KR20120100079A - Membrane having carbon polyaniline - Google Patents

Membrane having carbon polyaniline Download PDF

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KR20120100079A
KR20120100079A KR1020110018732A KR20110018732A KR20120100079A KR 20120100079 A KR20120100079 A KR 20120100079A KR 1020110018732 A KR1020110018732 A KR 1020110018732A KR 20110018732 A KR20110018732 A KR 20110018732A KR 20120100079 A KR20120100079 A KR 20120100079A
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polyaniline
membrane
separator
polymer
present
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KR1020110018732A
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Korean (ko)
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윤호성
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윤호성
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Separators (AREA)

Abstract

PURPOSE: A membrane with polyaniline is provided to eliminate ionic components dissolved in water by absorbing the ionic components through an ion-absorbing function of polyaniline. CONSTITUTION: A polymer membrane with polyaniline includes 0.001 to 70 wt% of polyaniline in the total weight of the membrane. The polymer in the polymer membrane is one or more selected from a group including polypropylene, polysulfone, polyether sulfone, polyacyrlonitrile, polyvinylidene fluoride, and polyurethane.

Description

폴리아닐린을 포함하는 분리막{MEMBRANE HAVING CARBON POLYANILINE}Separation membrane containing polyaniline {MEMBRANE HAVING CARBON POLYANILINE}

본 발명은 폴리아닐린을 포함하는 분리막에 관한 발명으로서, 분리막에 폴리아닐린을 기능성 성분으로 포함시켜 폴리아닐린의 기능을 부여한 기능성 분리막에 관한 발명이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a separator comprising polyaniline, and relates to a functional separator in which polyaniline is included in the separator as a functional component to impart a polyaniline function.

분리막은 일정한 기공을 가지고 있어 기공의 크기에 따라 물질을 분리할 수 있는 소재로서 통상적으로는 시트(sheet) 또는 중공사(hollow fiber)의 형태를 가지고 있다.Separation membrane is a material capable of separating the material according to the size of the pore having a certain pore is usually in the form of a sheet (sheet) or hollow fiber (hollow fiber).

이러한 분리막을 기공의 크기에 따라 분류하면 정밀여과(MF, micro filtration), 한외여과(UF, ultra filtration), 나노여과(NF, nano filtration) 그리고 역삼투(RO, reverse osmosis)로 분류된다.These membranes are classified according to pore size and classified into microfiltration (MF), ultrafiltration (UF), ultrafiltration (NF, nano filtration) and reverse osmosis (RO).

통상적으로 분리막의 용도는 기공의 크기에 따라 결정되는데 위에서 언급한 정밀여과 막의 경우 입자상 물질 또는 미생물을 제거하는데 사용되며, 한외여과막은 바이러스의 제거 또는 단백질의 분리에 사용된다. 마지막의 역삼투 막의 경우는 기공의 크기가 매우 작아 이온성 물질을 제거하는데 사용되며, 이러한 용도로서는 해수에서 염 성분을 제거하는 해수 담수화용의 역삼투 막이 널리 사용되고 있다.In general, the use of the separation membrane is determined according to the pore size. The above-mentioned microfiltration membrane is used to remove particulate matter or microorganisms, and the ultrafiltration membrane is used to remove viruses or isolate proteins. In the case of the last reverse osmosis membrane, the pore size is so small that it is used to remove ionic substances. For this purpose, reverse osmosis membrane for seawater desalination to remove salt components from seawater is widely used.

한편 상기의 분리막에 기능성 성분을 첨가하여 일정한 기능을 가진 분리막도 소개되고 있는데, 가장 널리 알려진 것이 정밀여과(MF) 분리막에 항균 성분을 첨가하여 미생물을 여과하면서도 장기간 사용시 미생물에 오염되지 않도록 한 분리막의 예가 알려져 있다.Meanwhile, a membrane having a certain function by introducing a functional component to the membrane is also introduced. The most widely known membrane is a microfiltration filter that adds an antimicrobial component to prevent microbial contamination during long-term use. Examples are known.

