KR101746764B1 - Non-woven web with improved mechanical properties and shrinkage and method of making the same - Google Patents

Non-woven web with improved mechanical properties and shrinkage and method of making the same Download PDF

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KR101746764B1
KR101746764B1 KR1020130116924A KR20130116924A KR101746764B1 KR 101746764 B1 KR101746764 B1 KR 101746764B1 KR 1020130116924 A KR1020130116924 A KR 1020130116924A KR 20130116924 A KR20130116924 A KR 20130116924A KR 101746764 B1 KR101746764 B1 KR 101746764B1
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nonwoven fabric
nanoparticles
fibrils
organic polymer
mechanical properties
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KR1020130116924A
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Korean (ko)
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KR20150037391A (en
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임정호
윤경환
강정안
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주식회사 엘지화학
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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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D04H1/4291—Olefin series
    • 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
    • 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
    • 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
    • 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
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • 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
    • D04H13/00—Other non-woven fabrics
    • 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
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/10—Physical properties porous
    • 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

Abstract

본 발명의 부직포는 표면 개질된 나노입자가 균일하게 분산된 피브릴에 의해 제조되며, 상기 나노입자가 보강재 역할을 하여 부직포의 기계적 물성을 향상시키고, 나노입자 표면을 개질시킴으로써 부직포의 수축특성이 더욱 개선되는 효과를 갖게 된다. 본 발명의 부직포는 이차전지의 분리막으로도 적합하다.The nonwoven fabric of the present invention is produced by fibrils in which surface-modified nanoparticles are uniformly dispersed. The nanoparticles serve as a reinforcing material to improve the mechanical properties of the nonwoven fabric and modify the surface of the nanoparticle, And an improvement effect is obtained. The nonwoven fabric of the present invention is also suitable as a separation membrane of a secondary battery.

Description

기계적 물성 및 수축특성이 향상된 부직포 및 그의 제조방법 {Non-woven web with improved mechanical properties and shrinkage and method of making the same}BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nonwoven fabric having improved mechanical properties and shrinking properties,

본 발명은 기계적 물성 및 수축특성이 향상된 부직포 및 그의 제조방법에 관한 것으로, 보다 구체적으로는 고분자 피브릴(fibril)에 나노입자가 균일하게 분산되어 있어 향상된 기계적 물성 및 수축특성을 갖는 부직포 및 그의 제조방법에 관한 것이다.
The present invention relates to a nonwoven fabric having improved mechanical properties and shrinking properties and a method for producing the same. More specifically, the present invention relates to a nonwoven fabric having nanoparticles uniformly dispersed in a polymeric fibril and having improved mechanical properties and shrinking properties, ≪ / RTI >

부직포는 다양한 용도에서 광범위하게 이용되고 있는데, 예를 들면, 정수용 필터, 공기 정화용 필터, 복합재료, 연료전지용 전해질막 또는 이차전지용 분리막 등으로 이용될 수 있다.Nonwoven fabrics are widely used in various applications such as water purification filters, air purification filters, composite materials, electrolyte membranes for fuel cells, separators for secondary batteries, and the like.

이러한 부직포는 연신 공정을 거쳐 제조될 수 있는데, 기계적 물성은 연신에 비례하여 향상되는 한편, 수축특성 역시 연신에 비례하여 증가하는 경향이 있다. 이는, 연신 공정을 거치면서 부직포를 이루고 있는 고분자 사슬 사이에서 응력 유도 결정화(stress induced crystallization)가 일어나서 기계적 물성이 향상되지만, 연신을 많이 할수록 복원력도 강해지기 때문에 시간이 오래 경과하거나 일정 온도 이상에서는 부직포를 이루는 피브릴이 연신 전의 형태로 되돌아가려 하고, 그 결과 바람직하지 않은 수축률을 나타내게 된다. 부직포는 그 사용 용도에 따라 높은 기계적 물성과 낮은 수축특성 둘다를 만족시키는 것이 요구될 수 있는데, 예컨대, 이차전지용 분리막 기재로 부직포가 사용되는 경우가 그러하다.Such a nonwoven fabric can be produced through a stretching process. The mechanical properties of the nonwoven fabric are improved in proportion to the elongation, while the shrinking properties tend to increase in proportion to the elongation. This is because the stress induced crystallization occurs between the polymer chains forming the nonwoven fabric through the stretching process so that the mechanical properties are improved. However, since the longer the stretching time is, the longer the time is elapsed or the nonwoven fabric Is intended to return to the form before stretching, resulting in an undesirable shrinkage ratio. The nonwoven fabric may be required to satisfy both of high mechanical properties and low shrinkage characteristics depending on the intended use thereof, for example, when a nonwoven fabric is used as a separator for a secondary battery.

