KR19990086308A - All-lithiation method of carbon electrode and manufacturing method of lithium secondary battery using same - Google Patents

All-lithiation method of carbon electrode and manufacturing method of lithium secondary battery using same Download PDF

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KR19990086308A
KR19990086308A KR1019980019243A KR19980019243A KR19990086308A KR 19990086308 A KR19990086308 A KR 19990086308A KR 1019980019243 A KR1019980019243 A KR 1019980019243A KR 19980019243 A KR19980019243 A KR 19980019243A KR 19990086308 A KR19990086308 A KR 19990086308A
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carbon electrode
lithium
electrode
carbon
secondary battery
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KR100291067B1 (en
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윤경석
조병원
조원일
백지흠
김형선
김운석
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박호군
한국과학기술연구원
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 발명은 카본 전극의 전리튬화 방법과 이를 이용한 리튬 이차전지 제조방법에 관한 것으로, 종래의 리튬 이차전지는 음극으로 사용된 카본 전극이 피막형성 반응의 비가역적 반응으로 리튬 이온의 소모를 가져와 전지의 용량을 감소시키는 역효과와 싸이클 수명이 저하하게 되는 문제점이 있는 바, 본 발명은 카본 전극과 리튬 금속을 저항으로 연결하거나 직접 접촉시킨 상태에서 온도와 전해질의 이온전도도를 변화시켜서 카본 전극이 리튬화 되는 속도와 양을 조절하고, 리튬화 후에 일정 온도와 시간 동안 안정화 시킴으로써 카본 전극 표면상에 안정한 피막을 형성하여 카본 전극의 가역성을 향상시키고, 리튬화된 카본 전극으로 리튬 이차전지를 제조하여, 카본 전극에서의 비가역용량에 의한 용량저하를 방지함으로써 용량증가와 충방전시 충방전 효율 문제로 인하여 소모되는 리튬의 양을 보충해줌으로써 싸이클 수명을 향상시키도록 한 것이다.The present invention relates to a method of prelithiation of a carbon electrode and a method of manufacturing a lithium secondary battery using the same. In the conventional lithium secondary battery, a carbon electrode used as a negative electrode causes consumption of lithium ions due to an irreversible reaction of a film forming reaction. There is a problem in that the adverse effect of reducing the capacity and the cycle life is reduced, the present invention is to change the temperature and the ion conductivity of the electrolyte in the state in which the carbon electrode and lithium metal connected by resistance or in direct contact with the lithification of the carbon electrode By controlling the rate and amount of the oxidization and stabilizing for a certain temperature and time after lithiation, a stable film is formed on the surface of the carbon electrode to improve the reversibility of the carbon electrode, and a lithium secondary battery is manufactured by using a lithiated carbon electrode. Capacity increase and charging / discharging by preventing capacity decrease by irreversible capacity at electrode By giving prior year due to efficiency issues supplement the amount of consumed lithium it will have to improve the cycle life.

Description

카본 전극의 전리튬화 방법과 이를 이용한 리튬 이차전지 제조방법All-lithiation method of carbon electrode and manufacturing method of lithium secondary battery using same

본 발명은 카본 전극의 전리튬화 방법과 이를 이용한 리튬 이차전지 제조방법에 관한 것으로 카본 전극의 전리튬화는 카본 전극과 리튬 금속을 저항으로 연결하거나 직접 접촉시킨 상태에서 온도와 전해질의 이온전도도를 변화시켜서 카본 전극이 리튬화 되는 속도와 양을 조절하고, 리튬화 후에 일정 온도에서, 일정 시간동안 안정화 시킴으로써 카본 전극 표면상에 안정한 피막을 형성하여 카본 전극의 가역성을 향상시키고, 리튬화된 카본 전극으로 리튬 이차전지를 제조하여, 초기 충전시 나타나는 카본 전극에서의 비가역용량에 의한 용량저하를 방지함으로써 용량증가를 가져오고, 또한 충방전시 충방전 효율 문제로 인하여 소모되는 리튬의 양을 보충해줌으로써 싸이클 수명을 향상시키는 카본 전극의 전리튬화 방법과 이를 이용한 리튬 이차전지 제조방법에 관한 것이다.The present invention relates to a method of prelithiation of a carbon electrode and a method of manufacturing a lithium secondary battery using the same. The prelithiation of a carbon electrode is characterized in that the temperature and the ion conductivity of the electrolyte in the state in which the carbon electrode and the lithium metal are directly connected or directly contacted By changing the rate and amount of lithiation of the carbon electrode, and stabilizing the carbon electrode at a constant temperature for a certain time after lithiation to form a stable film on the surface of the carbon electrode, thereby improving the reversibility of the carbon electrode, and lithiated carbon electrode. By manufacturing a lithium secondary battery, by increasing the capacity by preventing the capacity decrease due to irreversible capacity in the carbon electrode appearing during the initial charge, and also by replenishing the amount of lithium consumed due to charge and discharge efficiency problems during charging and discharging All-lithiation method of carbon electrode to improve cycle life and lithium secondary battery using same It relates to a process for producing the same.

