KR20080073969A - Separator for battery coated by polyurethane polymer and li/socl2 battery comprising the same - Google Patents

Separator for battery coated by polyurethane polymer and li/socl2 battery comprising the same Download PDF

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KR20080073969A
KR20080073969A KR1020070012881A KR20070012881A KR20080073969A KR 20080073969 A KR20080073969 A KR 20080073969A KR 1020070012881 A KR1020070012881 A KR 1020070012881A KR 20070012881 A KR20070012881 A KR 20070012881A KR 20080073969 A KR20080073969 A KR 20080073969A
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battery
separator
socl
coated
polyurethane
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KR100859755B1 (en
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박정기
이준영
이용민
김상필
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한국과학기술원
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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 Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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Abstract

A separator for a battery coated with a polyurethane polymer is provided to prevent a voltage delay phenomenon by virtue of excellent physical and chemical properties derived from the polyurethane polymer, to ensure good insulation between a cathode and an anode, and to impart high energy density to a Li/SOCl2 battery. A separator for a battery comprises glass fibers coated with a polyurethane polymer compound. The polyurethane polymer compound is coated in an amount of 0.1-5 wt%. The polyurethane polymer compound contains an amide(-NCO-) group. The coating is formed by a coating process selected from the group consisting of spray coating, dip coating, screen printing, spin coating and ink spraying. The separator has a thickness of 250-400 micrometers.

Description

폴리우레탄계 고분자 화합물이 코팅된 전지용 분리막 및 이를 포함하는 Ｌｉ／ＳＯＣｌ２ 전지{Separator for Battery Coated by Polyurethane Polymer and Li/SOCl2 Battery Comprising the Same}Separator for Battery Coated by Polyurethane Polymer and Li / SOCl2 Battery Comprising the Same

도 1은 실시예 3 내지 실시예 4 및 비교예 1 내지 비교예 3에서 제조한 Li/SOCl2 전지의 방전특성을 나타낸 그래프이다.1 is a Li / SOCl 2 prepared in Examples 3 to 4 and Comparative Examples 1 to 3 A graph showing the discharge characteristics of the battery.

본 발명은 폴리우레탄계 고분자 화합물이 코팅된 전지용 분리막 및 이를 포함하는 Li/SOCl2 전지에 관한 것으로, 보다 상세하게는 폴리우레탄계 고분자 화합물로 코팅하여 우수한 방전 특성과 고에너지 밀도를 갖는 유리섬유 재질의 전지용 분리막 및 이를 포함하는 Li/SOCl2 전지에 관한 것이다.The present invention relates to a separator for a battery coated with a polyurethane-based polymer compound and a Li / SOCl2 battery comprising the same, and more particularly, a separator for a battery made of glass fiber material having excellent discharge characteristics and high energy density by coating with a polyurethane-based polymer compound And it relates to a Li / SOCl 2 battery comprising the same.

전자기기의 휴대편의에 따른 소형 경량화 추세에 맞춰 전지분야의 기술도 눈부시게 발전을 거듭해 왔으며, 전자 기기의 경박단소를 달성하기 위해서는 고에너 지 고밀도형 전지는 절대적으로 필요하다. 이러한 추세에 맞춰 제안된 것이 리튬 전지로서, 리튬을 음극으로 사용하는 리튬전지의 에너지 밀도는 양극 활물질에 크게 좌우 된다. 그의 한 종류로 Li/SOCl2 전지는 에너지 밀도가 크고, 사용온도 범위가 넓으며, 연간 자가방전률이 1~2%의 매우 낮은 수준으로 저장 특성이 뛰어나다.In accordance with the trend of small size and light weight due to the convenience of portable electronic devices, the technology of the battery field has been remarkably developed, and high energy high density type batteries are absolutely necessary to achieve light and small size of electronic devices. Proposed in accordance with this trend is a lithium battery, the energy density of a lithium battery using lithium as a negative electrode largely depends on the positive electrode active material. One type of Li / SOCl 2 battery has a high energy density, a wide operating temperature range, and excellent storage characteristics with an annual low self discharge rate of 1 to 2%.

