KR101447564B1 - A method for preparing separator for secondary batteries by using Bottom-up electrospinning and separator for secondary batteries using the same - Google Patents
A method for preparing separator for secondary batteries by using Bottom-up electrospinning and separator for secondary batteries using the same Download PDFInfo
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- KR101447564B1 KR101447564B1 KR1020130026998A KR20130026998A KR101447564B1 KR 101447564 B1 KR101447564 B1 KR 101447564B1 KR 1020130026998 A KR1020130026998 A KR 1020130026998A KR 20130026998 A KR20130026998 A KR 20130026998A KR 101447564 B1 KR101447564 B1 KR 101447564B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
- D04H1/4342—Aromatic polyamides
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/498—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres entanglement of layered webs
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- H01M10/04—Construction or manufacture in general
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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
- H01M50/423—Polyamide 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
본 발명은 고분자를 용매에 용해시켜 고분자 용액을 제조하는 단계; 및 상기 고분자 용액을 상향식 전기방사 장치로 전기방사하여 나노섬유 웹을 제조하는 단계;를 포함하는 이차전지용 분리막의 제조방법을 제공한다.
본 발명에 따르면 본 발명에 따른 이차전지용 분리막은 전기 방사를 통해 제조된 나노섬유 웹으로 이루어져 있기 때문에 다공성이며 이로부터 제조된 이차전지는 전지 성능이 우수한 효과가 있고, 상향식 전기방사 공정을 이용함으로써, 종래의 하향식 전기방사에서 발생한 드롭렛(Droplet)이 발생하지 않아 나노섬유 웹 및 분리막의 품질 저하를 방지할 수 있는 효과가 있다.The present invention relates to a method for producing a polymer solution, comprising: preparing a polymer solution by dissolving the polymer in a solvent; And preparing a nanofiber web by electrospinning the polymer solution with a bottom-up electrospinning apparatus. The present invention also provides a method of manufacturing a separation membrane for a secondary battery.
According to the present invention, since the separator for a secondary battery according to the present invention is made of a nanofiber web produced by electrospinning, the secondary battery manufactured from the porous separator has an excellent cell performance. By using a bottom-up electrospinning process, There is no droplet generated in the conventional top-down electrospinning, so that deterioration of the quality of the nanofiber web and separation membrane can be prevented.
Description
본 발명은 전기방사를 이용한 이차전지용 분리막의 제조방법 및 그에 따라 제조된 분리막에 관한 것으로, 보다 구체적으로는 상향식 전기방사를 이용하여 이차전지용 분리막을 제조하는 상향식 전기방사를 이용한 이차전지용 분리막의 제조방법 및 그에 따라 제조된 분리막에 관한 것이다.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a separator for a secondary battery using electrospinning and a separator prepared thereby, and more particularly, to a method for manufacturing a separator for a secondary battery using a bottom- And a separation membrane produced thereby.
일반적으로, 나노섬유(Nano Fiber)란, 지름이 수십에서 수백 나노미터에 불과한 초극세사(超極細絲)를 지칭하는 것으로서, 나노섬유로 구성된 부직포, 멤브레인 및 브레이드 등의 제품은 생활용품, 농업용, 의류용 및 산업용 등으로 널리 사용된다.In general, nanofiber refers to ultra-fine fibers having a diameter of only a few tens to several hundreds of nanometers. Non-woven fabrics, membranes and braids made of nanofibers are used in daily necessities, agriculture, clothing It is widely used for industrial and industrial applications.
상술한 바와 같은 나노섬유는 전기장에 의해 생산된다. 즉, 나노섬유는 원료인 고분자 물질에 고전압의 전기장을 걸어서 원료인 고분자 물질 내부에 전기적인 반발력을 발생시키고, 이로 인해 분자들이 뭉쳐 나노 크기의 실 형태로 갈라짐으로써 나노섬유가 제조 및 생산된다.The nanofibers as described above are produced by an electric field. That is, nanofibers generate electrical repulsive force inside the polymer material by applying a high voltage electric field to the polymer material, which is the raw material, and the nanofibers are manufactured and produced by breaking the molecules into a nano-sized yarn shape.
이때, 전기장이 강할수록 원료인 고분자 물질이 가늘게 찢어지기 때문에 10 내지 1000nm의 가늘기를 갖는 나노섬유를 얻을 수 있다.At this time, as the electric field becomes stronger, the polymer material as the raw material is finely torn, so that a nanofiber having a thinning of 10 to 1000 nm can be obtained.