종래의 리튬 이차전지는 양극으로 LiCoO2, LiMn2O4등 리튬이 삽입되어 있는 화합물을 사용하기 때문에 음극으로 사용되는 카본 전극에 리튬이 삽입되어 있지 않는 상태로 전지가 제조되고 있다. 카본 전극인 경우는 초기 충전시 카본 전극 표면상에 부동태 피막이 형성되는데, 이 피막은 카본 격자층 사이로 유기용매가 삽입되지 않도록 방해하여 유기용매의 분해반응을 억제함으로써 카본 구조의 안정화 및 카본 전극의 가역성을 향상시켜 리튬 이차전지용 음극으로의 사용을 가능케 한다. 그러나 이러한 피막형성 반응은 비가역적 반응이기 때문에 리튬 이온의 소모를 가져와 전지의 용량을 감소시키는 역효과도 있다. 또한 카본 전극 및 양극은 충방전 효율이 완전히 100%가 아니기 때문에 싸이클수가 진행됨에 따라 리튬 이온의 소모가 발생하게 되어 전극용량의 감소를 일으키므로 결국 싸이클 수명이 저하하게 된다. 따라서 본 발명에서처럼 전리튬화된 카본 전극을 음극으로 사용하면 초기 충전시 나타나는 피막형성 반응을 미리 시켰기 때문에 용량의 저하 없이 고용량의 리튬 이차전지를 제조할 수 있을 뿐만 아니라 싸이클수가 증가함에 따라서 나타나는 리튬 이온의 소모를 보충해 주기 때문에 싸이클 수명을 대폭 향상시킬 수 있다.Since a conventional lithium secondary battery uses a compound containing lithium, such as LiCoO 2 and LiMn 2 O 4 , as a positive electrode, a battery is manufactured in a state in which lithium is not inserted into a carbon electrode used as a negative electrode. In the case of the carbon electrode, a passivation film is formed on the surface of the carbon electrode during initial charging, which prevents the organic solvent from intercalating between the carbon lattice layers and suppresses decomposition reaction of the organic solvent, thereby stabilizing the carbon structure and reversibility of the carbon electrode. It can be used as a negative electrode for a lithium secondary battery. However, since the film forming reaction is an irreversible reaction, there is also an adverse effect of reducing the capacity of the battery by the consumption of lithium ions. In addition, since the charge and discharge efficiency of the carbon electrode and the positive electrode is not 100% completely, as the number of cycles progresses, consumption of lithium ions occurs, which leads to a decrease in electrode capacity, resulting in a decrease in cycle life. Therefore, when the pre-lithiated carbon electrode is used as a negative electrode as in the present invention, since the film formation reaction during initial charging is performed in advance, not only a lithium secondary battery having a high capacity can be manufactured without a decrease in capacity but also lithium ions appearing as the number of cycles increases. The cycle life can be significantly improved by replenishing the consumption of.