이와 같은 특성으로 인해 Li/SOCl2 전지는 메모리 백업(memory backup) 전원으로 널리 이용되고, 또한 소형 전자기기의 전원으로 사용되고 있는 바, 그 사용범위는 점차 확대 될 것으로 예상된다.Due to these characteristics, Li / SOCl 2 battery is widely used as a memory backup power source, and also used as a power source for small electronic devices, and its range of use is expected to be gradually expanded.

Li/SOCl2 전지는 양극(anode)으로서 리튬 또는 리튬 합금, 음극(cathode)으로서 폴리(테트라플루오로에틸렌) 바인더(PTFE binder)가 포함된 무결정 카본을 사용한다. 상기 전지의 전해액으로는 리튬염( lithium salt)가 해리된 SOCl2 용액을 사용하고, 양극과 음극 사이를 격리하는 분리막을 포함한다.Li / SOCl 2 cells use amorphous carbon containing lithium or a lithium alloy as an anode and a poly (tetrafluoroethylene) binder as a cathode. As the electrolyte of the battery, a SOCl 2 solution in which lithium salt is dissociated is used, and a separator is isolated between the positive electrode and the negative electrode.

종래의 분리막의 경우, 코팅을 하지 않은 유리섬유(glass fiber)를 사용하여 왔는데, 상기의 무코팅한 분리막의 경우, SOCl2에 내화학성을 가지고 있으나 고온 하에서는 양극 표면에 두꺼운 LiCl 피막을 형성으로써, 전지의 방전시 전압강하(voltage delay) 현상을 야기 시키는 문제점이 있었다.Conventional separators have been using uncoated glass fibers. The uncoated separators have chemical resistance to SOCl 2 but by forming a thick LiCl film on the surface of the anode under high temperature, There was a problem that caused a voltage delay phenomenon during discharge of the battery.

상기와 같은 문제점을 해결하고자 기존에는 아크릴(acryl) 계의 물질을 리튬 음극 표면에 코팅제로 사용하는 시도가 있었으나, 상기 아크릴계 코팅제는 상온에서는 전압강하 방지효과가 있지만 150℃ 이상의 고온에서는 쉽게 녹아버리기 때문 에 전압강하 방지효과를 나타낼 수 없는 문제점을 지니고 있었다.In order to solve the above problems, there have been attempts to use an acryl-based material as a coating on the surface of the lithium anode, but the acrylic coating has an effect of preventing voltage drop at room temperature, but easily melts at a temperature higher than 150 ° C. Had a problem in that it could not exhibit a voltage drop prevention effect.

본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로, 본 발명의 하나의 목적은 우레탄결합의 우수한 성질을 이용하여 내마모성, 내약품성, 내기후성, 부착성 및 오염방지성 등이 우수하며, 강인하고 경제적인 코팅재료로서 널리 사용되고 있는 폴리우레탄계 고분자 화합물이 코팅됨으로써 전압지연 현상을 방지할 수 있을 뿐만 아니라, 전지의 양극과 음극의 접촉으로 인한 단락을 방지할 수 전지용 분리막을 제공하는 것이다. The present invention is to solve the problems of the prior art as described above, one object of the present invention is excellent in abrasion resistance, chemical resistance, weather resistance, adhesion and anti-fouling, using the excellent properties of the urethane bond, The polyurethane-based polymer compound, which is widely used as a tough and economical coating material, is coated to not only prevent voltage delay, but also provide a battery separator capable of preventing a short circuit due to contact between a cathode and an anode of a battery.

본 발명의 다른 목적은 상기 전지용 분리막을 포함함으로써, 전압강하 현상이 없고 양극과 음극의 격리성 및 방전특성이 우수하고 고에너지 밀도를 갖는 Li/SOCl2 전지를 제공하는 것이다.Another object of the present invention is to provide a Li / SOCl 2 battery having a high energy density by including the separator for the battery, there is no voltage drop phenomenon, excellent isolation and discharge characteristics of the positive electrode and the negative electrode.