이러한 가늘기를 갖는 나노섬유를 제조 및 생산하기 위한 전기방사장치는 방사용액이 내부에 충진되는 방사용액 주탱크, 방사용액의 정량 공급을 위한 계량 펌프, 방사용액을 토출하기 위한 노즐이 다수 개 배열 설치되는 노즐블록, 노즐 하단에 위치하여 방사되는 섬유들을 집적하는 컬렉터 및 전압을 발생시키는 전압 발생장치를 포함하여 구성된다.An electrospinning device for manufacturing and producing nanofibers having such thin fibers includes a spinning liquid main tank filled with a spinning solution, a metering pump for supplying a fixed amount of spinning solution, a plurality of nozzles for discharging spinning solution A collector for collecting the fibers that are positioned at the lower end of the nozzle to emit radiation, and a voltage generator for generating a voltage.
상술한 바와 같은 구조로 이루어지는 전기방사장치를 통한 나노섬유 웹의 제조방법은 방사용액이 충진되는 방사용액 주탱크 내의 방사용액이 계량 펌프를 통해 높은 전압이 부여되는 다수의 노즐 내에 연속적으로 정량 공급되고, 노즐로 공급되는 방사용액은 높은 전압이 걸려있는 컬렉터 상에 노즐을 통하여 방사, 집속되어 단섬유 웹이 형성되며, 형성된 단섬유 웹을 엠보싱 또는 니들펀칭하여 부직포로 제조한다.The method of manufacturing a nanofiber web through the electrospinning device having the above-described structure is characterized in that the spinning liquid in the spinning liquid main tank filled with spinning liquid is continuously supplied in a constant amount into a plurality of nozzles to which a high voltage is applied through a metering pump The spinning solution supplied to the nozzle is radiated and condensed through a nozzle on a collector having a high voltage to form a monofilament web, and the formed monofilament web is embossed or needle-punched into a nonwoven fabric.
여기서, 전기방사장치는 컬렉터 상의 위치하는 방향에 따라 상향식 전기방사장치, 하향식 전기방사장치 및 수평식 전기방사장치로 나뉜다. 즉, 전기방사장치는 컬렉터가 노즐의 상단에 위치하는 구성으로 이루어지는 상향식 전기방사장치, 컬렉터가 노즐의 하단에 위치하는 구성으로 이루어지는 하향식 전기방사장치 및 컬렉터와 노즐이 수평방향으로 배열되는 수평식 전기방사장치로 나뉜다.Here, the electrospinning device is divided into a bottom-up electrospinning device, a top-down electrospinning device, and a horizontal electrospinning device depending on the direction on the collector. That is, the electrospinning device includes a bottom-up electrospinning device in which the collector is located at the top of the nozzle, a top-down electrospinning device in which the collector is located at the bottom of the nozzle, Radiating device.
종래의 하향식 전기방사 장치를 이용한 나노섬유의 제조는 방사 시 방사액이 물방울 형태로 그대로 낙하하는 현상(이하 "드롭렛(Droplet)"이라고 한다)이 발생하여 제품의 품질이 저하되는 문제가 있었다.
The production of nanofibers using a conventional top-down electrospinning device has a problem that the quality of the product deteriorates due to the phenomenon (hereinafter referred to as "droplet") in which the spinning liquid falls as a droplet as it is in spinning.
본 발명은 상기 종래의 문제점을 해결하기 위해 고안된 것으로서, 본 발명은 상향식 전기방사를 이용하여 다공성이며, 드롭렛(Droplet)이 없는 고품질의 나노섬유 웹으로 제조된 이차전지용 분리막을 제조할 수 있는 상향식 전기방사를 이용한 이차전지용 분리막의 제조방법 및 그에 따라 제조된 분리막을 제공하는 것을 목적으로 한다.
The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a separator for a secondary battery made of a high-quality nanofiber web, which is porous and has no droplet, It is another object of the present invention to provide a method for manufacturing a separator for a secondary battery using electrospinning and a separator prepared by the method.