종래의 카본 전극의 전리튬화 방법은 카본 활물질을 물리화학적인 방법으로 리튬화 시킨 후 전극을 제조하는 방법 (K. Zaguib, R. Yazami and M. Broussely, 8th International Meeting on Lithium Batteries, 192(1996))과 카본 전극을 전기화학적으로 전리튬화 하는 방법 (X. Y. Song and K. Kinoshita, J. Electrochem. Soc., 143, L120(1996), L L Olsen and R. Koksbang, US Pat. 5,595,837(1997))이 있는데 물리화학적 방법은 고온에서 실시하여야 하기 때문에 화재 및 폭발 등의 위험성이 내포되어 있다. 이에 반하여 전기화학적 방법은 상온에서 실시할 수 있는 장점이 있으나, 공정 상에 다소 어려운 점이 있다. 본 발명과의 차별화를 위해 기존의 전기화학적 방법의 문제점을 살펴보면 전원을 사용하여 전류를 조정함으로써 리튬화 반응속도를 조정하므로서 전원을 설치하고 제어해야 하는 단점이 있고, 안정화 과정이 없기 때문에 카본 전극 내에서 리튬이 골고루 분산되지 못하여 전지특성, 특히 싸이클 수명 특성이 불량하게 나타나는 단점이 있다.The conventional method of prelithiation of a carbon electrode is a method of preparing an electrode after lithiating a carbon active material by a physicochemical method (K. Zaguib, R. Yazami and M. Broussely, 8th International Meeting on Lithium Batteries, 192 (1996). And electrochemically prelithiation of carbon electrodes (XY Song and K. Kinoshita, J. Electrochem. Soc., 143, L120 (1996), LL Olsen and R. Koksbang, US Pat. 5,595,837 (1997) There are risks such as fire and explosion because the physicochemical method must be carried out at high temperature. In contrast, the electrochemical method has an advantage that can be carried out at room temperature, but there are some difficulties in the process. Looking at the problems of the conventional electrochemical method for differentiation from the present invention has the disadvantage of having to install and control the power supply by adjusting the lithiation reaction rate by adjusting the current using the power supply, there is no stabilization process in the carbon electrode Lithium is not evenly dispersed in the battery characteristics, in particular the cycle life characteristics have a disadvantage that appears poor.

따라서, 본 발명은 상기와 같은 문제점을 감안하여 안출한 것으로, 온도와 전해질의 이온전도도를 변화시켜 카본 전극이 리튬화 되는 속도와 양을 조절하고, 카본 전극의 가역성을 향상시킨 리튬화된 카본 전극으로 리튬 이차전지를 제조하여, 용량증가와 싸이클 수명의 향상가능한 카본 전극의 전리튬화 방법과 이를 이용한 리튬 이차전지 제조방법을 제공하는 것을 그 목적으로 한다.Accordingly, the present invention has been made in view of the above problems, and the lithiated carbon electrode which changes the temperature and ion conductivity of the electrolyte to control the rate and amount of lithiation of the carbon electrode and improves the reversibility of the carbon electrode. The purpose of the present invention is to provide a lithium secondary battery, and to provide a lithium secondary battery manufacturing method using the same and a lithium secondary battery that can increase capacity and improve cycle life.

도 1은 본 발명에 의한 카본 전극의 전리튬화 방법-1을 나타낸 그래프이다.1 is a graph showing a method of prelithiation of a carbon electrode according to the present invention.

도 2는 본 발명에 의한 카본 전극의 전리튬화 방법-2를 나타낸 그래프이다.2 is a graph showing a method of prelithiation of a carbon electrode according to the present invention.

도 3은 본 발명에 의한 카본 전극으로 제조한 리튬 이차전지의 실시예 1과 비교예 1에 대한 충방전 특성을 나타낸 그래프이다.3 is a graph showing charge and discharge characteristics of Example 1 and Comparative Example 1 of a lithium secondary battery manufactured by a carbon electrode according to the present invention.

도 4는 본 발명에 의한 카본 전극으로 제조한 리튬 이차전지와 비교예 1의 전극용량 및 수명 시험결과를 나타낸 그래프이다.4 is a graph showing the electrode capacity and the life test results of the lithium secondary battery manufactured by the carbon electrode according to the present invention and Comparative Example 1.

본 발명에서는 카본 전극의 전리튬화 방법과 이를 이용한 리튬 이차전지 제조방법에 있어서, 카본 전극과 리튬 금속을 저항으로 연결하거나 직접 접촉시킨 상태에서 온도와 전해질의 이온전도도를 변화시켜 카본 전극이 리튬화되는 반응속도를 일정하게 조절하고, 또한 리튬화 후 일정 온도 하에서 일정 시간동안 안정화시킴으로써 리튬이 카본 전극내 골고루 분산되도록 함으로써 전지의 용량 및 싸이클 수명을 대폭 향상시켰다.In the present invention, in the method of prelithiation of a carbon electrode and a method of manufacturing a lithium secondary battery using the same, the carbon electrode is lithiated by changing the temperature and the ion conductivity of the electrolyte in a state in which the carbon electrode and the lithium metal are connected or connected in direct contact with each other. By controlling the reaction rate to be constant and stabilizing for a certain period of time after lithiation, lithium is evenly dispersed in the carbon electrode, thereby greatly improving the battery capacity and cycle life.

