WO2002061862A1 - A lithium-metal composite electrode, its preparation method and lithium secondary battery - Google Patents

A lithium-metal composite electrode, its preparation method and lithium secondary battery Download PDF

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Publication number
WO2002061862A1
WO2002061862A1 PCT/KR2001/000131 KR0100131W WO02061862A1 WO 2002061862 A1 WO2002061862 A1 WO 2002061862A1 KR 0100131 W KR0100131 W KR 0100131W WO 02061862 A1 WO02061862 A1 WO 02061862A1
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lithium
electrode
metal
metal composite
composite electrode
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PCT/KR2001/000131
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French (fr)
Inventor
Byung-Won Cho
Won-Il Cho
Hyung-Sun Kim
Young-Soo Yoon
Un-Sek Kim
Sang-Cheol Nam
Sung-Won Lee
Ho-Young Park
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Korea Institute Of Science And Technology
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Priority to PCT/KR2001/000131 priority Critical patent/WO2002061862A1/en
Publication of WO2002061862A1 publication Critical patent/WO2002061862A1/en

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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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a lithium-metal composite electrode prepared with a thin film fabrication technique and pressing method, a preparation method thereof and a lithium battery comprising the same.
  • the lithium-metal composite electrode of the present invention can be prepared by depositing lithium or a lithium alloy together with a metal onto a current collector with a thin film fabrication technique and then pressing the obtained current collector, if it is necessary.
  • the lithium-metal composite electrode according to the present invention increases the conductivity of the lithium electrode and maintains the electrical potential distribution on the surface of the electrode uniformly, and accordingly, increases the utilization of lithium and cycle life of the electrode and improves high rate charge and discharge characteristics of a lithium secondary battery.
  • Lithium batteries are generally divided into lithium primary batteries and lithium secondary batteries according to whether or not they can be recharged.
  • lithium primary batteries lithium is used as a negative electrode material, and Li-MnO 2 , Li-(CF) n , Li-SOCI 2 , etc. are used as a positive electrode material according to the type of cathode. These batteries are presently commercialized. (J. O. Basenhard, Handbook of Battery Materials, Wiley-VCH, Weinheim (1999)).
  • the lithium primary batteries are disadvantageous in that non-uniform potential distribution occurs due to local dissolution of a lithium electrode, resulting in degradation in the utilization of the electrode.
  • lithium secondary batteries Although batteries using an anode made of a carbon group material and a cathode made of LiCoO 2 or LiMn 2 0 4 are presently commercialized, many studies of lithium anodes for increasing the energy density of cells have been made. (D. Linden, Handbook of Batteries, McGraw-Hill Inc., New York (1995)). Although a lithium electrode has a very high theoretical capacity of
  • Figure 1 is a cross-sectional view showing a lithium-metal composite electrode according to the present invention.
  • Figure 2 is a graph showing test results of the electrode capacity and cycle characteristics of the lithium secondary batteries obtained in Examples 1 to 5 according to the present invention and a lithium battery obtained in Comparative Example.
  • Figure 3 is a graph showing test results of high-rate discharge characteristics of the lithium battery obtained in Example 1 and Comparative
  • the present invention relates to a lithium-metal composite electrode prepared by using a thin film fabrication technique and pressing method, a preparation method thereof and a lithium battery comprising the same.
  • the lithium-metal composite electrode of the present invention which lithium or a lithium alloy is mixed with a metal can be prepared by coating lithium or a lithium alloy together with a metal onto a current collector using a thin film
  • the lithium-metal composite electrode according to the present invention can increase the conductivity of the lithium electrode and maintain the electrical potential distribution on the surface of an electrode uniformly, and accordingly increase the utilization of lithium and cycle life of the electrode and improve high rate charge and discharge characteristics of a lithium secondary battery.
  • FIG 1 is a cross-sectional view showing a lithium-metal composite electrode according to the present invention.
  • a lithium electrode 100 according to the present invention has a structure that lithium or the lithium alloy 101 and a metal 102 are uniformly mixed on the current collector 103. It is preferred that the diameter of lithium or the lithium alloy 101 and the metal used for fabricating the lithium electrode is typically no more than nano-meters.
  • the current collector may include current collector made of copper, nickel, silver and the like, but not limited thereto, and there is no particular limitation as long as the substance is conventionally used for a battery.
  • Examples of the metal may include Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Si, Sb or alloys thereof.
  • Examples of the lithium alloy may be an alloy of lithium with a metal selected from the group consisting of Al, Sn, Bi, Si, Sb, B and alloys thereof.
  • the lithium electrode according to the present invention is advantageous in that it can increase utilization and cycle life of the electrode because current and electrical potential can be maintained by improving electrical conductivity of the electrode, thereby to inhibit partial over-charge, and does not lower the delivery speed of lithium because the electrode layer has a porosity. In particular, the above effect is enlarged in large-size batteries.
