KR100477982B1 - Coating method of lithium battery metal grid - Google Patents

Coating method of lithium battery metal grid Download PDF

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KR100477982B1
KR100477982B1 KR1019970051259A KR19970051259A KR100477982B1 KR 100477982 B1 KR100477982 B1 KR 100477982B1 KR 1019970051259 A KR1019970051259 A KR 1019970051259A KR 19970051259 A KR19970051259 A KR 19970051259A KR 100477982 B1 KR100477982 B1 KR 100477982B1
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metal
metal grid
lithium battery
conductive polymer
grid
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KR1019970051259A
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KR19990030825A (en
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서현미
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삼성에스디아이 주식회사
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

도전성 폴리머와 음이온을 포함하는 전해질 용액을 제공하고, 양극에 제1금속으로서 리튬 전지의 금속 그리드를 연결하고, 음극에 제2금속을 연결하고, 양(兩) 극에 전위차를 가하는 과정을 포함하는 리튬 전지 금속 그리드의 코팅 방법은 상기 금속 그리드 표면에 상기 도전성 폴리머를 단시간 내에 균일하게 코팅할 수 있다.Providing an electrolyte solution containing a conductive polymer and an anion, connecting a metal grid of a lithium battery as a first metal to a positive electrode, connecting a second metal to a negative electrode, and applying a potential difference to a positive electrode; In the method of coating a lithium battery metal grid, the conductive polymer may be uniformly coated on the metal grid surface in a short time.

Description

리튬 전지 금속 그리드의 코팅 방법Coating Method of Lithium Battery Metal Grid

[산업상 이용 분야][Industrial use]

본 발명은 도전성 폴리머(conductive polymer)를 전기 화학적 방법(electrochemical method)으로 금속 그리드(grid) 표면에 코팅(coating)하는 방법에 관한 것으로서, 보다 상세하게는 리튬(Lithium)군 전지에서 도전성 폴리머를 전기 화학적인 방법으로 집전체(current collector)로 사용되는 금속 그리드 표면에 코팅하는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of coating a conductive polymer on a surface of a metal grid by an electrochemical method, and more particularly, to conducting a conductive polymer in a lithium group battery. The present invention relates to a method of coating a metal grid surface used as a current collector by a chemical method.

[종래기술][Private Technology]

일반적으로 전지는 망간 전지, 알칼리 전지, 수은 전지 및 산화은 전지 등과 같이 1회로 사용이 제한되는 1차 전지와 납축전지, 니켈-메탈하이드라이드(Nickel-Metalhydride) 전지, 니켈-카드뮴(Nickel-Cadmium) 전지 및 리튬-금속(Lithium-Metal)·리튬-이온(Lithium-Ion)·리튬-폴리머(Lithium-Polymer) 전지와 같은 리튬군 전지 등과 같이 충전하여 재사용이 가능한 2차 전지로 대별할 수 있다.In general, batteries include primary and lead-acid batteries, nickel-metal hydride batteries, and nickel-cadmium, which are limited in one use, such as manganese, alkaline, mercury, and silver oxide batteries. Batteries and lithium group metals such as lithium-metal, lithium-ion, and lithium-polymer batteries can be roughly classified into secondary batteries that can be charged and reused.

상기한 리튬군 전지는 양극으로 전이 금속 산화물(transition metal oxide) 또는 산화물 고용체(LiMxCO1-xO2, LiMxCO1-xO2, M; Ni, Co, Fe, Mn, Cr 등)를 사용하고 음극으로 리튬을 사용하는 것으로서, 캠코더, 휴대폰, 노트북 PC 등의 보조 전원 장치로 주로 사용되고 있다.The lithium group battery has a transition metal oxide or an oxide solid solution (LiM x CO 1-x O 2 , LiM x CO 1-x O 2 , M; Ni, Co, Fe, Mn, Cr, etc.) as a positive electrode. ) And lithium as a negative electrode, which is mainly used as an auxiliary power supply for camcorders, mobile phones, notebook PCs, etc.