이하에서는 첨부도면에 의거하여 본 발명을 보다 상세하게 설명하고자 한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

본 발명에 의한 카본 전극의 전리튬화 방법은 크게 두가지로 나눌 수 있는데, 첫 번째는 도 1과 같이 저항으로 조절하여 리튬화 시키고 안정화시키는 방법과, 둘째로는 도 2와 같이 직접 접촉시켜서 리튬화 하고 안정화시키는 방법이 있다. 우선 도 1의 저항으로 하는 방법을 구체적으로 살펴보면 초기에는 1∼5kΩ/g(carbon) 정도의 고저항체를 연결하여 리튬화되는 속도를 느리게 함으로써 카본 전극 표면에 안정한 부동태 피막을 형성하게 하고, 그 후에 50∼500Ω/g(carbon) 정도의 저저항체를 연결하여 반응속도를 빠르게 함으로써 카본격자 사이로 리튬이온이 삽입되도록 하는 것이다. 특히 초기의 피막형성 반응시에는 온도를 낮게 하면 부동태 피막을 더욱 치밀하게 할 수 있는 장점이 있다. 리튬화 반응 후에는 연결을 차단한 상태로 30∼100℃의 온도에서 하루 정도 안정화시켜 리튬화가 전극 활물질에 골고루 이루어지도록 한다. 리튬 금속은 접착력 및 가공성이 우수하므로 압연 롤러 상에 압착하여 피복시켜 리튬 전극으로 사용하였으며, 그 위에 분리막을 감싸주어 이 분리막이 카본 전극과 리튬 전극 사이의 단락을 방지하고 유기용매 전해질을 함침하게하여 전류가 흐르도록 하였다. 도 2의 직접 접촉시켜 리튬화 하는 방법은 카본 전극과 리튬 금속을 직접 접촉시키는 방법으로 단순히 접촉만 시키면 초기에 리튬화 속도가 빠르게 일어나고, 시간 경과에 따라서 점차적으로 리튬화 속도가 감소한다. 그러나 초기에 리튬화 속도가 빠르면 부동태 피막형성 반응과 카본 격자 안으로의 리튬 삽입반응이 동시에 일어나기 때문에 카본 구조의 파괴가 일어나게 된다. 따라서 본 발명에서는 초기에 안정한 부동태 피막형성이 이루어지고 나중에 리튬 삽입반응이 잘 이루어지도록 적절한 온도와 전해질의 이온전도도를 조절하였다. 구체적으로 설명하면 1단계에서는 저온(-10∼15℃)과 이온전도도가 낮은 전해질(∼10-3S/cm) 하에서 리튬화 반응을 실시하여 리튬화 반응이 서서히 일어나도록하여 부동태 피막이 잘 형성되도록 하고 2 단계에서는 상온과 이온전도도가 높은 전해질(∼10-2S/cm) 하에서 리튬화 반응을 시켜 카본격자 내로 리튬이 삽입되도록 하였다. 리튬화 반응 후에는 리튬 금속을 떼어내고 30∼100℃의 온도에서 12∼36 시간 사이의 일정시간 하에서 안정화시켜 리튬화가 전극 활물질에 골고루 이루어지도록 하였다.The method of prelithiation of a carbon electrode according to the present invention can be broadly divided into two methods. First, a method of controlling lithium by adjusting the resistance as shown in FIG. 1 and stabilizing it, and second, by direct contact as shown in FIG. There is a way to stabilize. First, the method of using the resistor of FIG. 1 will be described in detail. Initially, by connecting a high resistor of about 1 to 5 kΩ / g (carbon) to slow the lithiation rate, a stable passivation film may be formed on the surface of the carbon electrode. By connecting a low-resistance of about 50 ~ 500Ω / g (carbon) to increase the reaction rate is to insert lithium ions between the carbon grid. In particular, during the initial film formation reaction, lowering the temperature has the advantage of making the passivation film more dense. After the lithiation reaction is stabilized for about one day at a temperature of 30 ~ 100 ℃ in a state in which the connection is blocked so that the lithiation is evenly made on the electrode active material. Since lithium metal has excellent adhesion and workability, it is compressed and coated on a rolling roller to be used as a lithium electrode. The separator is wrapped thereon to prevent short circuit between the carbon electrode and the lithium electrode and to impregnate the organic solvent electrolyte. An electric current was made to flow. The method of lithiation by direct contact of FIG. 2 is a method of directly contacting a carbon electrode and a lithium metal. If only the contact is performed, the lithiation rate is initially increased, and the lithiation rate gradually decreases with time. However, if the lithiation rate is high initially, the passivation film formation reaction and the lithium insertion reaction into the carbon lattice simultaneously occur, resulting in the destruction of the carbon structure. Therefore, in the present invention, a stable passivation film is formed at an initial stage, and a proper temperature and ionic conductivity of the electrolyte are controlled so that a lithium insertion reaction is performed well later. Specifically, in the first step, lithiation reaction is performed under low temperature (-10-15 ° C.) and low ion conductivity electrolyte (˜10 -3 S / cm) so that lithiation reaction occurs gradually so that the passivation film is well formed. In step 2, lithium was reacted under an electrolyte having high temperature and ion conductivity (˜10 −2 S / cm) to allow lithium to be inserted into the carbon grid. After the lithiation reaction, the lithium metal was removed and stabilized at a temperature of 30 to 100 ° C. for 12 to 36 hours to allow lithiation to be uniformly applied to the electrode active material.