이차전지는 크게 음극(anode), 분리막(separator), 양극(cathode) 및 전해질 등으로 구성되며, 분리막은 이차전지의 음극과 양극을 분리하고 전해질을 통과시키는 역할을 한다. 만약, 분리막의 기계적 물성이 일정 수준 이하이거나 수축 특성이 지나치게 과도할 경우, 분리막이 쉽게 손상되거나 지나치게 수축되어 음극과 양극이 쉽게 단락을 일으키는 결과를 초래할 수 있다.
The secondary battery includes an anode, a separator, a cathode, and an electrolyte. The separator separates the cathode and the anode of the secondary battery and passes the electrolyte. If the mechanical properties of the membrane are below a certain level, or if the shrinkage characteristics are excessively high, the membrane may be easily damaged or excessively shrunk resulting in a short circuit between the cathode and the anode.

본 발명은 상기 종래의 문제점을 해결하기 위해 고안된 것으로서, 높은 기계적 물성과 낮은 수축특성을 가져서 이차전지용 분리막으로 사용하기에 적합한 부직포 및 그의 제조방법을 제공하고자 한다.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a nonwoven fabric having high mechanical properties and low shrinkage characteristics.

전술한 과제를 해결하기 위하여, 본 발명의 일 양태에 따르면, 부직포가 피브릴(fibril)에 의해 형성되고, 상기 피브릴이 유기 고분자 화합물과 나노입자를 포함하는 부직포가 제공된다.According to one aspect of the present invention, there is provided a nonwoven fabric in which a nonwoven fabric is formed by fibrils, and the fibrils comprise an organic polymer compound and nanoparticles.

상기 유기 고분자 화합물에 상기 나노입자가 분산되어 있을 수 있다.The nanoparticles may be dispersed in the organic polymer compound.

상기 유기 고분자 화합물은 폴리올레핀, 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈렌(PEN), 폴리에스테르, 나일론, 폴리이미드, 폴리벤즈옥사졸, 폴리테트라플루오로에틸렌, 폴리아릴렌에테르술폰, 폴리에테르에테르케톤 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물일 수 있다.Wherein the organic polymer compound is selected from the group consisting of polyolefin, polyethylene terephthalate (PET), polyethylene naphthalene (PEN), polyester, nylon, polyimide, polybenzoxazole, polytetrafluoroethylene, polyarylene ether sulfone, And mixtures of two or more thereof selected from the group consisting of these copolymers.

상기 나노입자는 입자 종횡비(aspect ratio)가 큰 것을 특징으로 할 수 있다.The nanoparticles may have a high aspect ratio.

상기 나노입자는 세피오라이트(sepiorite), 나노클레이(nanoclay) 및 침상 탈크(talc)로 이루어진 군에서 선택된 1종 또는 2종 이상의 혼합물일 수 있다.The nanoparticles may be one or a mixture of two or more selected from the group consisting of sepiolite, nanoclay, and acicular talc.

상기 나노입자는 표면 개질될 수 있다.The nanoparticles may be surface modified.