상기의 목적을 달성하기 위한 본 발명의 하나의 양상은 유리섬유에 폴리우레탄이 코팅된 전지용 분리막을 제공하는 것이다.One aspect of the present invention for achieving the above object is to provide a separator for a battery coated with a polyurethane on a glass fiber.

상기의 목적을 달성하기 위한 본 발명의 다른 양상은 상기 전지용 분리막을 포함하는 Li/SOCl2 전지를 제공하는 것이다.Another aspect of the present invention for achieving the above object is to provide a Li / SOCl 2 battery comprising the battery separator.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 의한 전지용 분리막은 유리섬유에 폴리우레탄계 고분자 화합물이 코팅되어 있는데, 상기 유리섬유의 코팅제로 사용될 수 있는 폴리우레탄계 고분자 화합물로는 통상적으로 상용화되어 사용되고 있는 폴리우레탄 화합물이라면 제한없이 사용될 수 있으나, 아미드기(-NCO-)를 포함하는 것이 바람직하다.The separator for a battery according to the present invention is coated with a polyurethane-based polymer compound on the glass fiber, the polyurethane-based polymer compound that can be used as a coating agent of the glass fiber can be used without limitation as long as it is a commercially available polyurethane compound, It is preferable to include an amide group (-NCO-).

상기 코팅제로서 폴리우레탄계 고분자 화합물을 사용할 경우, 높은 온도에 대한 저항성이 크기 때문에 두꺼운 형태의 피막을 형성하지 않아 전압지연 현상을 방지할 수 있을 뿐만 아니라, 코팅 처리되지 않은 유리섬유 분리막의 경우에 발생하는 문제점인 장기간 방전시의 분리막의 약화에 기인하는 양극과 음극의 접촉으로 인한 단락을 방지할 수 있다. When the polyurethane-based polymer compound is used as the coating agent, since the resistance to high temperature is large, it does not form a thick film and prevents voltage delay, and occurs in the case of uncoated glass fiber separator. It is possible to prevent a short circuit due to contact between the positive electrode and the negative electrode due to the weakening of the separator during prolonged discharge.

본 발명에 의한 전지용 분리막은 유리섬유에 상기 폴리우레탄계 고분자 화합물이 0.1~5 중량%로 코팅되는 것이 바람직하다.In the separator for batteries according to the present invention, the polyurethane-based polymer compound is preferably coated with 0.1 to 5 wt% of glass fibers.

유리섬유에 폴리우렌탄계 고분자 화합물을 코팅하는 방법은 통상의 방법을 사용할 수 있으나, 스크린 인쇄법, 프린팅법, 스핀코팅법, 딥핑법(dipping) 또는 잉크분사법 등이 바람직하다.The method of coating the polyurethane-based polymer compound on the glass fiber may be a conventional method, but screen printing, printing, spin coating, dipping or ink spraying is preferable.

본 발명에 의한 전지용 분리막의 두께는 100~1,000 ㎛ 정도이나, 250~400㎛인 것이 바람직하다.분리막의 두께가 250㎛ 미만이면 전지의 단락현상이 발생할 수 있고, 분리막의 두께가 400㎛을 초과하면 그 두께가 너무 두꺼워져서 분리막이 전지내에서 반응할 수 있는 전해액의 함량이 줄어들고, 이에 따라 에너지 밀도를 저하시키는 문제점이 발생할 수 있다.The thickness of the separator for a battery according to the present invention is about 100-1,000 μm, but preferably 250-400 μm. If the thickness of the separator is less than 250 μm, a short circuit of the battery may occur, and the thickness of the separator exceeds 400 μm. If the thickness is too thick, the content of the electrolyte that the separator can react in the battery is reduced, thereby lowering the energy density.

본 발명에 의한 분리막은 Li/SOCl2 전지용 분리막에 사용될 수 있으나, 이에 한정되는 것은 아니다.The separator according to the present invention is Li / SOCl 2 It may be used in the battery separator, but is not limited thereto.