다음은 본 발명의 제조방법을 사용하여 카본 전극 및 리튬 이차전지를 제조하고 성능시험을 실시한 실시예 및 비교예로써, 이에 의하여 본 발명을 보다 명확하게 이해할 수 있을 것이다.The following are examples and comparative examples in which a carbon electrode and a lithium secondary battery were manufactured using the manufacturing method of the present invention and performance tests were performed, whereby the present invention may be more clearly understood.

비교예에 대한 바람직한 실시예Preferred Example for Comparative Example

실시예 1Example 1

카본 음극은 Gr. 6g, AB 0.3g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 구리박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 도 1과 같이 이 전극의 양쪽에 분리막을 대고 그 바깥쪽에 리튬 금속을 댄 다음 1M LiPF6가 용해된 EC-DEC 용액을 적신 후 2.5kΩ/g(carbon) 정도의 고저항체를 연결하여 2시간 정도 리튬화 시킨다. 그 후에 저항체를 250Ω/g(carbon) 정도의 저저항체로 교체 연결하여 3시간 정도 리튬화 시킨다. 리튬화된 카본전극을 50℃에서 하루정도 방치하여 안정화시킨다. LiCoO2양극은 LiCoO25.7g, AB 0.6g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 알루미늄 박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 리튬 이차전지는 리튬화된 카본 음극, PP 분리막, LiCoO2양극을 적층하여 구성하고 1M LiPF6가 용해된 EC-DEC 용액을 주입한 후 충방전율 C/3로 양극을 기준으로 한 전극용량 및 싸이클 수명을 조사하였다.The carbon cathode is Gr. 6g, 0.3g of AB, 0.4g of PVdF are mixed with an appropriate amount of NMP and acetone, and then cast on a copper foil, dried and rolled to obtain an electrode when a suitable viscosity is obtained. As shown in FIG. 1, a separator was placed on both sides of the electrode, and lithium metal was applied to the outside thereof. Then, a 1M LiPF 6 -dissolved EC-DEC solution was wetted, and a high resistance of about 2.5 kΩ / g (carbon) was connected. Lithiate. After that, the resistor is replaced with a low resistor of 250Ω / g (carbon) and lithiated for about 3 hours. The lithiated carbon electrode is left to stabilize at 50 ° C. for one day. The LiCoO 2 positive electrode is mixed with a composition of 5.7 g of LiCoO 2 , 0.6 g of AB, and 0.4 g of PVdF in an appropriate amount of NMP and acetone, and then cast on an aluminum sheet, dried, and rolled to obtain an electrode when an appropriate viscosity is obtained. Lithium secondary battery is composed by stacking lithiated carbon anode, PP separator and LiCoO 2 positive electrode, injecting EC-DEC solution in which 1M LiPF 6 is dissolved, and then charging / discharging rate C / 3 based on positive electrode capacity and cycle. The lifetime was investigated.