본 발명에서 개시하고자 하는 분리막은 상기 분리막에 폴리아닐린을 첨가하여 폴리아닐린이 가지고 있는 여러 가지 특성을 분리막에서 구현한 분리막이다.The separator to be disclosed in the present invention is a separator in which the polyaniline is added to the separator to realize various characteristics of the polyaniline in the separator.

상기 폴리아닐린은 전기를 통할 수 있는 전도성 고분자의 하나로서 이러한 도전성을 이용한 대전방지재, 전자파 차폐제, 부식방지 코팅재 및 이차전지용 양극활물질 등으로 널리 응용되고 있으나, 아직까지 분리막용 소재로서는 알려진 바가 없다.
The polyaniline is one of the electrically conductive polymers that can pass electricity, and is widely used as an antistatic material, an electromagnetic wave shielding agent, an anti-corrosion coating material, and a cathode active material for secondary batteries using such conductivity, but is not known as a separator material.

본 발명에서는 폴리아닐린을 포함하는 분리막을 제공하는 것을 본 발명의 목적으로 한다.In the present invention, it is an object of the present invention to provide a separator containing polyaniline.

본 발명에 따른 폴리아닐린을 포함하는 분리막은 분리막에 폴리아닐린을 0.001 내지 70 중량% 포함시켜 폴리아닐린이 가지고 있는 기능을 부가한 고분자 분리막임을 특징으로 한다.Separation membrane comprising a polyaniline according to the present invention is characterized in that the polymer membrane with a polyaniline added to the polyaniline containing 0.001 to 70% by weight.

이를 위하여 본 발명에서는 폴리아닐린을 도핑하여 사용하거나 또는 도핑되기 전의 폴리아닐린을 사용하여 고분자 분리막을 제조한다.To this end, in the present invention, a polymer separator is prepared by doping polyaniline or using polyaniline before doping.

만약 도핑이 얻고자 하는 물성을 구현하기 위하여 필요한 경우는 분리막 제조 후에 별도의 도핑 과정을 거쳐서 사용할 수 있으므로 도핑 여하에 본 발명이 구현하고자 하는 기능이 영향을 받지는 않는다.If the doping is necessary to achieve the desired physical properties can be used through a separate doping process after the membrane manufacturing, the function to be implemented in the present invention is not affected by the doping.

고분자 분리막은 통상적으로 폴리프로필렌(PP, polypropylene), 폴리에테르술폰(PES, polyether sulfone), 폴리술폰(PSf, polysulfone), 폴리아크릴로나이트릴(PAN, polyacrylonitrile), 폴리비닐리덴디플루오라이드(PVDF, polyvinylidene difluoride), 폴레우레탄(PU, polyurethane) 등의 고분자 소재를 용융압출 후 연신시켜 제조하거나, 고분자를 용매에 녹여 방사 또는 캐스팅하여 제조하는데, 본 발명의 폴리아닐린을 포함하는 분리막은 상기 소재와 재료에 모두 적용 가능하다.Polymer membranes are typically polypropylene (PP, polypropylene), polyether sulfone (PES), polysulfone (PSf, polysulfone), polyacrylonitrile (PAN, polyacrylonitrile), polyvinylidene difluoride (PVDF) , polyvinylidene difluoride), a polymer material such as polyurethane (PU, polyurethane) is prepared by melting and extruding after stretching, or by dissolving the polymer in a solvent to spin or cast, the membrane comprising the polyaniline of the present invention is the material and material Applicable to both.

즉, 용융 고분자를 압출 후 연신시켜 제조하는 분리막의 경우에는 고분자를 용융 및 혼련하는 고정에서 폴리아닐린을 포함시킨 후 이를 노즐을 통하여 압출 시켜 제조하는 방법을 사용한다.In other words, in the case of a membrane produced by stretching the molten polymer after extrusion, a method of manufacturing a polymer by including polyaniline in the fixing and melting and kneading of the polymer is extruded through a nozzle.

만약 고분자 분리막의 제조 공정이 용매에 고분자를 녹인 후 습식 방사하는 중공사 분리막 제조 공정이라면, 폴리아닐린을 고분자가 용해된 용액, 즉 도프(dope)에 분산시켜 습식방사(dry-wet spinning)하는 방식으로 제조할 수 있다.If the manufacturing process of the polymer membrane is a hollow fiber membrane manufacturing process in which the polymer is dissolved in a solvent and then wet spinning, the polyaniline is dispersed in a solution in which the polymer is dissolved, that is, in a dope to dry-wet spinning. It can manufacture.