상기한 리튬군 전지에 있어서, 금속 그리드, 특히 알루미늄 또는 구리 그리드가 집전체로서 사용되고, 상기 금속 그리드에 양극 또는 음극 활물질을 도포하여 극판을 형성하게 되는 바, 이 경우 상기 집전체, 특히 알루미늄 그리드 집전체의 표면에서는 옥사이드(oxide) 화합물이 쉽게 형성되고, 상기 옥사이드 화합물로 인하여 내부 전기 저항이 발생하게 된다. 또한, 전해질 용액이 침투하여 전극이 팽창하게 되고, 상기 전해질 용액이 활물질 도포층과 집전체 표면 사이에 스며들어 상기 활물질 도포층과 상기 집전체 간의 견고한 물리적 접촉을 저해함으로써 도전성을 저하시키게 되며, 이는 결국 전지의 수명을 단축시키고 전지의 방전 특성을 저하시키는 결과를 초래하게 된다. In the lithium group battery, a metal grid, in particular aluminum or copper grid, is used as a current collector, and the positive electrode or negative electrode active material is applied to the metal grid to form a pole plate. In this case, the current collector, in particular, an aluminum grid collector On the whole surface, an oxide compound is easily formed, and an internal electric resistance is generated due to the oxide compound. In addition, the electrolyte solution penetrates and the electrode expands, and the electrolyte solution penetrates between the active material coating layer and the current collector surface, thereby lowering conductivity by inhibiting a firm physical contact between the active material coating layer and the current collector, As a result, the battery life may be shortened and the discharge characteristics of the battery may be degraded.

상기한 문제점을 해결하기 위하여 미국 특허 제5,554,459호는 금속 그리드 표면의 절연성 물질을 제거한 후 금속에 높은 접착력을 가지는 도전성 폴리머를 금속 그리드 표면에 코팅하는 방법을 개시하고 있다. 그러나, 상기한 특허에서는 코팅을 위하여 일반적인 침적(dipping) 또는 스프레이(spraying) 방법을 사용하고 있는 바, 이 경우 금속 그리드 표면에 도전성 폴리머가 균일하게 코팅되는 것이 어려워 충분한 코팅 효과를 기대할 수 없다는 문제점이 있다. In order to solve the above problems, U. S. Patent No. 5,554, 459 discloses a method for coating a metal grid surface with a conductive polymer having high adhesion to the metal after removing the insulating material from the metal grid surface. However, the above patent uses a general dipping or spraying method for coating. In this case, it is difficult to uniformly coat the conductive polymer on the surface of the metal grid, so that a sufficient coating effect cannot be expected. have.

본 발명은 상기한 종래 기술의 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 리튬(Lithium)군 전지에서 집전체(current collector)로 사용되는 금속 그리드 표면에 도전성 폴리머를 단시간 내에 균일하게 코팅할 수 있는, 리튬 전지 그리드의 전기 화학적인 코팅 방법을 제공하는 것이다. The present invention is to solve the above problems of the prior art, an object of the present invention is to uniformly coat a conductive polymer on a metal grid surface used as a current collector in a lithium group battery in a short time. The present invention provides an electrochemical coating method of a lithium battery grid.

[과제를 해결하기 위한 수단][Means for solving the problem]

상기한 목적을 달성하기 위하여, 본 발명은 도전성 폴리머와 음이온을 포함하는 전해질 용액을 제공하고, 양극에 제1금속으로서 리튬 전지의 금속 그리드를 연결하고, 음극에 제2금속을 연결하고, 양(兩) 극에 전위차를 가하는 과정을 포함하는 리튬 전지 금속 그리드의 코팅 방법을 제공한다.In order to achieve the above object, the present invention provides an electrolyte solution containing a conductive polymer and an anion, connecting a metal grid of a lithium battery as a first metal to a positive electrode, a second metal to a negative electrode, Iii) a method of coating a lithium cell metal grid comprising a step of applying a potential difference to a pole.