비교예 1Comparative Example 1

카본 음극은 Gr. 6g, AB 0.3g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 구리박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. LiCoO2양극은 LiCoO25.7g, AB 0.6g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 알루미늄 박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 리튬 이차전지는 카본 음극, PP 분리막, LiCoO2양극을 적층하여 구성하고 1M LiPF6가 용해된 EC-DEC 용액을 주입한 후 층방전율 C/3로 양극을 기준으로 한 전극용량 및 싸이클 수명을 조사하였다.The carbon cathode is Gr. 6g, 0.3g of AB, 0.4g of PVdF are mixed with an appropriate amount of NMP and acetone, and then cast on a copper foil, dried and rolled to obtain an electrode when a suitable viscosity is obtained. The LiCoO 2 positive electrode is mixed with a composition of 5.7 g of LiCoO 2 , 0.6 g of AB, and 0.4 g of PVdF in an appropriate amount of NMP and acetone, and then cast on an aluminum sheet, dried, and rolled to obtain an electrode when an appropriate viscosity is obtained. Lithium secondary battery is composed by stacking carbon negative electrode, PP separator, LiCoO 2 positive electrode and injecting EC-DEC solution in which 1M LiPF 6 is dissolved. Investigate electrode capacity and cycle life based on positive electrode with layer discharge rate C / 3. It was.

실시예 2Example 2

카본 음극은 Gr. 6g, AB 0.3g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 구리박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 도 2와 같이 이 전극의 양쪽에 리튬 금속을 댄 후 분위기 온도를 0℃로 하고 1M LiPF6가 용해된 EC-DEC 용액을 적셔 2시간 정도 리튬화 시킨다. 그 후에 분위기 온도를 25℃로하여 3시간 정도 리튬화 시킨다. 리튬화된 카본전극을 50℃에서 하루정도 방치하여 안정화시킨다. LiCoO2양극은 LiCoO25.7g, AB 0.6g, PVdF 0.4g의 조성을 적당한 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 알루미늄 박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 리튬 이차전지는 리튬화된 카본 음극, PP 분리막, LiCoO2양극을 적층하여 구성하고 1M LiPF6가 용해된 EC-DEC 용액을 주입한 후 충방전율 C/3로 양극을 기준으로 한 전극용량 및 싸이클 수명을 조사하였다.The carbon cathode is Gr. 6g, 0.3g of AB, 0.4g of PVdF are mixed with an appropriate amount of NMP and acetone, and then cast on a copper foil, dried and rolled to obtain an electrode when a suitable viscosity is obtained. As shown in FIG. 2, lithium metal was placed on both sides of the electrode, and the ambient temperature was 0 ° C., followed by soaking the EC-DEC solution in which 1M LiPF 6 was dissolved. Thereafter, the mixture is lithiated for about 3 hours at an ambient temperature of 25 ° C. The lithiated carbon electrode is left to stabilize at 50 ° C. for one day. The LiCoO 2 positive electrode is mixed with a composition of 5.7 g of LiCoO 2 , 0.6 g of AB, and 0.4 g of PVdF to a suitable NMP and acetone, and then cast on an aluminum sheet, dried, and rolled to obtain an electrode when a suitable viscosity is obtained. Lithium secondary battery is composed by stacking lithiated carbon anode, PP separator and LiCoO 2 positive electrode, injecting EC-DEC solution in which 1M LiPF 6 is dissolved, and then charging / discharging rate C / 3 based on positive electrode capacity and cycle. The lifetime was investigated.