본 발명의 다른 측면은 상기한 전지용 분리막을 포함하는 Li/SOCl2 전지에 관한 것으로, 상기 전지는 양극(anode), 음극(cathode), 전해액 및 상기 분리막을 포함하나, 이에 한정되는 것은 아니다.Another aspect of the present invention relates to a Li / SOCl 2 battery including the battery separator, wherein the battery includes, but is not limited to, an anode, a cathode, an electrolyte, and the separator.

상기 양극으로는 리튬 금속 또는 리튬 합금이 사용될 수 있고, 음극으로는 폴리(테트라플루오로에틸렌) 바인더(PTFE binder)가 포함된 무결정 카본의 활물질이 사용될 수 있는데, 상기 무결정 카본으로는 케첸 블랙(Ketjen black) 또는 아세틸렌 블랙이 바람직하나, 이에 한정되는 것은 아니다.Lithium metal or a lithium alloy may be used as the positive electrode, and an active material of amorphous carbon including a poly (tetrafluoroethylene) binder (PTFE binder) may be used as the negative electrode, and Ketjen Black may be used as the amorphous carbon. (Ketjen black) or acetylene black is preferred, but is not limited thereto.

상기 전해액으로는 리튬염이 해리된 SOCl2 용액을 사용하는 것이 바람직하나 이에 한정되는 것은 아니고, 상기 리튬염으로는 LiAlCl4,LiCl, LiBr, LiBF4, LiSbF6, LiClO4, LiGaCl4, LiTFSI, LiPF6 , LiSCN, LiO3SCF2CF3, LiC6F5SO3, LiO2, LiO2CCF3, LiSO3F, LiCF3SO3 또는 이들의 혼합물 등이 사용될 수 있으나, 이에 한정되는 것은 아니다.Lithium salt dissociated SOCl 2 is preferably used as the electrolyte solution, but is not limited thereto. The lithium salt may be LiAlCl 4 , LiCl, LiBr, LiBF 4 , LiSbF 6 , LiClO 4 , LiGaCl 4 , LiTFSI, LiPF 6 , LiSCN, LiO 3 SCF 2 CF 3 , LiC 6 F 5 SO 3 , LiO 2 , LiO 2 CCF 3 , LiSO 3 F, LiCF 3 SO 3 Or a mixture thereof may be used, but is not limited thereto.

본 발명에 의한 Li/SOCl2 전지에 함유되는 리튬염의 농도는 0.1~2 M인 것이 바람직한데, 상기 농도가 0.1M 미만이면 해리된 리튬 이온의 양이 많지 않아 전지 성능에 문제가 발생할 수 있고, 농도가 2M을 초과하면 전해액의 점도 증가로 인한 이온전도도의 감소 등의 문제가 발생할 수 있다.Concentration of the lithium salt contained in the Li / SOCl 2 battery according to the present invention is preferably 0.1 ~ 2M, if the concentration is less than 0.1M does not have a large amount of dissociated lithium ions may cause problems in battery performance, If the concentration exceeds 2M, problems such as a decrease in ion conductivity due to an increase in viscosity of the electrolyte may occur.

상기 분리막은 양극과 음극 사이를 격리시켜 주는 기능을 하는데, 상기한 바와 같이 폴리우레탄계 고분자 화합물을 코팅제로 사용한 경우를 코팅을 하지 않은 경우와 비교하였을 때 현저한 전압강하(voltage delay) 현상이 발생하지는 않으나, 전지의 방전 정도가 진행됨에 따라 코팅된 미량의 폴리우레탄계 고분자 화합물이 SOCl2 전해액에 용해되어 유리섬유 분리막의 강도가 약화된 부분을 통해 양극과 음극의 물리적 접촉을 야기할 수 있기 때문에, 분리막을 250~400 ㎛의 두께로 함으로써 이러한 문제를 해결할 수 있다.The separator functions to insulate between the anode and the cathode. As described above, when the polyurethane-based polymer compound is used as a coating agent, a significant voltage delay does not occur when compared to the case where the coating is not coated. As the degree of discharge of the battery progresses, a small amount of the coated polyurethane-based polymer compound is dissolved in the SOCl 2 electrolyte and may cause physical contact between the positive electrode and the negative electrode through the weakened portion of the glass fiber separator. By setting it as the thickness of 250-400 micrometers, this problem can be solved.