양극, 음극, 및 상기 양극과 음극 사이에 개재된 분리막을 포함하는 전기화학소자에 있어서, 상기 분리막이 전술한 부직포인 것을 특징으로 하는 전기화학소자.An electrochemical device comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein the separator is the above-described nonwoven fabric.

본 발명의 다른 양태에서는, 유기 고분자 화합물과 나노입자를 포함하는 방사용액을 제조한 후 상기 방사용액을 전기방사하여 부직포 웹을 제조하는 단계를 포함하는 부직포의 제조방법이 제공된다.
In another aspect of the present invention, there is provided a method of manufacturing a nonwoven fabric comprising the steps of: preparing a spinning solution containing an organic polymer compound and nanoparticles, and then spinning the spinning solution to prepare a nonwoven web.

본 발명의 부직포는 나노입자가 피브릴에 분산되어 있어 높은 기계적 물성과 낮은 수축특성을 가질 수 있다. 또한, 본 발명의 부직포에서는 나노입자가 피브릴 자체에 분산되어 있으므로, 부직포 기공을 폐색시키지 않으면서 부직포의 기계적 물성과 수축특성을 향상시킬 수 있다. 또한, 표면 개질된 나노입자가 사용될 경우, 고분자와 나노입자간의 계면이 조절될 수 있다.The nonwoven fabric of the present invention can have high mechanical properties and low shrinkage properties because nanoparticles are dispersed in fibrils. Further, in the nonwoven fabric of the present invention, since the nanoparticles are dispersed in the fibril itself, the mechanical properties and shrinkage characteristics of the nonwoven fabric can be improved without blocking the nonwoven fabric pores. Also, when surface modified nanoparticles are used, the interface between the polymer and nanoparticles can be controlled.

이러한 부직포를 이차전지용 분리막으로 사용할 경우, 분리막의 기계적 물성 및 수축 특성이 개선될 수 있다.
When such a nonwoven fabric is used as a separation membrane for a secondary battery, mechanical properties and shrinkage characteristics of the separation membrane can be improved.

이하, 본 발명을 상세히 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

본 발명의 부직포는 피브릴을 구성하는 유기 고분자 화합물에 나노입자가 포함되어 있고, 바람직하게는 분산되어 있는 것을 특징으로 한다. The nonwoven fabric of the present invention is characterized in that the organic polymeric compound constituting the fibril contains nanoparticles, and is preferably dispersed therein.

피브릴은 천연 물질, 합성 물질 또는 이들의 혼합물과 같은 유기 고분자 화합물로부터 제조될 수 있다.The fibrils can be prepared from organic polymeric compounds such as natural materials, synthetic materials or mixtures thereof.

천연 물질로는 목재 유래의 셀룰로오스 섬유, 마, 면, 사탕수수등의 비목재 유래의 셀룰로오스 섬유, 바이오셀룰로오스 섬유, 양모, 비단 등을 들 수 있다.Natural materials include cellulosic fibers derived from wood, cellulose fibers derived from non-wood such as cotton, cotton and sugar cane, bio-cellulose fibers, wool, silk.

합성 물질로는 폴리올레핀, 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈렌(PEN), 폴리에스테르, 나일론, 폴리이미드, 폴리벤즈옥사졸, 폴리테트라플루오로에틸렌, 폴리아릴렌에테르술폰, 폴리에테르에테르케톤, 그들의 공중합체 또는 그들의 혼합물을 들 수 있으나, 반드시 이에 한정되는 것은 아니다.Examples of synthetic materials include polyolefin, polyethylene terephthalate (PET), polyethylene naphthalene (PEN), polyester, nylon, polyimide, polybenzoxazole, polytetrafluoroethylene, polyarylene ether sulfone, polyetheretherketone, Copolymers, or mixtures thereof, but are not limited thereto.