본 발명의 적절한 실시 형태에 따르면, 고분자를 용매에 용해시켜 고분자 용액을 제조하는 단계; 및 상기 고분자 용액을 상향식 전기방사 장치로 전기방사하여 나노섬유 웹을 제조하는 단계; 를 포함하는 것을 특징으로 하는 이차전지용 분리막의 제조방법을 제공한다.According to a preferred embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving a polymer in a solvent to prepare a polymer solution; And electrospinning the polymer solution with a bottom-up electrospinning device to produce a nanofiber web; The present invention also provides a method of manufacturing a separation membrane for a secondary battery.
본 발명의 다른 적절한 실시 형태에 따르면, 상기 고분자는 폴리비닐리덴플루오라이드, 폴리아크릴로니트릴, 메타아라미드 및 폴리이미드로 이루어진 군에서 선택되는 하나 이상의 고분자인 것을 특징으로 하는 이차전지용 분리막의 제조방법을 제공한다.According to another preferred embodiment of the present invention, the polymer is at least one polymer selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, meta-aramid and polyimide. to provide.
본 발명의 또 다른 적절한 실시 형태에 따르면, 상기 고분자 용액을 폴리올레핀 기재 또는 무기물로 코팅된 폴리올레핀 기재 상에 전기방사하는 것을 특징으로 하는 이차전지용 분리막의 제조방법을 제공한다.According to another preferred embodiment of the present invention, there is provided a method of manufacturing a separation membrane for a secondary battery, characterized in that the polymer solution is electrospun on a polyolefin substrate or a polyolefin substrate coated with an inorganic material.
본 발명의 다른 적절한 실시 형태에 따르면, 적어도 2개 이상의 고분자를 용매에 용해시켜 각각의 고분자 용액을 제조하는 단계; 및 상기 상향식 전기방사장치의 진행방향으로 적어도 2개 이상의 방사구간을 구획하고, 상기 각 고분자 용액을 구획된 각각의 방사구간에서 방사하는 단계; 를 포함하여 이루어지는 것을 특징으로 하는 이차전지용 분리막의 제조방법을 제공한다.According to another preferred embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving at least two polymers in a solvent to prepare respective polymer solutions; And dividing at least two radiation sections in the traveling direction of the bottom-up electrospinning device, and radiating the respective polymer solutions in respective divided radiation sections; The method of manufacturing a separator for a secondary battery according to the present invention comprises the steps of:
본 발명의 또 다른 적절한 실시 형태에 따르면, 3개 또는 4개의 고분자를 용매에 용해시켜 각각의 고분자 용액을 제조하는 단계; 및 상기 상향식 전기방사장치의 진행방향으로 3개 또는 4개의 방사구간을 구획하고, 상기 각 고분자 용액을 구획된 각각의 방사구간에서 방사하는 단계;를 포함하여 이루어지는 것을 특징으로 하는 이차전지용 분리막의 제조방법을 제공한다.According to another preferred embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving three or four polymers in a solvent to prepare a respective polymer solution; And separating three or four radiation sections in the traveling direction of the bottom-up electrospinning device, and radiating the polymer solution in each of the divided radiation sections. ≪ / RTI >
본 발명의 다른 적절한 실시 형태에 따르면 고분자를 용매에 용해시켜 고분자 용액을 제조하는 단계; 및 상기 고분자 용액을 상향식 전기방사 장치로 전기방사하여 나노섬유 웹을 제조하는 단계; 로 제조된 분리막을 제공한다.
According to another preferred embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: preparing a polymer solution by dissolving a polymer in a solvent; And electrospinning the polymer solution with a bottom-up electrospinning device to produce a nanofiber web; The present invention also provides a separation membrane made of the same.
본 발명에 따른 분리막은 상향식 전기방사 공정을 이용함으로써, 종래의 하향식 전기방사에서 발생한 드롭렛(Droplet)이 발생하지 않아 나노섬유 웹 및 분리막의 품질 저하를 방지할 수 있는 효과가 있다.The separation membrane according to the present invention uses a bottom-up electrospinning process to prevent deterioration of the nanofiber web and separation membrane due to no droplet generated in conventional top-down electrospinning.
또한, 전기 방사를 통해 제조된 나노섬유 웹으로 이루어져 있기 때문에 다공성이며 이로부터 제조된 이차전지는 전지 성능이 우수한 효과가 있다.
In addition, since it is made of a nanofiber web produced through electrospinning, the secondary battery manufactured from the porous material has an excellent effect on the battery performance.
도 1은 본 발명에 의한 상향식 전기방사를 이용한 이차전지용 분리막을 제조하기 위한 장치를 개략적으로 나타내는 도면.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view schematically showing an apparatus for manufacturing a separator for a secondary battery using bottom-up electrospinning according to the present invention. FIG.