이하, 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 하나 하기의 실시예는 설명의 목적을 위한 것으로서, 본 발명이 이에 국한되는 것은 아니다. Hereinafter, one embodiment of the present invention will be described in more detail with reference to the following examples, for the purpose of explanation, the present invention is not limited thereto.

실시예 1 : Li/SOCl2 전지용 분리막의 제조(1)Example 1 Preparation of Membrane for Li / SOCl 2 Battery (1)

스핀코팅 방법을 이용하여 유리섬유에 폴리우레탄(Selectophore, Fluka)을 5㎛ 두께로 코팅하여 두께 250㎛의 폴리우레탄계 고분자 화합물이 코팅된 유리섬유 분리막을 제조하였다.Polyurethane (Selectophore, Fluka) was coated on the glass fibers using a spin coating method with a thickness of 5 μm to prepare a glass fiber separator coated with a polyurethane polymer compound having a thickness of 250 μm.

실시예 2 : Li/SOCl2 전지용 분리막의 제조(2)Example 2 Preparation of Separator for Li / SOCl 2 Battery (2)

스핀코팅 방법을 이용하여 유리섬유에 폴리우레탄(Selectophore, Fluka)을 10㎛ 두께로 코팅하여 두께 400㎛의 폴리우렌탄계 고분자 화합물이 코팅된 유리섬유 분리막을 제조하였다.Polyurethane (Selectophore, Fluka) was coated on the glass fibers using a spin coating method with a thickness of 10 μm to prepare a glass fiber separator coated with a polyurethane polymer compound having a thickness of 400 μm.

실시예 3 : Li/SOCl2 전지의 제조(1)Example 3 Preparation of Li / SOCl 2 Battery (1)

양극으로 리튬, 음극으로 아세틸렌 블랙 활물질에 폴리(테트라플루오로에틸렌) 바인더(PTFE binder)가 포함된 무결정 탄소재, 양극과 음극의 사이를 격리하는 분리막으로 상기 실시예 1에서 제조한 250㎛ 두께의 폴리우렌탄계 고분자 화합물이 코팅된 유리섬유 분리막 및 전해액으로 AlCl3와 LiCl을 SOCl2에 용해시켜 제조한 1.25M의 LiAlCl4/SOCl2 용액을 전지내에 주입한 후, 레이저로 용접하여 Li/SOCl2 전지를 제조하였다.Lithium as a positive electrode, an amorphous carbon material containing a poly (tetrafluoroethylene) binder (PTFE binder) in an acetylene black active material as a negative electrode, a separator to isolate between the positive electrode and the negative electrode 250㎛ thickness prepared in Example 1 1.25M LiAlCl 4 / SOCl 2 solution prepared by dissolving AlCl 3 and LiCl in SOCl 2 with a glass fiber membrane coated with polyurethane polymer compound and an electrolyte solution was injected into the cell, and then welded with a laser to form Li / SOCl. 2 cells were prepared.

실시예 4 : Li/SOCl2 전지의 제조(2)Example 4 Preparation of Li / SOCl 2 Battery (2)

분리막으로 상기 실시예 2에서 제조한 400㎛ 두께의 폴리우렌탄계 고분자 화합물이 코팅된 유리섬유 분리막을 사용한 것 이외에는 실시예 3과 동일하게 실시하여 Li/SOCl2 전지를 제조하였다.Li / SOCl 2 batteries were prepared in the same manner as in Example 3, except that the glass fiber separator coated with the 400 μm-thick polyurethane-based polymer compound prepared in Example 2 was used as the separator.

비교예 1 : Li/SOCl2 전지의 제조(3)Comparative Example 1: Preparation of Li / SOCl 2 Battery (3)

분리막으로 코팅을 하지 않은 두께 250㎛의 유리섬유 분리막을 사용한 것 이외에는 실시예 3과 동일하게 실시하여 Li/SOCl2 전지를 제조하였다.A Li / SOCl 2 battery was prepared in the same manner as in Example 3, except that a glass fiber separator having a thickness of 250 μm was not coated with a separator.