이 중, 폴리올레핀의 구체적인 예로는 에틸렌과 하나 이상의 C3∼C12 알파올레핀을 공중합시켜 제조되는 폴리에틸렌을 포함하는 저밀도 폴리에틸렌, 고밀도 폴리에틸렌 및 직쇄의 저밀도 폴리에틸렌과 같은 폴리에틸렌; 및 이소택틱 폴리프로필렌, 어택틱(atactic) 폴리프로필렌, 신디오택틱(syndiotactic) 폴리프로필렌과 같은 폴리프로필렌을 들 수 있으나, 이에 한정되는 것은 아니다. 폴리올레핀은 이차전지 분리막 기재의 제조에 널리 사용되는 물질이다.Specific examples of the polyolefins include low density polyethylene including polyethylene produced by copolymerizing ethylene with at least one C 3 -C 12 alpha olefin, polyethylene such as low density polyethylene of high density polyethylene and linear low density polyethylene; And polypropylenes such as isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, but are not limited thereto. Polyolefins are widely used materials for the production of secondary battery separator film substrates.

피브릴은 전술한 천연 물질, 합성 물질 또는 이들의 혼합물와 같은 유기 고분자 화합물 이외에 나노입자를 포함한다. 나노입자의 함량은 부직포의 기계적 물성 및 수축특성 향상이라는 본 발명의 효과를 나타낼 수 있으면서 저항 증가와 같은 의도하지 않은 효과를 발생시키지 않아야 한다. The fibrils include nanoparticles in addition to the above-described organic polymer compounds such as natural materials, synthetic materials, or mixtures thereof. The content of the nanoparticles should not cause undesirable effects such as increased resistance while exhibiting the effects of the present invention in improving the mechanical properties and shrinkage properties of the nonwoven fabric.

나노입자는 침상 형태를 갖는 것이 바람직한데, 침상 형태의 나노입자가 보강재로 보다 우수하게 작용하여, 부직포의 기계적 물성을 향상시킬 수 있기 때문이다. 표면개질된 나노입자는 예컨대, 2:1 내지 20:1의 입자 종횡비(aspect ratio)를 가질 수 있다. 이러한 나노입자의 예로는 세피오라이트(sepiorite), 나노클레이(nanoclay) 및 침상 탈크(talc)로 이루어진 군에서 선택된 1종 또는 2종 이상의 혼합물일 수 있으나, 이에 한정되는 것은 아니다.It is preferable that the nanoparticles have an acicular shape, because the acicular nanoparticles act better as a reinforcing material, thereby improving the mechanical properties of the nonwoven fabric. The surface modified nanoparticles may have a particle aspect ratio of, for example, 2: 1 to 20: 1. Examples of such nanoparticles include, but are not limited to, a mixture of one or more selected from the group consisting of sepiolite, nanoclay, and acicular talc.

표면개질된 나노입자는 표면개질로 인해 피브릴과 나노입자 간의 계면이 조절되어 고분자 사슬의 움직임(mobility)을 제한할 수 있으며, 그 결과 부직포의 수축특성을 더욱 개선시킬 수 있다. The surface modified nanoparticles can regulate the interface between the fibrils and the nanoparticles due to the surface modification, thereby restricting the mobility of the polymer chain and consequently improving the shrinkage properties of the nonwoven fabric.

나노입자의 크기는 특별히 한정되지 않으나, 지나치게 작은 경우에는 분산성이 저하될 뿐만 아니라 크기가 미미하여 보강재 역할을 충분히 발휘하지 못하게 되고, 지나치게 큰 경우에는 피브릴 사이에 균일하게 분포되기 어렵고 부직포 두께를 증가시키는 요인이 될 수 있다.The size of the nanoparticles is not particularly limited. However, when the size of the nanoparticles is too small, the dispersibility of the nanoparticles is decreased and the size of the nanoparticles is too small to sufficiently exhibit the function as a reinforcing material. It can be a factor to make.