  • the lithium electrode according to the present invention is prepared with a thin film fabrication technique that is conventionally applied in a preparation process of an electrode, and then optionally with a pressing technology.
  • the "thin film fabrication technique” means a technology for physically depositing under a vacuum and an anhydrous condition. Examples of such thin film fabrication technique may include a thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition, laser ablation deposition and the like.
  • the thin film fabrication technique including the above deposition methods is advantageous in that it can freely coat a desired metal or metal alloy, coat a pure porous metal or porous carbon without external contamination and obtain a uniformly coated film.
  • the thickness of film and time for deposition can be adjusted by freely adjusting the deposition speed. It is preferred that lithium or a lithium alloy and metal deposited on the collector by the thin film fabrication technique is pressed.
  • the "pressing" means to make a film have a high density by applying pressure. Examples of means for pressing may include a roll press or plate press. The applied pressure is typically in the range of 10 kg/cm 2 - 100 ton/cm 2 .
  • the lithium electrode of the present invention can be prepared through the following steps: a) forming a film of lithium or a lithium alloy and a metal simultaneously
  • step a) pressing, if it is necessary, the obtained current collector in step a) with a roll press or plate press under a pressure of 10 kg/cm 2 - 100 ton/cm 2 , thereby to obtain the lithium electrode.
  • the lithium electrode can increase electrical conductivity of the lithium electrode and maintain a constant electrical potential distribution on the surface of the electrode, and accordingly, increase utilization of the lithium electrode and cycle life and improve high-rate charge and discharge characteristics.
  • the lithium electrode of the present invention can be applied to various types of lithium batteries, including lithium primary and secondary batteries.
  • a lithium primary battery can be made using the lithium electrode of the present invention and MnO 2 , (CF) n or SOCI 2 as a cathode
  • secondary battery can also be made using the lithium electrode of the present invention and LiCoO 2 , LiNi0 2 , LiNiCoO 2 , LiMn 2 O 4 , V 2 0 5 or V 6 O 13 as a cathode.
  • the lithium electrode of the present invention can be used as an anode of lithium ion batteries using polypropylene, polyethylene or the like as a separator film, lithium polymer batteries using polymer electrolyte and complete solid type lithium batteries using solid electrolyte among the lithium secondary batteries.
  • a lithium electrode was made by coating lithium and metallic silver at
  • a lithium electrode was prepared by coating lithium and metallic gold at a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50
  • a lithium battery was prepared in the same manner as in Example 1-b) using the obtained lithium-metal composite electrode.
  • Example 3 A lithium electrode was prepared by coating lithium and metallic titanium at a ratio of 2:1 by weight onto an extended copper foil at a thickness
  • a lithium battery was prepared in the same manner as in Example 1-b) using
  • a lithium electrode was prepared by coating a lithium-aluminum alloy at a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50 ⁇ m using a vacuum sputtering deposition method, and followed by pressing
  • a lithium battery was prepared in the same manner as in Example 1-b) using the obtained lithium-metal composite electrode.
  • a lithium electrode was prepared by coating a lithium and metallic tin at a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50
  • a lithium battery was prepared in the same manner as in Example 1-b) using the obtained lithium-metal composite electrode.
  • Comparative Example 1 A lithium anode was prepared by pressing a lithium foil having a
  • cathode was obtained by adding 5.7g of LiCo0 2 , 0.6g of acetylene black (AB) and 0.4g of PVdF into a mixture of NMP and acetone, casting the resultant onto an aluminum foil when an appropriate viscosity was obtained, and drying and rolling the obtained foil.
  • a lithium secondary battery was made by stacking the lithium electrode obtained, PP separator film and LiCoO 2 cathode, and then injecting 1 M LiPF 6 solution in PC/EMC.
  • Example 6 Electrode capacities and cycle life characteristics of the lithium secondary batteries obtained in Examples 1 to 5 and Comparative Example were examined (at a charge and discharge ratio of C/2), and the results were shown in Figure 2. As shown in Figure 2, the lithium batteries comprising the lithium electrode according to the present invention showed stable discharge capacities in spite of continuous charge and discharge and improved cycle life characteristics compared to the conventional lithium battery.
  • Example 7 High-rate discharge characteristics of the lithium secondary batteries prepared in Example 1 and Comparative Example were measured, and the results were shown in Figure 3.
  • Figure 3 shows that the lithium battery comprising the lithium electrode according to the present invention exhibited remarkably better high-rate discharge characteristic than the lithium battery obtained in Comparative Example.

Abstract

The present invention relates to a lithium-metal composite electrode, its preparation method and lithium secondary battery. The lithium-metal composite electrode comprises lithium particles or lithium alloy particles mixed with metal, and it is obtained by simultaneously depositing lithium or a lithium alloy with metal on a current collector using a thin fabrication technique, and pressing the obtained.