비교예 2 : Li/SOCl2 전지의 제조(4)Comparative Example 2: Preparation of Li / SOCl 2 Battery (4)

분리막으로 150㎛ 두께의 폴리우렌탄계 고분자 화합물이 코팅된 유리섬유 분리막을 사용한 것 이외에는 실시예 3과 동일하게 실시하여 Li/SOCl2 전지를 제조하 였다.Li / SOCl 2 batteries were prepared in the same manner as in Example 3, except that the glass fiber separator coated with the polyurethane polymer compound having a thickness of 150 μm was used as the separator.

비교예 3 : Li/SOCl2 전지의 제조(5)Comparative Example 3: Preparation of Li / SOCl 2 Battery (5)

분리막으로 500㎛ 두께의 폴리우렌탄계 고분자 화합물이 코팅된 유리섬유 분리막을 사용한 것 이외에는 실시예 3과 동일하게 실시하여 Li/SOCl2 전지를 제조하였다. Li / SOCl 2 batteries were prepared in the same manner as in Example 3, except that the glass fiber separator coated with the polyurethane polymer compound having a thickness of 500 μm was used as the separator.

도 1은 상기 실시예 3 내지 실시예 4 및 비교예 1 내지 비교예 3에서 제조한 Li/SOCl2 전지를 60℃에서 20일간 저장한 후 100mA로 방전시의 최저 전압을 나타낸 것으로, 본 발명에 의한 Li/SOCl2 전지는 코팅을 하지 않은 비교예 1의 전지와 비교했을 때 보다 높은 전압과 우수한 방전 성능을 지니고 있음을 확인할 수 있다.1 shows the lowest voltage at the time of discharging at 100 mA after storing the Li / SOCl 2 batteries prepared in Examples 3 to 4 and Comparative Examples 1 to 3 at 60 ° C. for 20 days, By Li / SOCl 2 It can be seen that the battery has a higher voltage and excellent discharge performance when compared with the battery of Comparative Example 1, which is not coated.

본 발명에 의하면, 250~400㎛ 두께를 가진 폴리우레탄계 고분자 화합물이 코팅된 분리막을 사용함으로써, 전압강하 현상이 없고 양극과 음극의 격리성 또한 우수하며, 우수한 방전특성과 높은 에너지 밀도를 갖는 Li/SOCl2 전지를 제공할 수 있다.According to the present invention, by using a separator coated with a polyurethane-based polymer compound having a thickness of 250 ~ 400㎛, there is no voltage drop phenomenon, excellent isolation between the anode and the cathode, Li / SOCl having excellent discharge characteristics and high energy density 2 batteries can be provided.

Claims (12)