본 발명에서는 피브릴 자체에 나노입자가 분산되어 있기 때문에, 종래 피브릴 사이에 무기입자가 존재하거나 부직포 일면에 무기물층이 코팅되어 있는 부직포가 이차전지용 분리막으로 사용되는 경우에 발생하였던 기공 폐색이나 저항 증가와 같은 악영향을 최소화할 수 있다. In the present invention, since nanoparticles are dispersed in the fibrils themselves, there is a problem in that a nonwoven fabric in which inorganic particles are present between fibrils or an inorganic layer is coated on one surface of the nonwoven fabric is used as a separator for a secondary battery, Can be minimized.

피브릴은 0.005 ~ 5 ㎛의 평균 직경을 가질 수 있는데, 피브릴의 평균 직경이 0.005 ㎛ 미만일 경우는 부직포의 기계적 강도가 저하될 수 있고, 피브릴의 평균 직경이 5 ㎛를 초과하는 경우에는 부직포의 다공도 및 두께 조절이 용이하지 않을 수 있다.The fibrils may have an average diameter of 0.005 to 5 탆. If the average diameter of the fibrils is less than 0.005 탆, the mechanical strength of the nonwoven fabric may be lowered. If the average diameter of the fibrils exceeds 5 탆, It may not be easy to control the porosity and thickness of the substrate.

이러한 피브릴에 의해 제조된 부직포는 0.05 ~ 30 ㎛ 직경의 기공을 가질 수 있다. 부직포가 상기 수치 범위의 기공 직경을 만족시키면, 상기 부직포가 이차전지 분리막 기재로 사용되는 경우에도 목적하는 이온 전도도 및 기계적 강도를 수득할 수 있다.The nonwoven fabric produced by this fibril may have pores having a diameter of 0.05 to 30 탆. If the nonwoven fabric satisfies the pore diameter in the above-mentioned numerical range, the desired ionic conductivity and mechanical strength can be obtained even when the nonwoven fabric is used as the secondary battery separator base material.

또한, 부직포는 50 ~ 80 % 범위의 다공도를 가질 수 있다. 부직포가 상기 수치 범위의 다공도를 만족시키면, 상기 부직포가 이차전지 분리막 기재로 사용되는 경우에도 목적하는 이온 전도도, 기계적 강도 및 형태 안정성을 수득할 수 있다.Further, the nonwoven fabric may have a porosity ranging from 50 to 80%. If the nonwoven fabric satisfies the porosity in the above-mentioned numerical range, the desired ionic conductivity, mechanical strength and shape stability can be obtained even when the nonwoven fabric is used as a secondary battery separator base material.

본 발명의 나노입자를 포함하는 피브릴로부터 부직포를 제조하는 방법은 유기 고분자 화합물과 나노입자를 포함하는 방사용액을 제조한 후 상기 방사용액을 전기방사하여 부직포 웹을 제조하는 단계를 포함한다. The method for producing the nonwoven fabric from the fibrils comprising the nanoparticles of the present invention includes preparing a spinning solution containing the organic polymer compound and the nanoparticles, and then electrospinning the spinning solution to prepare a nonwoven web.

보다 구체적으로, 본 발명에 따른 부직포 웹을 제조하는 단계는, 유기 고분자를 용매에 녹여 방사용액을 제조한 후, 상기 방사용액을 전압이 인가된 방사 노즐(spinneret nozzle)에 공급하고 토출시켜 피브릴을 형성하고 상기 피브릴들을 집전체에 집전시키는 공정으로 이루어질 수 있다.More specifically, the step of preparing the nonwoven web according to the present invention comprises: preparing a spinning solution by dissolving an organic polymer in a solvent, supplying the spinning solution to a spinneret nozzle to which a voltage is applied, And collecting the fibrils in the current collector.

상기 전기방사는 나노 단위의 직경을 갖는 피브릴들을 용이하게 제조할 수 있는 이점이 있으며, 피브릴은 거미줄처럼 서로 엉켜 부직포 웹을 형성한다. 이러한 전기방사는 박막화 및 다공도를 용이하게 조절할 수 있는 부직포 웹을 제조할 수 있다. The electrospinning has the advantage that it is easy to produce fibrils having a diameter of nano units, and the fibrils are tangled together like webs to form a nonwoven web. Such electrospinning can produce a nonwoven web capable of easily controlling the thickness and porosity.