상기 도전성 폴리머는 금속에 대한 접착력이 강하고 에테르, 에스테르 및 알콜과 같은 용매, 전극과 세퍼레이터(separater)로부터 가소제(예를 들면, DBP)를 추출하는데 사용되는 용매, 활성 전해질 용액을 포함하는 사이클릭(cyclic) 또는 어사이클릭(acyclic) 카보네이트(carbonate)와 같은 리튬염 용매에 불용성이며, 상기 용매 내에서 팽창되지 않는 성질을 가지는 것으로서, 폴리파이롤(polypyrrole), 폴리티오펜(polythiophene), 폴리아닐린(polyaniline)으로 이루어진 군에서 선택되는 것이 바람직하다.The conductive polymer has a strong adhesion to metals and includes a cyclic compound containing a solvent such as ethers, esters and alcohols, a solvent used to extract a plasticizer (e.g., DBP) from an electrode and a separator, and an active electrolyte solution. Insoluble in a lithium salt solvent such as cyclic or acyclic carbonate, and insoluble in the solvent, polypyrrole, polythiophene, polyaniline ( polyaniline).

상기 음이온은 LiClO4 또는 LiBF4로부터 제공되는 것이 바람직하다.The anion is preferably provided from LiClO 4 or LiBF 4 .

상기 제1금속, 즉 상기 금속 그리드는 알루미늄 또는 구리 그리드인 것이 바람직하며, 상기 제2금속은 백금(Pt)인 것이 바람직하다.Preferably, the first metal, ie, the metal grid, is an aluminum or copper grid, and the second metal is preferably platinum (Pt).

또한, 상기 전위차는 0.7～1.0V인 것이 바람직하다.Moreover, it is preferable that the said potential difference is 0.7-1.0V.

상기 전위차가 0.7V 미만인 경우에는 폴리머의 합성이 일어나지 않는 문제점이 있고, 1.0V를 초과하는 경우에는 폴리머의 분해가 발생하는 문제점이 있다.If the potential difference is less than 0.7V, there is a problem that the synthesis of the polymer does not occur, and if it exceeds 1.0V, there is a problem that the decomposition of the polymer occurs.

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

본 발명에 따른 도전성 폴리머와 음이온을 포함하는 전해질 용액, 양극에 연결된 제1금속으로서의 리튬 전지의 금속 그리드 및 음극에 연결된 제2금속을 포함하는 리튬 전지 금속 그리드의 코팅 장치를 도 1에 도식적으로 나타내었다. 상기 도전성 폴리머는 전기적 활성과 약 100 정도의 전도도(s/cm)를 가지는 물질로서, 금속 그리드 표면에 코팅되면 전도성이 없는 활물질 도포층과 집전체 간에 전기 저항을 감소시키며, 상기 활물질 도포층에 상기 집전체가 도포(laminated)될 때, 양자 간의 접착력을 강화시키는 작용을 하게 된다.1 shows a coating apparatus of a lithium battery metal grid including an electrolyte solution containing a conductive polymer and an anion, a metal grid of a lithium battery as a first metal connected to a positive electrode, and a second metal connected to a negative electrode, according to the present invention. It was. The conductive polymer is a material having an electrical activity and a conductivity (s / cm) of about 100. When the conductive polymer is coated on the metal grid surface, the conductive polymer reduces electrical resistance between the non-conductive active material coating layer and the current collector. When the current collector is laminated, it serves to enhance the adhesion between the two.

상기한 바와 같이, 양(兩) 극에 전위차를 가하게 되면, 양전위가 걸리는 금속 그리드 표면에 도전성 폴리머가 중합되어 코팅이 일어나게 된다.As described above, when a potential difference is applied to the positive pole, the conductive polymer is polymerized on the surface of the metal grid which is subjected to the positive potential, thereby causing a coating.

상기 전위차를 가하는 시간은 수 초로도 충분하다.A few seconds may be sufficient for adding the potential difference.

이 때, 산화 전위로 인하여 폴리머가 가지게 되는 양전위는 전해질 용액으로부터 제공되는 상기 음이온에 의해 상쇄될 수 있다.At this time, the positive potential of the polymer due to the oxidation potential may be offset by the anion provided from the electrolyte solution.

더욱이, 본 발명에 따른 코팅 방법은 전류 밀도, 용매, 전해질 및 전극 전위 등의 전기적 조건을 변화시켜 줌으로써 코팅되는 폴리머의 성질을 용이하게 조절할 수 있도록 한다. Moreover, the coating method according to the present invention makes it possible to easily control the properties of the coated polymer by changing the electrical conditions such as current density, solvent, electrolyte and electrode potential.