이하, 본 발명에 대해서 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 분리막을 구성하는 나노섬유 웹은 고분자를 용매에 용해시켜 고분자 용액을 제조하는 단계; 및 상기 고분자 용액을 상향식 전기방사 장치로 전기방사하여 나노섬유 웹을 제조하는 단계; 를 포함하는 것을 특징으로 하는 분리막의 제조방법 및 그에 따라 제조된 분리막에 관한 것이다.The nanofiber web constituting the separation membrane according to the present invention comprises the steps of preparing a polymer solution by dissolving a polymer in a solvent; And electrospinning the polymer solution with a bottom-up electrospinning device to produce a nanofiber web; The present invention relates to a method for producing a separation membrane, and a separation membrane produced thereby.
본 발명에 따른 고분자는 폴리비닐리덴플루오라이드, 폴리비닐리덴 플루오라이드-헥사플루오르 프로필렌 공중합체, 혹은 이들의 복합 조성물, 폴리아믹산, 폴리아마이드, 폴리이미드, 폴리아미드이미드, 폴리(메타-페닐렌 이소프탈아미이드), 메타아라미드, 폴리에틸렌클로로트리플루오로에틸렌, 폴리클로로트리플루오로에틸렌, 폴리메틸메타크릴레이트, 폴리아크릴로니트릴, 폴리비닐리덴클로라이드-아크릴로니트릴 공중합체, 폴리아크릴아미드 등으로 구성되는 군에서 선택된 어느 하나 이상의 물질이다. The polymer according to the present invention may be at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or a composite composition thereof, polyamic acid, polyamide, polyimide, polyamideimide, poly (meta-phenylene isoprene Polyacrylonitrile, polyvinylidene chloride-acrylonitrile copolymer, polyacrylamide, and the like), polyvinylidene chloride-acrylonitrile copolymer, polyvinylidene chloride-acrylonitrile copolymer, Is one or more substances selected from the group consisting of
사용 가능한 용매로는 아세톤, 테트라하이드로퓨란, 메틸렌클로라이드, 클로로포름, 디메틸포름아마이드, 디메틸아세트아마이드, N-메틸-2-피롤리돈, 시클로헥산, 물 또는 이들의 혼합체 등이 있으나 반드시 이에 한정 되는 것은 아니다.Examples of usable solvents include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, cyclohexane, water or a mixture thereof. no.
본 발명에 의한 상향식 전기방사장치는 도 1에서 도시하고 있는 바와 같이, 방사용액이 충진되는 방사용액 주탱크(1), 방사용액 정량 공급을 위한 계량펌프(2), 상기 계량펌프와 노즐블록(4) 사이에 위치하여 방사용액을 공급하는 방사용액 드롭장치(3), 다수개의 핀으로 구성되는 노즐(5)이 블록형태로 조합되며, 방사용액을 섬유상으로 토출하는 상향식 노즐블록(4), 상기 노즐블록 상부에 위치하여 방사되는 단섬유들을 집적하는 컬렉터(7), 고전압을 발생시키는 전압 발생장치(8) 및 노즐 블록의 최상부에 연결된 방사용액 배출장치(10)를 포함하여 구성된다.As shown in FIG. 1, the bottom-up electrospinning apparatus according to the present invention includes a spinning liquid main tank 1 filled with a spinning solution, a
여기서, 상기 노즐블록(4) 상에 위치하는 노즐(5)들은 대각선 또는 일직선상으로 배열되며, 노즐의 출구가 상부방향으로 형성되어 있고, 컬렉터(7)가 노즐블록(4)의 상부에 위치하여 방사용액을 상부 방향으로 방사한다. Here, the
또한, 상기 노즐블록(4) 전체는 전기 방사되는 나노섬유(6)의 분포를 균일하게 하기 위해서 노즐블록 좌우 왕복운동장치(9)에 의해 전기 방사되는 나노섬유(6)의 진행 방향과 직각방향으로 좌우 왕복운동을 한다. In order to uniformize the distribution of the
그리고, 상기 노즐블록(4)의 최상부에는 노즐블록에 과잉 공급된 방사용액을 방사용액 주탱크(1)로 강제 이송시키는 방사용액 배출장치(10)가 연결되어 있다.A spinning
상기 방사용액 배출장치(10)는 노즐블록 내로 과잉 공급된 방사용액을 방사용액 주탱크(1) 로 강제 이송시킨다.The spinning
또한, 본 발명의 컬렉터(7)에는 직접가열 방식 또는 간접가열 방식의 가열장치(미도시)가 설치되고, 상기 컬렉터(7)는 고정 또는 연속 회전한다.The
이하, 본 발명에 의한 상향식 전기방사를 이용한 이차전지용 분리막의 제조방법을 설명한다.Hereinafter, a method for manufacturing a secondary battery separator using bottom-up electrospinning according to the present invention will be described.