그 밖에도, 나노입자가 부직포 피브릴에 분산되도록 하여 부직포 웹을 제조할 수 있는 임의의 부직포 제조방법이 사용될 수 있다.In addition, any nonwoven fabric manufacturing method capable of producing a nonwoven web by allowing nanoparticles to be dispersed in nonwoven fibrils can be used.

본 발명의 부직포는 그 용도가 특별히 한정되는 것은 아니며, 정수용 필터, 공기 정화용 필터, 복합재료, 연료전지용 전해질막 또는 이차전지용 분리막 등에 이용할 수 있다. 특히, 향상된 기계적 물성 및 수축특성으로 인해 이차전지용 분리막으로 적합하다.The nonwoven fabric of the present invention is not particularly limited in its use, and can be used for a water purification filter, an air purification filter, a composite material, an electrolyte membrane for a fuel cell, or a separation membrane for a secondary battery. In particular, it is suitable as a separator for a secondary battery due to its improved mechanical properties and shrinkage characteristics.

이와 같이 제조된 본 발명의 일 실시예에 따른 분리막은 양극과 음극 사이에 개재시켜 전기화학소자에 이용된다. 전기화학소자는 전기 화학 반응을 하는 모든 소자를 포함하며, 구체적인 예를 들면, 모든 종류의 1차, 이차 전지, 연료 전지, 태양 전지 또는 수퍼 캐패시터 소자와 같은 캐퍼시터(capacitor) 등이 있다. 특히, 상기 2차 전지 중 리튬 금속 이차 전지, 리튬 이온 이차 전지, 리튬 폴리머 이차 전지 또는 리튬 이온 폴리머 이차 전지 등을 포함하는 리튬 이차전지가 바람직하다.The separator according to one embodiment of the present invention thus fabricated is used in an electrochemical device interposed between an anode and a cathode. The electrochemical device includes all devices that perform an electrochemical reaction, and specific examples include capacitors such as all kinds of primary, secondary cells, fuel cells, solar cells, or super capacitor devices. Particularly, a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery is preferable.

전기화학소자는 당 기술 분야에 알려진 통상적인 방법에 따라 제조될 수 있으며, 이의 일 실시예를 들면 양극과 음극 사이에 전술한 분리막을 개재(介在)시켜 조립한 후 전해액을 주입함으로써 제조될 수 있다.The electrochemical device may be manufactured according to a conventional method known in the art, and may be manufactured, for example, by assembling the positive electrode and the negative electrode with the separator interposed therebetween, and then injecting an electrolyte solution .

상기 분리막과 함께 적용될 전극으로는 특별히 제한되지 않으며, 당업계에 알려진 통상적인 방법에 따라 전극활물질이 전극 전류집전체에 결착된 형태로 제조할 수 있다. The electrode to be used together with the separator is not particularly limited and may be manufactured in a manner that an electrode active material is bound to an electrode current collector according to a conventional method known in the art.

상기 전극활물질 중 양극활물질의 비제한적인 예로는 종래 전기화학소자의 양극에 사용될 수 있는 통상적인 양극활물질이 사용 가능하며, 특히 리튬망간산화물, 리튬코발트산화물, 리튬니켈산화물, 리튬철산화물 또는 이들을 조합한 리튬복합산화물을 사용하는 것이 바람직하다. Examples of the cathode active material include, but are not limited to, lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide, or a combination thereof It is preferable to use a lithium composite oxide.