[실시예]EXAMPLE

이하 본 발명의 바람직한 실시예 및 비교예를 기재한다. 그러나 하기한 실시예는 본 발명의 구성 및 효과를 설명하기 위한 바람직한 일 실시예일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments for explaining the construction and effects of the present invention, and the present invention is not limited to the following examples.

[실시예 1]Example 1

0.1M 파이롤과 0.1M LiClO4를 함유한 전해질 용액 내에 양극에는 알루미늄 그리드를 연결시키고 음극에는 백금 금속을 연결시킨 후 5초 간 1.0V의 전위차를 가하였다.In an electrolyte solution containing 0.1 M pyrrole and 0.1 M LiClO 4 , an aluminum grid was connected to the positive electrode and platinum metal to the negative electrode, and a potential difference of 1.0 V was applied for 5 seconds.

본 발명에 의한 리튬 전지 금속 그리드의 코팅 방법을 사용하면, 단시간 내에 도전성 폴리머를 금속 그리드 표면에 균일하게 코팅할 수 있으므로 집전체와 활물질 도포층 간의 접착력을 강화하고 상기 집전체와 상기 활물질 도포층 간의 전기 저항을 최소화하여 향상된 수명 특성과 고효율의 방전 특성을 가지는 리튬 전지를 제공할 수 있게 된다.By using the lithium battery metal grid coating method according to the present invention, the conductive polymer can be uniformly coated on the surface of the metal grid within a short time, thereby enhancing the adhesion between the current collector and the active material coating layer and between the current collector and the active material coating layer. By minimizing the electrical resistance it is possible to provide a lithium battery having improved life characteristics and high efficiency discharge characteristics.

도 1은 본 발명에 따른 리튬 전지 금속 그리드의 코팅 장치의 개략도이다.1 is a schematic view of a coating apparatus of a lithium battery metal grid according to the present invention.

Claims (5)

도전성 폴리머와 음이온을 포함하는 전해질 용액을 제공하고;Providing an electrolyte solution comprising a conductive polymer and an anion; 양극에 제1금속으로 리튬 전지의 금속 그리드를 연결하고;Connecting a metal grid of a lithium battery to a positive electrode with a first metal; 음극에 제2금속을 연결하고;Connecting a second metal to the cathode; 양(兩) 극간에 0.7～1.0V의 전위차를 가하는 과정:The process of applying a potential difference of 0.7 to 1.0 V between the two poles: 을 포함하는 리튬 전지 금속 그리드의 코팅 방법.Coating method of a lithium battery metal grid comprising a. 제1항에 있어서, 상기 도전성 폴리머는 폴리파이롤, 폴리티오펜 및 폴리아닐린으로 이루어진 군에서 선택되는 리튬 전지 금속 그리드의 코팅 방법.The method of claim 1, wherein the conductive polymer is selected from the group consisting of polypyrrole, polythiophene, and polyaniline. 제1항에 있어서, 상기 음이온은 LiClO4 또는 LiBF4로부터 제공되는 것인 리튬 전지 금속 그리드의 코팅 방법.The method of claim 1, wherein the anion is provided from LiClO 4 or LiBF 4 . 제1항에 있어서, 상기 금속 그리드는 알루미늄 또는 구리 그리드인 리튬 전지 금속 그리드의 코팅 방법.The method of claim 1, wherein the metal grid is an aluminum or copper grid. 제1항에 있어서, 상기 제2금속은 백금인 것인 리튬 전지 금속 그리드의 코팅 방법.The method of claim 1, wherein the second metal is platinum.
KR1019970051259A 1997-10-06 1997-10-06 Coating method of lithium battery metal grid KR100477982B1 (en)

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JPS61245468A (en) * 1985-04-23 1986-10-31 Toyota Central Res & Dev Lab Inc Nonaqueous electrolyte storage battery
JPH0750110A (en) * 1991-09-27 1995-02-21 Kazuo Ikezaki Manufacture of conductive composite film
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JPH0750110A (en) * 1991-09-27 1995-02-21 Kazuo Ikezaki Manufacture of conductive composite film
KR960027024A (en) * 1994-12-01 1996-07-22 김광호 Nickel hydroxide electrode for alkaline secondary battery and manufacturing method thereof
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KR200491012Y1 (en) 2019-10-01 2020-02-06 장준호 Watered Tissue Cap

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