먼저, 방사용액 주탱크(1) 내에 구비된 고분자 방사용액을 계량펌프(2)로 계량하여 정량씩 방사용액 드롭장치(3)로 공급한다. First, the polymer spinning solution contained in the spinning solution main tank 1 is metered by the
이 때, 방사용액은 폴리비닐리덴플루오라이드, 폴리비닐리덴 플루오라이드-헥사플루오르 프로필렌 공중합체, 혹은 이들의 복합 조성물, 폴리아마이드, 폴리이미드, 폴리아미드이미드, 폴리(메타-페닐렌 이소프탈아미이드), 메타아라미드, 폴리에틸렌클로로트리플루오로에틸렌, 폴리클로로트리플루오로에틸렌, 폴리메틸메타크릴레이트, 폴리아크릴로니트릴, 폴리비닐리덴클로라이드-아크릴로니트릴 공중합체, 폴리아크릴아미드 등으로 구성되는 군에서 선택된 어느 하나 이상의 고분자 물질이 용매에 용해된 용액을 사용할 수 있다.In this case, the spinning solution may be at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, or a composite composition thereof, polyamide, polyimide, polyamideimide, poly (meta-phenylene isophthalamide ), Methacrylamide, polyethylene chlorotrifluoroethylene, polychlorotrifluoroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride-acrylonitrile copolymer, polyacrylamide and the like A solution in which any one or more selected polymer substances are dissolved in a solvent may be used.
상기한 바와 같이, 상기 방사용액 드롭장치(3) 내로 공급된 방사용액은 방사용액 드롭장치(3)를 통과하면서 노즐블록(4)에 공급된다.As described above, the spinning solution supplied into the spinning
계속해서 상기 노즐블록(4)에서는 방사액을 상향식 노즐(5)을 통해 높은 전압이 걸려있는 상부의 컬렉터(7)로 상향 토출하여 나노섬유(6)를 제조한다. Subsequently, in the
여기서, 상기 컬렉터에 폴리올레핀 기재 상에 또는 무기물로 코팅된 폴리올레핀 기재를 위치 및 투입한 후 상기 노즐을 통하여 방사되는 방사용액을 각 기재 상에 상향 토출하여 복합막을 제조하는 것도 가능하다. Here, it is also possible to prepare a composite membrane by placing and injecting a polyolefin substrate coated on a polyolefin substrate or an inorganic material into the collector, and then discharging spinning solution radiated through the nozzle upward on each substrate.
상기 폴리올레핀 기재의 두께는 5 내지 50, 공극율은 30 내지 80%인 것이 바람직하다. The thickness of the polyolefin substrate is preferably 5 to 50, and the porosity is preferably 30 to 80%.