음극활물질의 비제한적인 예로는 종래 전기화학소자의 음극에 사용될 수 있는 통상적인 음극활물질이 사용 가능하며, 특히 리튬 금속 또는 리튬 합금, 탄소, 석유코크(petroleum coke), 활성화 탄소(activated carbon), 그래파이트(graphite) 또는 기타 탄소류 등과 같은 리튬 흡착물질 등이 바람직하다. 양극 전류집전체의 비제한적인 예로는 알루미늄, 니켈 또는 이들의 조합에 의하여 제조되는 호일 등이 있으며, 음극 전류집전체의 비제한적인 예로는 구리, 금, 니켈 또는 구리 합금 또는 이들의 조합에 의하여 제조되는 호일 등이 있다.As a non-limiting example of the negative electrode active material, a conventional negative electrode active material that can be used for a negative electrode of an electrochemical device can be used. In particular, lithium metal or a lithium alloy, carbon, petroleum coke, activated carbon, Lithium-adsorbing materials such as graphite or other carbon-based materials and the like are preferable. Non-limiting examples of the positive current collector include aluminum, nickel, or a combination thereof. Examples of the negative current collector include copper, gold, nickel, or a copper alloy or a combination thereof Foil to be manufactured, and the like.

본 발명의 일 실시예에서 사용될 수 있는 전해액은 A+B-와 같은 구조의 염으로서, A+는 Li+, Na+, K+와 같은 알칼리 금속 양이온 또는 이들의 조합으로 이루어진 이온을 포함하고 B-는 PF6 -, BF4 -, Cl-, Br-, I-, ClO4 -, AsF6 -, CH3CO2 -, CF3SO3 -, N(CF3SO2)2 -, C(CF2SO2)3 -와 같은 음이온 또는 이들의 조합으로 이루어진 이온을 포함하는 염이 프로필렌 카보네이트(PC), 에틸렌 카보네이트(EC), 디에틸카보네이트(DEC), 디메틸카보네이트(DMC), 디프로필카보네이트(DPC), 디메틸설폭사이드, 아세토니트릴, 디메톡시에탄, 디에톡시에탄, 테트라하이드로퓨란, N-메틸-2-피롤리돈(NMP), 에틸메틸카보네이트(EMC), 감마-부티로락톤 또는 이들의 혼합물로 이루어진 유기 용매에 용해 또는 해리된 것이 있으나, 이에만 한정되는 것은 아니다.The electrolyte solution that can be used in one embodiment of the present invention is a salt having a structure such as A + B - , where A + includes ions consisting of alkali metal cations such as Li + , Na + , K + - it is PF 6 -, BF 4 -, Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2) 3 - anion, or a salt containing an ion composed of a combination of propylene carbonate (PC) such as, ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl (DMP), dimethylsulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethyl carbonate (EMC), gamma-butyrolactone Or an organic solvent composed of a mixture thereof, but the present invention is not limited thereto.

상기 전해액 주입은 최종 제품의 제조 공정 및 요구 물성에 따라, 전지 제조 공정 중 적절한 단계에서 행해질 수 있다. 즉, 전지 조립 전 또는 전지 조립 최종 단계 등에서 적용될 수 있다.The electrolyte injection may be performed at an appropriate stage of the battery manufacturing process, depending on the manufacturing process and required properties of the final product. That is, it can be applied before assembling the cell or at the final stage of assembling the cell.

본 발명의 일 실시예에 따른 분리막을 전지로 적용하는 공정으로는 일반적인 공정인 권취(winding) 이외에도 분리막과 전극의 적층(lamination, stack) 및 접음(folding) 공정이 가능하다.
As a process for applying the separator according to an embodiment of the present invention to a battery, a lamination, stacking and folding process of a separator and an electrode can be performed in addition to a general winding process.