또한 고분자 용액을 캐스팅하여 평막을 제조하는 공정에서는 상기 용액에 폴리아닐린을 분산시켜 같이 캐스팅하는 방법으로 폴리아닐린을 포함하는 분리막, 즉 평막을 생산할 수 있다.In addition, in the process of manufacturing a flat membrane by casting a polymer solution, it is possible to produce a separator, that is, a flat membrane containing polyaniline by dispersing the polyaniline in the solution and casting together.

상기한 방법으로 제공되는 폴리아닐린을 포함하는 고분자 분리막은 고분자 분리막 최종 제품에 폴리아닐린이 중량기준으로 0.001% 내지 70% 포함되는 것을 특징으로 한다.The polymer separator including the polyaniline provided by the above method is characterized in that the polyaniline is contained 0.001% to 70% by weight in the polymer separator final product.

상기 하한 비율인 0.001% 이하의 함량에서는 폴리아닐린의 특성을 고분자 분리막에서 구현하기가 매우 어려우며, 상기 상한 70%를 초과하는 비율에서는 폴리아닐린의 비율이 너무 많아서 분리막의 기공이 형성되기 어렵다.
In the lower limit of 0.001% or less, it is very difficult to realize the characteristics of polyaniline in the polymer membrane, and in the ratio exceeding the upper limit of 70%, the ratio of polyaniline is too large to form pores in the separator.

본 발명에 따른 폴리아닐린을 포함하는 고분자 분리막을 사용하면 폴리아닐린의 본래 기능인 전기 전도성, 부식 방지성, 대전 방지성, 전자파 차폐 특성을 지닌 고분자 분리막을 제조할 수 있다.By using the polymer membrane comprising the polyaniline according to the present invention, it is possible to produce a polymer membrane having an electric conductivity, corrosion resistance, antistatic properties, and electromagnetic shielding properties, which are the original functions of the polyaniline.

특히 폴리아닐린을 포함하는 고분자 분리막의 경우 폴리아닐린을 포함함으로써 2차전지용의 분리막과 양극 활물질의 특성을 통시에 나타낼 수 있어 기능성 전지 소재로서 널리 사용될 수 있는 특성이 있다.In particular, in the case of the polymer separator including polyaniline, the polyaniline may be used to show the characteristics of the separator and the positive electrode active material for a secondary battery at a time, and thus may be widely used as a functional battery material.

또한 폴리아닐린은 이온을 흡착하는 특성이 있으므로 분리막에 사용되면 물속에 용해되어 있는 이온성 성분을 분리막이 제거할 수 있는 성능을 나타내게 된다.In addition, since polyaniline has a property of adsorbing ions, when used in a separator, the separator exhibits a capability of removing an ionic component dissolved in water.

이하 본 발명을 실시하기 위한 구체적인 내용을 실시예를 통하여 보다 상세히 설명한다.
Hereinafter will be described in more detail through examples for carrying out the present invention.

[실시예1][Example 1]

폴리술폰 20g, 폴리에틸렌글리콜 15g, DMAC(dimethyl acetamide)60g, PVP(polyvynylpyrrolidone)5g을 잘 섞어 교반 한 후에 에머랄딘 폴리아닐린 분말 5g을 잘 분산시켜 도프(dope)를 제조한다.20 g polysulfone, 15 g polyethylene glycol, 60 g DMAC (dimethyl acetamide), PVP (polyvynylpyrrolidone) 5g is mixed and stirred well, 5g of the emeraldine polyaniline powder is dispersed well to prepare a dope (dope).

상기 도프(dope)를 이중관을 가지는 방사 구금으로 토출시켜 중공사 분리막을 중공사 막을 제조한다. 이때 내부 코어(core)액으로는 100% DMAC를 사용하고 물로 구성된 응고조에 상기 도프와 코어액을 방사하여 중공사 분리막을 제조한다.The dope is discharged into a spinneret having a double tube to produce a hollow fiber membrane. In this case, 100% DMAC is used as the inner core liquid and the hollow fiber separator is manufactured by spinning the dope and the core liquid in a coagulation bath composed of water.