유리섬유에 폴리우레탄계 고분자 화합물이 코팅된 전지용 분리막. Battery separator coated with a polyurethane-based polymer compound on glass fiber. 제 1항에 있어서, 상기 폴리우레탄계 고분자 화합물이 0.1~5 중량%로 코팅된 것을 특징으로 하는 전지용 분리막.The battery separator according to claim 1, wherein the polyurethane-based high molecular compound is coated at 0.1 to 5 wt%. 제 1항 또는 제2항에 있어서, 상기 폴리우레탄계 고분자 화합물은 아미드기(-NCO-)를 포함하는 것을 특징으로 전지용 분리막.The battery separator according to claim 1 or 2, wherein the polyurethane-based polymer compound includes an amide group (-NCO-). 제 1항 또는 제 2항에 있어서, 상기 코팅이 스크린 인쇄법, 프린팅법, 스핀코팅법, 딥핑법(dipping) 및 잉크분사법으로 이루어진 군으로부터 선택되는 코팅방법에 의해서 형성되는 것을 특징으로 하는 전지용 분리막.3. The battery according to claim 1 or 2, wherein the coating is formed by a coating method selected from the group consisting of screen printing, printing, spin coating, dipping and ink spraying. Separator. 제 1항에 있어서, 상기 분리막의 두께가 250~400㎛인 것을 특징으로 하는 전지용 분리막.The battery separator according to claim 1, wherein the separator has a thickness of 250 to 400 µm. 제 1항에 있어서, 상기 분리막이 Li/SOCl2 전지용인 것을 특징으로 하는 전지용 분리막. The method of claim 1, wherein the separator is Li / SOCl 2 Battery separator, characterized in that the battery. 제 1항의 전지용 분리막을 포함하는 Li/SOCl2 전지.Li / SOCl 2 battery comprising the battery separator of claim 1. 제 7항에 있어서, 상기 전지의 양극(anode)은 리튬 금속 또는 리튬 합금인 것을 특징으로 하는 Li/SOCl2 전지. The Li / SOCl 2 battery according to claim 7, wherein the anode of the battery is lithium metal or a lithium alloy. 제 7항에 있어서, 상기 전지의 음극(cathode)은 케첸 블랙(Ketjen black) 또는 아세틸렌 블랙의 활물질에 폴리(테트라플루오로에틸렌) 바인더(PTFE binder)가 포함되는 것을 특징으로 하는 Li/SOCl2 전지.8. The Li / SOCl 2 battery of claim 7, wherein the cathode of the battery comprises a poly (tetrafluoroethylene) binder in an active material of Ketjen black or acetylene black. . 제 7항에 있어서, 상기 전지의 전해액으로 리튬염이 해리된 SOCl2 용액을 사용하는 것을 특징으로 하는 Li/SOCl2 전지. 8. The Li / SOCl 2 battery according to claim 7, wherein an SOCl 2 solution in which lithium salt is dissociated is used as an electrolyte of the battery. 제 10항에 있어서, 상기 리튬염은 LiAlCl4,LiCl, LiBr, LiBF4, LiSbF6, LiClO4, LiGaCl4, LiTFSI, LiPF6 , LiSCN, LiO3SCF2CF3, LiC6F5SO3, LiO2, LiO2CCF3, LiSO3F 및 LiCF3SO3로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 Li/SOCl2 전지.The method according to claim 10, wherein the lithium salt is LiAlCl 4 , LiCl, LiBr, LiBF 4 , LiSbF 6 , LiClO 4 , LiGaCl 4 , LiTFSI, LiPF 6 , LiSCN, LiO 3 SCF 2 CF 3 , LiC 6 F 5 SO 3 , LiO 2 , LiO 2 CCF 3 , LiSO 3 F and LiCF 3 SO 3 Li / SOCl 2 battery, characterized in that at least one selected from the group consisting of. 제 10항 또는 제 11항에 있어서, 상기 리튬염의 농도는 0.1~2M인 것을 특징으로 하는 Li/SOCl2 전지.The Li / SOCl 2 battery according to claim 10 or 11, wherein the lithium salt has a concentration of 0.1 to 2 M.
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EP2541644A2 (en) * 2010-02-25 2013-01-02 LG Chem, Ltd. Manufacturing method for separator, separator made therefrom, and manufacturing method for electrochemical device containing same
CN112331849A (en) * 2020-10-30 2021-02-05 武汉昊诚能源科技有限公司 Lithium thionyl chloride battery positive electrode material and application thereof

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EP2541644A2 (en) * 2010-02-25 2013-01-02 LG Chem, Ltd. Manufacturing method for separator, separator made therefrom, and manufacturing method for electrochemical device containing same
EP2541644A4 (en) * 2010-02-25 2014-03-12 Lg Chemical Ltd Manufacturing method for separator, separator made therefrom, and manufacturing method for electrochemical device containing same
US8815433B2 (en) 2010-02-25 2014-08-26 Lg Chem, Ltd. Method for manufacturing separator, separator manufactured by the method and method for manufacturing electrochemical device including the separator
US9985260B2 (en) 2010-02-25 2018-05-29 Lg Chem, Ltd. Separator for electrochemical device and electrochemical device including the separator
CN112331849A (en) * 2020-10-30 2021-02-05 武汉昊诚能源科技有限公司 Lithium thionyl chloride battery positive electrode material and application thereof

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