Cm2/S | 뚫림강도gf | 인장강도Kgf/Cm2 | 열안정성(수축율 %) | |||||||
MD | TD | 95℃ | 125℃ | 150℃ | ||||||
MD | TD | MD | TD | MD | TD | |||||
제조예 1 | 0.2 | 330 | 440 | 350 | 0 | 0 | 0 | 0 | 0 | 0 |
제조예 2 | 1.0 | 415 | 630 | 510 | 0 | 0 | 0 | 0 | 0 | 0 |
제조예 3 | 1.3 | 425 | 770 | 603 | 0 | 0 | 0 | 0 | 0 | 0 |
제조예 4 | 1.5 | 430 | 820 | 690 | 0 | 0 | 0 | 0 | 0 | 0 |
제조예5 | 1.7 | 427 | 780 | 614 | 0 | 0 | 0 | 0 | 0 | 0 |
제조예6 | 1.9 | 380 | 610 | 470 | 0 | 0 | 0 | 0 | 0 | 0 |
제조예7 | 2.8 | 290 | 420 | 330 | 0 | 0 | 0 | 0 | 0 | 0 |
셀가드분리막(20㎛) | 0.07 | 360 | 2,000 | 150 | 5 | 0 | 38 | 19 | 56 | 32 |
Claims (6)
- 나노섬유층과;상기 나노섬유층이 개재되도록 접합되어 최외곽층을 형성하는 부직포인 기재층;으로 이루어진 것을 특징으로 하는 역구조를 갖는 하이브리드 난워븐 세퍼레이터.
- 제1항에 있어서,상기 나노섬유층을 형성하는 나노섬유는폴리이미드(PI), 아라미드, 폴리비닐리덴플로라이드(PVDF),폴리테트라플루오로에틸렌(PTFE), 폴리클로로트리플루오로에틸렌(PCTFC), 폴리비닐리덴플로라이드-헥사플루오르프로필렌(PVDF-HFP) 및 이들의 혼합물로 이루어진 군에서 선택된 소재이며, 상기 기재층의 소재는 폴리에틸렌테레프탈레이트(PET)인 것을 특징으로 하는 역구조를 갖는 하이브리드 난워븐 세퍼레이터.
- 제2항에 있어서,상기 나노섬유층과 상기 기재층 사이의 계면에는 별도의 접합용 나노섬유가 용융된 핫멜트층이 구비된 것을 특징으로 하는 역구조를 갖는 하이브리드 난워븐 세퍼레이터.
- 제3항에 있어서,상기 나노섬유층은 복수층으로 이루어지고, 상기 나노섬유층 각각의 계면에도 별도의 접합용 나노섬유가 용융된 핫멜트층이 구비된 것을 특징으로 하는 역구조를 갖는 하이브리드 난워븐 세퍼레이터.
- 제1항 내지 제4항 중 어느 한 항에 있어서,상기 기재층은, 용융점(Melting Temperature)이 서로 다른 2종의 PET섬유를 포함하되,240℃이상의 용융점을 갖고 직경이 0.6㎛ 이상 3.0㎛ 미만인 PET로 이루어진 '제1PET섬유'와, 100℃ 내지 150℃ 에서 바인더 기능을 갖고 직경이 1.2㎛ 이상 6.0㎛ 미만인 PET로 이루어진 '제2PET섬유'를 포함하는 것을 특징으로 하는 역구조를 갖는 하이브리드 난워븐 세퍼레이터.
- 제5항에 있어서,상기 제1PET섬유 및 상기 제2PET섬유의 엑스펙트비가 500 내지 2,000인 것을 특징으로 하는 역구조를 갖는 하이브리드 난워븐 세퍼레이터.