상기 무기물은 SiO2, Al2O3, TiO2, Li3PO4, 제올라이트, MgO, CaO, BaTiO3, Li2O, LiF, LiOH, Li3N, BaO, Na2O, Li2CO3, CaCO3, LiAlO2, SiO, SnO, SnO2, PbO2, ZnO, P2O5, CuO, MoO, V2O5, B2O3, Si3N4, CeO2, Mn3O4, Sn2P2O7, Sn2B2O5, Sn2BPO6 및 이들의 혼합물 등으로 구성된 군에서 선택된 어느 하나 이상인 것이 바람직하다.The inorganic substance is SiO 2, Al 2 O 3,
계속해서 상기 노즐(5)을 통해서 섬유화 되지 못하고 과잉 방사된 용액은 방사용액 배출장치(10)에 의해 방사용액 주탱크(1)로 강제 이송된다.Subsequently, the solution which has not been fiberized through the
이 때, 전기력에 의한 섬유형성을 촉진하기 위하여 노즐블록(4) 하단부의 도전체판과 컬렉터(7)에는 전압발생장치(8)에서 발생된 1kV 이상, 더욱 바람직하게는 20kV 이상의 전압을 걸어준다. 상기 컬렉터(7)로는 엔드레스(Endless) 벨트를 사용하는 것이 생산성 측면에서 더욱 유리하다. 상기 컬렉터(7)는 부직포의 밀도를 균일하게하기 위하여 좌우로 일정거리를 왕복 운동하는 것이 바람직하다.At this time, a voltage of 1 kV or more, more preferably 20 kV or more, generated by the
이와 같이 컬렉터(7) 상에 형성된 나노섬유 웹(12)은 나노섬유 웹 지지 로울러(11)를 거쳐서 나노섬유 웹 권취 로울러(13)에 권취하면 나노섬유 웹 제조 공정이 완료된다.As described above, the
본 발명의 상향식 전기방사장치는 드롭렛(Droplet) 현상을 효과적으로 방지하여 나노섬유 웹의 품질을 향상시킬 수 있으며 제조된 나노섬유 웹은 얇은 두께와 높은 다공도를 갖게 되어 이차전지용 분리막으로 사용되어 이차전지의 성능을 향상시킬 수 있다.The bottom-up electrospinning apparatus of the present invention can effectively prevent the droplet phenomenon and improve the quality of the nanofiber web. The nanofiber web produced has a thin thickness and a high porosity to be used as a separator for a secondary battery, Can be improved.
또한 적어도 2개 이상의 고분자를 각각 용매에 용해시킨 고분자 용액을 제조하고, 상기 상향식 전기방사장치의 노즐블럭(4)이 진행방향으로 적어도 2개 이상의 방사구간을 구획하고, 상기 각 고분자 용액을 구획된 각각의 방사구간에서 토출하여 2층 이상의 다층 분리막을 제조하는 것도 가능하며, 각각의 방사구간에서 토출하는 고분자 용액은 상호 다른 것으로 이루어지는 것도 가능하다.A polymer solution in which at least two or more polymers are respectively dissolved in a solvent is prepared, at least two radiation sections are divided in the direction of travel of the nozzle block (4) of the bottom-up electrospinning device, It is also possible to manufacture a multilayer separation membrane of two or more layers by discharging in each radiation section, and the polymer solution to be discharged in each emission section may be made different from each other.
이하에서는 구체적 실시예를 통하여 본 발명의 효과를 보다 구체적으로 살펴보도록 한다. 이들 실시예는 단지 본 발명의 이해를 돕기 위한 것으로서 본 발명의 권리범위를 제한하지는 않는다.
Hereinafter, the effects of the present invention will be described in more detail with reference to concrete examples. These embodiments are only for the understanding of the present invention and do not limit the scope of the present invention.
실시예1Example 1
중량평균분자량이 100,000인 폴리아믹산을 디메틸아세트아미드(DMAc)에 녹여 방사용액을 제조하였다. 방사용액을 상향식 전기방사장치에 투입하고 방사노즐에 공급하여 컬렉터 상에 상향식으로 전기방사하였다. 이 때 방사노즐당 토출양은 10㎖/분이었으며, 전극과 컬렉터 간의 거리는 40cm, 인가전압은 20kV였다. 나노섬유 웹의 두께는 10㎛였으며, 전기방사 후에는 300℃에서 열처리를 하여 폴리아믹산을 이미드화 시켰다.
Polyamic acid having a weight average molecular weight of 100,000 was dissolved in dimethylacetamide (DMAc) to prepare a spinning solution. The spinning solution was charged into a bottom-up electrospinning apparatus and fed to a spinning nozzle to electrospray on a collector in a bottom-up manner. At this time, the discharge amount per spinneret was 10 ml / min, the distance between the electrode and the collector was 40 cm, and the applied voltage was 20 kV. The thickness of the nanofiber web was 10 탆, and after electrospinning, the polyamic acid was imidized by heat treatment at 300 캜.
실시예2Example 2
중량평균분자량이 157,000인 폴리아크릴로니트릴(한일합섬)을 디메틸포름아마이드(DMF)에 녹여 폴리아크릴로니트릴 방사용액을 제조하고 공급장치에 투입하고 5㎛ 두께의 폴리프로필렌(Celgard 2400) 분리막 상에 상향식으로 전기방사를 하였다. 이 때 방사노즐당 토출양은 10㎖/분이었으며, 전극과 컬렉터 간의 거리는 40cm, 인가전압은 20kV였다. 나노섬유 웹의 두께는 5㎛로 제조하였다.