제조된 분리막은 물로 세척한 후 건조시키면 폴리아닐린을 포함하는 MF 등급의 중공사 분리막이 완성 된다.
The prepared separator is washed with water and dried to complete the MF grade hollow fiber separator containing polyaniline.

[실시예2][Example 2]

폴리술폰 20g, 폴리에틸렌글리콜 15g, DMAC(dimethyl acetamide)60g, PVP(polyvynylpyrrolidone)5g을 잘 섞어 교반 한 후에 에머랄딘 폴리아닐린 분말 5g을 잘 분산시켜 도프(dope)를 제조한다.20 g polysulfone, 15 g polyethylene glycol, 60 g DMAC (dimethyl acetamide), PVP (polyvynylpyrrolidone) 5g is mixed and stirred well, 5g of the emeraldine polyaniline powder is dispersed well to prepare a dope (dope).

상기 도프를 독터 블레이드를 이용하여 유리 판위에 일정한 두께로 캐스팅 한 후에 이를 물속에 침지시켜 시트 형태의 분리막을 제조한다. 제조된 분리막은 유리 판위에서 제거된 후에 추가적인 세정 후 건조시켜 MF 등급의 평막으로 제조된다.
The dope is cast to a certain thickness on a glass plate using a doctor blade, and then immersed in the water to prepare a separator in the form of a sheet. The separator thus prepared is removed on a glass plate and then further washed and dried to prepare a MF grade flat membrane.

본 발명에 따른 폴리아닐린을 포함하는 분리막은 2차전지 양극 소재, 전자파 차폐재, 부식방지용 시트 소재 등으로 사용될 수 있다.The separator including the polyaniline according to the present invention may be used as a secondary battery positive electrode material, electromagnetic shielding material, anti-corrosion sheet material and the like.

Claims (2)

고분자 분리막에 폴리아닐린이 중량기준으로 0.001% 내지 70% 포함되는 것을 특징으로 하는 폴리아닐린이 포함된 분리막.
A polyaniline separator in which the polyaniline is included in the polymer separator in an amount of 0.001% to 70% by weight.
제 1항에 있어서 고분자는 폴리프로필렌(polypropylene), 폴리술폰(polysulfone), 폴리에테르술폰(polyether sulfone), 폴리아크릴로나이트릴(polyacrylonitrile), 폴리비닐리덴디플루오라이드(polyvinylidenedifluoride), 폴리우레탄(PU, polyurethane)으로 구성되는 군에서 선택되는 어느 1종 또는 2종 이상인 것을 특징으로 하는 폴리아닐린이 포함된 분리막.According to claim 1, wherein the polymer is polypropylene, polysulfone, polyether sulfone, polyacrylonitrile, polyvinylidenedifluoride, polyurethane , polyurethane) separation membrane comprising polyaniline, characterized in that any one or two or more selected from the group consisting of.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160008621A (en) * 2013-05-15 2016-01-22 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 Polyaniline membranes formed by phase inversion for forward osmosis applications
KR20190066257A (en) 2017-12-05 2019-06-13 주식회사 파라 A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof
KR20190089576A (en) 2018-01-23 2019-07-31 주식회사 파라 A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof
KR20200048706A (en) 2018-10-30 2020-05-08 주식회사 파라 Filter using nanoporous polyaniline complex

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160008621A (en) * 2013-05-15 2016-01-22 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 Polyaniline membranes formed by phase inversion for forward osmosis applications
KR20190066257A (en) 2017-12-05 2019-06-13 주식회사 파라 A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof
KR20190089576A (en) 2018-01-23 2019-07-31 주식회사 파라 A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof
US10829592B2 (en) 2018-01-23 2020-11-10 Para Co., Ltd. Method for preparing polyaniline complex with antimicrobial activity and heavy metal removal efficiency using conductive poly aniline polymer doped with organic acid and metal ion in defined order
KR20200048706A (en) 2018-10-30 2020-05-08 주식회사 파라 Filter using nanoporous polyaniline complex

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