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JP2014560846A JP5823067B2 (ja) | 2013-02-06 | 2013-02-18 | 逆構造を有するハイブリッドノンウーブンセパレータ |
US14/369,162 US20150372273A1 (en) | 2013-02-06 | 2013-02-18 | Hybrid nonwoven separator having inverted structure |
DE112013000385.6T DE112013000385T5 (de) | 2013-02-06 | 2013-02-18 | Hybrider Vliesseparator mit invertierter Struktur |
CN201380003316.XA CN104160527A (zh) | 2013-02-06 | 2013-02-18 | 具有倒置结构的复合无纺布隔膜 |
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KR10-2013-0013255 | 2013-02-06 | ||
KR1020130013255A KR101292657B1 (ko) | 2013-02-06 | 2013-02-06 | 역구조를 갖는 하이브리드 난워븐 세퍼레이터 |
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JP (1) | JP5823067B2 (ko) |
KR (1) | KR101292657B1 (ko) |
CN (1) | CN104160527A (ko) |
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KR101543399B1 (ko) * | 2013-10-07 | 2015-08-11 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유와 이성분 기재를 포함하는 필터 및 이의 제조방법 |
KR101527500B1 (ko) * | 2013-10-07 | 2015-06-10 | (주)에프티이앤이 | 나일론 나노섬유와 이성분 기재를 포함하는 필터 및 이의 제조방법 |
KR101521598B1 (ko) * | 2013-10-07 | 2015-05-20 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101543398B1 (ko) * | 2013-10-07 | 2015-08-11 | (주)에프티이앤이 | 다중 섬유직경군을 갖는 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101543397B1 (ko) * | 2013-10-07 | 2015-08-11 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101618793B1 (ko) * | 2013-10-07 | 2016-05-04 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101543407B1 (ko) * | 2013-10-07 | 2015-08-11 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101521597B1 (ko) * | 2013-10-07 | 2015-05-20 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유와 이성분 기재를 포함하는 필터 및 이의 제조방법 |
KR101521596B1 (ko) * | 2013-10-07 | 2015-05-20 | (주)에프티이앤이 | 폴리비닐리덴 플루오라이드 나노섬유와 이성분 기재를 포함하는 필터 및 이의 제조방법 |
KR101778249B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 다중 섬유직경군을 갖는 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778250B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 직경이 상이한 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778254B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 기재 사이에 폴리비닐리덴 나노섬유가 저융점 고분자 접착층을 통해 부착된 나노섬유필터 및 이의 제조방법 |
KR101778247B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 3중 나노섬유층을 갖는 필터 및 이의 제조방법 |
KR101778267B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 3중 나노섬유층을 갖는 필터 및 이의 제조방법 |
KR101778248B1 (ko) * | 2015-04-23 | 2017-09-26 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 다중 섬유직경군을 갖는 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778264B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 폴리아크릴로니트릴 나노섬유 및 소수성 고분자 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101753054B1 (ko) * | 2015-04-23 | 2017-07-04 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 내열성 고분자 나노섬유 및 친수성 고분자 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778255B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 나노섬유필터 및 이의 제조방법 |
KR101778253B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 나일론 나노섬유 및 폴리비닐리덴 플루오라이드 나노섬유가 저융점 고분자 접착층을 통해 기재의 양면에 부착된 나노섬유필터 및 이의 제조방법 |
KR101778265B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 폴리비닐알콜 나노섬유 및 소수성 고분자 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778263B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 내열성 고분자 나노섬유 및 친수성 고분자 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778246B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 3중 나노섬유층을 갖는 필터 및 이의 제조방법 |
KR101778266B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 내열성 고분자 나노섬유 및 소수성 고분자 나노섬유를 포함하는 필터 및 이의 제조방법 |
KR101778251B1 (ko) * | 2015-04-23 | 2017-09-13 | (주)에프티이앤이 | 저융점 고분자 접착층이 형성된 폴리우레탄 나노섬유 및 폴리비닐리덴 플루오라이드 나노섬유를 포함하는 필터 및 이의 제조방법 |
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CN110998911B (zh) * | 2017-09-26 | 2022-10-14 | 东丽株式会社 | 多孔性膜、二次电池用隔膜及二次电池 |
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CN113604970B (zh) * | 2021-08-10 | 2022-07-12 | 苏州大学 | 一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法 |
JP2023034887A (ja) * | 2021-08-31 | 2023-03-13 | 株式会社東芝 | 電解コンデンサの製造方法、電解コンデンサ及び電解コンデンサの製造装置 |
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- 2013-02-18 DE DE112013000385.6T patent/DE112013000385T5/de not_active Withdrawn
- 2013-02-18 US US14/369,162 patent/US20150372273A1/en not_active Abandoned
- 2013-02-18 CN CN201380003316.XA patent/CN104160527A/zh active Pending
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JP5823067B2 (ja) | 2015-11-25 |
DE112013000385T5 (de) | 2014-10-30 |
KR101292657B1 (ko) | 2013-08-23 |
CN104160527A (zh) | 2014-11-19 |
JP2015513189A (ja) | 2015-04-30 |
US20150372273A1 (en) | 2015-12-24 |
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