Polyacrylonitrile (Hanil Synthetic Fiber) having a weight average molecular weight of 157,000 was dissolved in dimethylformamide (DMF) to prepare a polyacrylonitrile spinning solution. The polyacrylonitrile spinning solution was added to a feeding device, and the mixture was placed on a polypropylene (Celgard 2400) Electrospinning was carried out in a bottom-up manner. At this time, the discharge amount per spinneret was 10 ml / min, the distance between the electrode and the collector was 40 cm, and the applied voltage was 20 kV. The thickness of the nanofiber web was 5 μm.
실시예3Example 3
폴리비닐리덴플루오라이드(KYNAR741)와 중량평균분자량이 300,000인 메타아라미드(E. I. du Pont de Nemours and Company)를 각각 디메틸아세트아미드(DMAc)와 디메틸포름아마이드(DMF)에 녹여 방사용액을 제조하였다. 상향식 전기방사장치의 방사구역을 2구간으로 구획하고, 제1 방사구간에 연결설치된 제1 공급장치에는 폴리비닐리덴플루오라이드 방사용액을 투입하고, 제2 방사구간에 연결설치된 제2 공급장치에는 메타아라미드 방사용액을 투입하여 연속적으로 상향식으로 전기방사를 실시하였다. 제1 공급장치가 연결된 제1 구간에서는 컬렉터상에 폴리비닐리덴플루오라이드 나노섬유 웹이 형성되고 일정속도로 컬렉터가 이동하여 제2 공급장치가 연결된 제2 구간에서는 상기 폴리비닐리덴플루오라이드 나노섬유 웹 상부면에 메타아라미드가 적층형성된 2층 분리막이 형성되었다. 이 때 방사노즐당 토출양은 10㎖/분이었으며, 전극과 컬렉터 간의 거리는 40cm, 인가전압은 20kV였다. 제조된 분리막 총 두께는 10㎛이었다.
Polyvinylidene fluoride (KYNAR 741) and a meta-aramid (EI du Pont de Nemours and Company) having a weight average molecular weight of 300,000 were dissolved in dimethylacetamide (DMAc) and dimethylformamide (DMF), respectively. The second supply device connected to the second radiation section is connected to the first radiation section and the second radiation section is connected to the first radiation section. The first radiation section is connected to the first radiation section, Aramid spinning solution was added and electrospinning was performed continuously upside down. In the first section where the first feeding device is connected, the polyvinylidene fluoride nanofiber web is formed on the collector, the collector is moved at a constant speed, and in the second section in which the second feeding device is connected, the polyvinylidene fluoride nanofiber web A two-layer separation membrane having meta-aramid laminated on its upper surface was formed. At this time, the discharge amount per spinneret was 10 ml / min, the distance between the electrode and the collector was 40 cm, and the applied voltage was 20 kV. The total thickness of the prepared separator was 10 탆.
비교예1Comparative Example 1
실시예1과 비교해서 전기방사 방식을 하향식으로 한 것을 제외하고는 동일한 조건으로 실험을 실시하였다.
Experiments were conducted under the same conditions except that the electrospinning method was top down as compared with Example 1. [
본 발명의 실시예 1 내지 4와 비교예 1을 비교한 결과, 실시예1 내지 4에서 제조된 나노섬유 웹은 비교예 1 에 비해 비교적으로 섬유직경이 균일하여 섬유균일도가 우수했다. 또한, 드롭렛 현상이 비교예1에는 발생한 반면, 실시예 1 내지 4에는 발생하지 않아 분리막의 품질이 우수함을 알 수 있다.
As a result of comparing Examples 1 to 4 of the present invention and Comparative Example 1, the nanofiber webs prepared in Examples 1 to 4 were comparatively uniform in fiber diameter and excellent in fiber uniformity as compared with Comparative Example 1. In addition, although the droplet phenomenon occurred in Comparative Example 1, it did not occur in Examples 1 to 4, indicating that the quality of the separation membrane was excellent.