Claims (11)

피브릴로 형성되고, 상기 피브릴이 유기 고분자 화합물 및 나노입자를 포함하는 부직포에 있어서,
상기 부직포가 이차전지 분리막용 부직포이고,
상기 피브릴은 0.005 내지 5 ㎛의 평균 직경을 가지며,
상기 부직포는 0.05 내지 30 ㎛ 직경의 기공을 갖고, 50 내지 80 % 범위의 다공도를 가지며,
상기 유기 고분자 화합물이 폴리올레핀, 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈렌(PEN), 폴리에스테르, 나일론, 폴리이미드, 폴리벤즈옥사졸, 폴리테트라플루오로에틸렌, 폴리아릴렌에테르술폰, 폴리에테르에테르케톤 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물이고,
상기 나노입자가 세피오라이트(sepiorite), 침상 탈크(talc) 또는 이들의 혼합물이며, 상기 피브릴에 분산되어 있고,
상기 나노입자가 2:1 내지 20:1의 입자 종횡비(aspect ratio)를 가지는 것을 특징으로 하는 부직포.
A nonwoven fabric formed from a fibril, wherein the fibril comprises an organic polymer compound and nanoparticles,
Wherein the nonwoven fabric is a nonwoven fabric for a secondary battery separator,
The fibrils have an average diameter of 0.005 to 5 mu m,
The nonwoven fabric has pores with a diameter of 0.05 to 30 탆, a porosity ranging from 50 to 80%
Wherein the organic polymer compound is selected from the group consisting of polyolefin, polyethylene terephthalate (PET), polyethylene naphthalene (PEN), polyester, nylon, polyimide, polybenzoxazole, polytetrafluoroethylene, polyarylene ether sulfone, polyether ether ketone, Or a mixture of two or more selected from the group consisting of these copolymers,
Wherein the nanoparticles are sepiolite, acicular talc, or a mixture thereof, dispersed in the fibrils,
Wherein the nanoparticles have a particle aspect ratio of from 2: 1 to 20: 1.
삭제delete 삭제delete 삭제delete 삭제delete 제1항에 있어서,
상기 나노입자가 표면 개질된 것을 특징으로 하는 부직포.
The method according to claim 1,
Wherein the nanoparticles are surface-modified.
양극, 음극, 및 상기 양극과 음극 사이에 개재된 분리막을 포함하는 전기화학소자에 있어서,
상기 분리막이 제1항 또는 제6항중 어느 한 항에 기재된 부직포인 것을 특징으로 하는 전기화학소자.
An electrochemical device comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode,
The electrochemical device according to any one of claims 1 to 6, wherein the separator is a nonwoven fabric.
유기 고분자 화합물과 나노입자를 포함하는 방사용액을 제조한 후 상기 방사 용액을 방사하여 부직포 웹을 제조하는 단계를 포함하고, 이 때
상기 유기 고분자 화합물이 폴리올레핀, 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈렌(PEN), 폴리에스테르, 나일론, 폴리이미드, 폴리벤즈옥사졸, 폴리테트라플루오로에틸렌, 폴리아릴렌에테르술폰, 폴리에테르에테르케톤 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물이고,
상기 나노입자가 2:1 내지 20:1의 입자 종횡비(aspect ratio)를 가지며,
상기 나노입자가 세피오라이트(sepiorite), 침상 탈크(talc) 또는 이들의 혼합물인 것을 특징으로 하는 제1항에 기재된 부직포의 제조방법.Preparing a spinning solution containing an organic polymer compound and nanoparticles, and spinning the spinning solution to prepare a nonwoven web,
Wherein the organic polymer compound is selected from the group consisting of polyolefin, polyethylene terephthalate (PET), polyethylene naphthalene (PEN), polyester, nylon, polyimide, polybenzoxazole, polytetrafluoroethylene, polyarylene ether sulfone, polyether ether ketone, Or a mixture of two or more selected from the group consisting of these copolymers,
Wherein the nanoparticles have a particle aspect ratio of 2: 1 to 20: 1,
The method for producing a nonwoven fabric according to claim 1, wherein the nanoparticles are sepiolite, acicular talc, or a mixture thereof. 삭제delete 삭제delete 삭제delete
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070264897A1 (en) * 2006-05-15 2007-11-15 The Procter & Gamble Company Polymeric webs with nanoparticles

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