실시예 3Example 3

카본 음극은 Gr. 6g, AB 0.3g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 구리박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 도 2와 같이 이 전극의 양쪽에 리튬 금속을 댄 후 분위기 온도를 10℃로 하고 0.1M LiPF6가 용해된 EC-DEC 용액을 적셔 2시간 정도 리튬화 시킨다. 그 후에 분위기 온도를 25℃로하여 1M LiPF6가 용해된 EC-DEC 용액을 추가로 주입한 후 3시간 정도 리튬화 시킨다. 리튬화된 카본 전극을 50℃에서 하루정도 방치하여 안정화 시킨다. LiCoO2양극은 LiCoO25.7g, AB 0.6g, PVdF 0.4g의 조성을 적당량의 NMP 및 아세톤에 혼합한 후 적당한 점도가 얻어졌을 때 알루미늄 박판 위에 캐스팅하여 건조시킨 후 압연하여 전극을 얻는다. 리튬 이차전지는 리튬화된 카본 음극, PP 분리막, LiCoO2양극을 적층하여 구성하고 1M LiPF6가 용해된 EC-DEC 용액을 주입한 후 충방전율 C/3로 양극을 기준으로 한 전극용량 및 싸이클 수명을 조사하였다.The carbon cathode is Gr. 6g, 0.3g of AB, 0.4g of PVdF are mixed with an appropriate amount of NMP and acetone, and then cast on a copper foil, dried and rolled to obtain an electrode when a suitable viscosity is obtained. As shown in FIG. 2, lithium metal was placed on both sides of the electrode, and the ambient temperature was 10 ° C., and the resultant solution was lithiated for 2 hours with an EC-DEC solution in which 0.1M LiPF 6 was dissolved. Thereafter, the mixture was further infused with an EC-DEC solution in which 1M LiPF 6 was dissolved at an atmospheric temperature of 25 ° C. and then lithiated for about 3 hours. The lithiated carbon electrode is left to stabilize at 50 ° C. for one day. The LiCoO 2 positive electrode is mixed with a composition of 5.7 g of LiCoO 2 , 0.6 g of AB, and 0.4 g of PVdF in an appropriate amount of NMP and acetone, and then cast on an aluminum sheet, dried, and rolled to obtain an electrode when an appropriate viscosity is obtained. Lithium secondary battery is composed by stacking lithiated carbon anode, PP separator and LiCoO 2 positive electrode, injecting EC-DEC solution in which 1M LiPF 6 is dissolved, and then charging / discharging rate C / 3 based on positive electrode capacity and cycle. The lifetime was investigated.

상기의 방법대로 제조한 리튬 이차전지(실시예 1, 비교예 1)의 충방전 특성을 조사한 결과 도 3과 같이 나타났는데, 본 발명의 전지는 초기의 비가역 반응이 나타나지 않고 충방전 효율이 거의 100%이었으며, 전극용량도 크게 나타났다. 이에 반하여 기존의 방법인 비교예 1은 비가역 반응이 나타나서 층방전 효율과 전극용량이 낮게 나타났다. 도 4는 상기의 방법대로 제조한 리튬 이차전지들의 전극용량(LiCoO2활물질 기준) 및 싸이클 특성을 나타낸 것으로 본 발명의 방법으로 제조한 전지들은 전극용량 및 싸이클 수명 특성이 우수하게 나타났으나, 비교예 1의 방법으로 제조한 전지는 전극용량 및 싸이클 수명 특성이 다소 나쁘게 나타났다.The charge and discharge characteristics of the lithium secondary battery (Example 1, Comparative Example 1) prepared according to the above method was as shown in Figure 3, the battery of the present invention does not show an initial irreversible reaction, the charge and discharge efficiency is almost 100 %, The electrode capacity was also large. In contrast, Comparative Example 1, a conventional method, showed an irreversible reaction, resulting in low layer discharge efficiency and electrode capacity. 4 shows the electrode capacity (based on LiCoO 2 active material) and the cycle characteristics of the lithium secondary batteries manufactured according to the above method, the batteries produced by the method of the present invention showed excellent electrode capacity and cycle life characteristics, but the comparison The battery prepared by the method of Example 1 showed a slightly poor electrode capacity and cycle life characteristics.

본 발명에 따라 카본 전극과 리튬 금속을 저항으로 연결하거나 직접 접촉시킨 상태에서 온도와 전해질의 이온전도도를 변화시켜 카본 전극이 리튬화되는 반응속도를 일정하게 조절하고, 또한 리튬화 후 일정 온도 하에서 일정 시간동안 안정화시킴으로써 리튬이 카본 전극내 골고루 분산되도록 함으로써 전지의 용량 및 싸이클 수명을 대폭 향상시킬 수 있다.According to the present invention, the reaction rate at which the carbon electrode is lithiated is constantly controlled by changing the temperature and the ionic conductivity of the electrolyte in a state in which the carbon electrode and the lithium metal are connected with resistance or in direct contact with each other. Stabilization over time allows lithium to be evenly dispersed in the carbon electrode, thereby significantly improving battery capacity and cycle life.