1 : 방사용액 주탱크 2 : 계량 펌프
3 : 방사용액 드롭장치 4 : 노즐블록
5 : 노즐 6 : 나노섬유
7 : 컬렉터 8 : 전압발생장치
9 : 노즐블록 좌우 왕복운동장치 10 : 방사용액 배출장치
11 : 나노섬유 웹 지지 로울러 12 : 나노섬유 웹
13 : 나노섬유 웹 권취 로울러 1: Fluid Main tank 2: Metering pump
3: Fluid drop device 4: Nozzle block
5: nozzle 6: nanofiber
7: Collector 8: Voltage generator
9: a reciprocating motion device for the left and right of the nozzle block 10:
11: Nano fiber web support roller 12: Nano fiber web
13: Nano fiber web winding roller
Claims (6)
상기 고분자 용액을 전기방사장치로 전기방사하여 나노섬유 웹을 제조하는 이차전지용 분리막의 제조방법에 있어서,
상기 전기방사장치의 진행방향으로 2개의 방사구간을 구획하고, 상기 고분자로서 폴리비닐리덴 플루오라이드와 메타아라미드를 각각 용매에 용해시켜 폴리비닐리덴 플루오라이드 방사용액과 메타아라미드 방사용액을 제조하는 단계;
상기 폴리비닐리덴 플루오라이드 방사용액을 제1 방사구간에 투입하고 상기 메타아라미드 방사용액을 제2 방사구간에 투입하는 단계;
상기 제1 방사구간에서는 폴리비닐리덴 플루오라이드 방사용액이 전기방사되어 컬렉터 상에 폴리비닐리덴 플루오라이드 나노섬유 웹이 형성되는 단계; 및
상기 제2 방사구간에서는 상기 폴리비닐리덴 플루오라이드 나노섬유 웹 상에 메타아라미드 방사용액이 전기방사되어 메타아라미드 나노섬유 웹이 적층형성되는 단계;를 포함하며 상기 전기방사장치는 상향식 전기방사장치인 것을 특징으로 하는 이차전지용 분리막의 제조방법.Dissolving the polymer in a solvent to prepare a polymer solution; And
A method for producing a separation membrane for a secondary battery, which comprises preparing a nanofiber web by electrospinning the polymer solution with an electrospinning device,
Dividing two radiation sections in the traveling direction of the electrospinning apparatus and dissolving polyvinylidene fluoride and meta-aramid as a polymer in a solvent to prepare a polyvinylidene fluoride spinning solution and a methaaramide spinning solution;
Introducing the polyvinylidene fluoride spinning solution into a first spinning zone and injecting the meta-aramid spinning solution into a second spinning zone;
Forming a polyvinylidene fluoride nanofiber web on the collector by electrospinning the polyvinylidene fluoride spinning solution in the first radiation section; And
And a step of electrospinning a methacrylamide spinning solution on the polyvinylidene fluoride nanofiber web to form a laminate of a meta-aramid nanofiber web in the second radiation section, wherein the electrospinning device is a bottom-up electrospinning device Wherein the separator is formed of a metal.
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| KR20110026186A (en) * | 2009-09-07 | 2011-03-15 | 한국생산기술연구원 | Hydrophilic polyolefin separator, method for manufacturing the production and secondary battery using thereof |
| KR20110093714A (en) * | 2010-02-12 | 2011-08-18 | 주식회사 아모그린텍 | Ultrafine fibrous separator with high heat-resistance and high strength and method of manufacturing the same |
| KR20110105365A (en) * | 2010-03-18 | 2011-09-26 | 주식회사 아모그린텍 | Ultrafine fibrous separator having shutdown function, method and apparatus for manufacturing the same |
| KR101213567B1 (en) | 2011-08-05 | 2012-12-18 | 신슈 다이가쿠 | A separator containing adhesive nano-fiber layer and inorganic particles, a method and an apparatus for manufacturing the same |
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| KR20110026186A (en) * | 2009-09-07 | 2011-03-15 | 한국생산기술연구원 | Hydrophilic polyolefin separator, method for manufacturing the production and secondary battery using thereof |
| KR20110093714A (en) * | 2010-02-12 | 2011-08-18 | 주식회사 아모그린텍 | Ultrafine fibrous separator with high heat-resistance and high strength and method of manufacturing the same |
| KR20110105365A (en) * | 2010-03-18 | 2011-09-26 | 주식회사 아모그린텍 | Ultrafine fibrous separator having shutdown function, method and apparatus for manufacturing the same |
| KR101213567B1 (en) | 2011-08-05 | 2012-12-18 | 신슈 다이가쿠 | A separator containing adhesive nano-fiber layer and inorganic particles, a method and an apparatus for manufacturing the same |
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