Claims (8)

카본 전극과 리튬 금속을 저항으로 연결하거나 직접 접촉시킨 상태에서 온도와 전해질의 이온전도도를 변화시켜서 리튬화 시키고, 상기 리튬화 후에 일정 온도에서 일정 시간동안 안정화 시킴으로써 카본 전극 표면상에 안정한 피막을 형성하여 가역성을 향상시키는 것을 특징으로 하는 카본 전극의 전리튬화 방법.Lithium is formed by varying the temperature and the ion conductivity of the electrolyte in the state in which the carbon electrode and the lithium metal are connected by resistance or in direct contact with each other, and a stable film is formed on the surface of the carbon electrode by stabilizing at a predetermined temperature after the lithiation. A method of prelithiation of a carbon electrode characterized by improving reversibility. 제 1 항에 있어서, 상기 저항으로 연결하는 전리튬화는 1단계에서는 1∼5kΩ/g(carbon)의 고저항체를 연결하여 실시하고, 2단계에서는 50∼500Ω/g(carbon) 의 저저항체를 연결하여 실시하는 것을 특징으로 하는 카본 전극의 전리튬화 방법.The method of claim 1, wherein the prelithiation connected by the resistor is performed by connecting a high resistance of 1 to 5 kΩ / g (carbon) in the first step, and a low resistance of 50 to 500 Ω / g (carbon) in the second step. A method of prelithiation of a carbon electrode, characterized in that the connection is carried out. 제 1 항에 있어서, 상기 직접 접촉시킨 전리튬화는 1 단계에서는 -10∼15℃의 저온, 그리고/혹은 ∼10-3S/cm 의 저이온전도도 전해질 하에서 실시하고, 2단계에서는 상온과 ∼10-2S/cm 의 리튬이온 전지용 전해질 하에서 실시하는 것을 특징으로 하는 카본 전극의 전리튬화 방법.The method of claim 1, wherein the direct contact lithiation is carried out under a low temperature of -10 to 15 DEG C and / or a low ion conductivity of -10 -3 S / cm in the first step, and in the second step to room temperature and- A method of prelithiation of a carbon electrode, which is carried out under an electrolyte for a lithium ion battery of 10 -2 S / cm. 제 1 항에 있어서, 상기 안정화는 30∼100℃ 사이의 일정 온도와 12∼36시간 사이의 일정시간 하에서 실시하는 것을 특징으로 하는 카본 전극의 전리튬화 방법.The method of claim 1, wherein the stabilization is performed under a constant temperature between 30 and 100 ° C and a constant time between 12 and 36 hours. 제 1 항에 있어서, 상기 리튬화를 두 단계로 실시하는데, 제 1 단계는 1∼5시간 실시하고, 제 2 단계는 2∼10시간 실시하는 것을 특징으로 하는 카본 전극의 전리튬화 방법.The method of claim 1, wherein the lithiation is carried out in two stages, wherein the first stage is carried out for 1 to 5 hours and the second stage is carried out for 2 to 10 hours. 제 1 항에 있어서, 상기 카본 전극은 흑연, 코크스, 하드카본 등의 활물질로 제조하고 이를 전리튬화 시키는 것을 특징으로 하는 카본 전극의 전리튬화 방법.The method of claim 1, wherein the carbon electrode is made of an active material such as graphite, coke, hard carbon, and the like to be prelithiated. 초기 충전시 나타나는 비가역용량에 의한 용량저하 방지와 충방전시 충방전 효율 문제로 인하여 소모되는 리튬의 양을 보충해줌으로써 싸이클 수명을 향상시키는 리튬화된 카본 전극을 이용한 것을 특징으로 하는 리튬 이차전지 제조방법.Lithium secondary battery manufacturing, characterized by using a lithiated carbon electrode to improve the cycle life by replenishing the amount of lithium consumed due to prevention of capacity reduction due to irreversible capacity appearing during the initial charging and charging and discharging efficiency problems Way. 제 7 항에 있어서, 상기 리튬화된 카본 전극과 LiCoO2, LiMn2O4, V6O13, V2O5등의 양극으로 리튬이온 전지 및 리튬 고분자 전지를 제조하는 것을 특징으로 하는 리튬 이차전지 제조방법.The lithium secondary battery of claim 7, wherein a lithium ion battery and a lithium polymer battery are manufactured by using the lithiated carbon electrode and LiCoO 2 , LiMn 2 O 4 , V 6 O 13 , V 2 O 5, and the like. Battery manufacturing method.
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