Description

A LITHIUM-METAL COMPOSITE ELECTRODE. ITS PREPARATION METHOD AND LITHIUM SECONDARY BATTERY
TECHNICAL FIELD The present invention relates to a lithium-metal composite electrode prepared with a thin film fabrication technique and pressing method, a preparation method thereof and a lithium battery comprising the same. The lithium-metal composite electrode of the present invention can be prepared by depositing lithium or a lithium alloy together with a metal onto a current collector with a thin film fabrication technique and then pressing the obtained current collector, if it is necessary. The lithium-metal composite electrode according to the present invention increases the conductivity of the lithium electrode and maintains the electrical potential distribution on the surface of the electrode uniformly, and accordingly, increases the utilization of lithium and cycle life of the electrode and improves high rate charge and discharge characteristics of a lithium secondary battery.
BACKGROUND ART
Lithium batteries are generally divided into lithium primary batteries and lithium secondary batteries according to whether or not they can be recharged. In the case of lithium primary batteries, lithium is used as a negative electrode material, and Li-MnO2, Li-(CF)n, Li-SOCI2, etc. are used as a positive electrode material according to the type of cathode. These batteries are presently commercialized. (J. O. Basenhard, Handbook of Battery Materials, Wiley-VCH, Weinheim (1999)). However, the lithium primary batteries are disadvantageous in that non-uniform potential distribution occurs due to local dissolution of a lithium electrode, resulting in degradation in the utilization of the electrode. Meanwhile, in the case of lithium secondary batteries, although batteries using an anode made of a carbon group material and a cathode made of LiCoO2 or LiMn204 are presently commercialized, many studies of lithium anodes for increasing the energy density of cells have been made. (D. Linden, Handbook of Batteries, McGraw-Hill Inc., New York (1995)). Although a lithium electrode has a very high theoretical capacity of
3,860 mAh/g, it has a low charge and discharge efficiency, and dendrites are deposited on the surface of the lithium electrode during charging. The deposited dendrites cause an internal short-circuit, so there is a possibility of explosion. Recently, there have been attempts to solve these problems by means of studies for increasing the charge and discharge efficiency by changing the form of lithium deposition by adding an additive to an electrolyte solution, studies for mixing fine metallic particles such as Ni and Cu, and studies for changing a lithium alloy composition (Handbook 103 of the 35th Forum for Discussion on Batteries (1994), Handbook 103 of the 35th Forum for Discussion on Batteries (1994), J.O. Basenhard, Handbook of Battery Materials, Wiley-VCH, Weinheim (1999)). However, no particular solution has been proposed yet. SUMMARY OF THE INVENTION
Therefore, it is an object of the present invention to provide a novel lithium electrode by which the utilization and cycle life of the electrode are increased and the high-rate charge and discharge characteristics are improved.
It is another object of the present invention to provide a lithium electrode which lithium or a lithium alloy is mixed with a metal.
It is still another object of the present invention to provide a preparation method of the above lithium electrode. It is another object of the present invention to provide a lithium battery comprising the above lithium electrode.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing a lithium-metal composite electrode according to the present invention.
Figure 2 is a graph showing test results of the electrode capacity and cycle characteristics of the lithium secondary batteries obtained in Examples 1 to 5 according to the present invention and a lithium battery obtained in Comparative Example.
Figure 3 is a graph showing test results of high-rate discharge characteristics of the lithium battery obtained in Example 1 and Comparative
Example. DESCRIPTION OF THE INVENTION
The present invention relates to a lithium-metal composite electrode prepared by using a thin film fabrication technique and pressing method, a preparation method thereof and a lithium battery comprising the same. The lithium-metal composite electrode of the present invention which lithium or a lithium alloy is mixed with a metal can be prepared by coating lithium or a lithium alloy together with a metal onto a current collector using a thin film
fabrication technique at a thickness of from several A to several hundreds μm
and then pressing the obtained current collector, if it is necessary. It is advantageous in that the lithium-metal composite electrode according to the present invention can increase the conductivity of the lithium electrode and maintain the electrical potential distribution on the surface of an electrode uniformly, and accordingly increase the utilization of lithium and cycle life of the electrode and improve high rate charge and discharge characteristics of a lithium secondary battery.
Figure 1 is a cross-sectional view showing a lithium-metal composite electrode according to the present invention. As shown in Figure 1 , a lithium electrode 100 according to the present invention has a structure that lithium or the lithium alloy 101 and a metal 102 are uniformly mixed on the current collector 103. It is preferred that the diameter of lithium or the lithium alloy 101 and the metal used for fabricating the lithium electrode is typically no more than nano-meters. Examples of the current collector may include current collector made of copper, nickel, silver and the like, but not limited thereto, and there is no particular limitation as long as the substance is conventionally used for a battery. Examples of the metal may include Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Si, Sb or alloys thereof. Examples of the lithium alloy may be an alloy of lithium with a metal selected from the group consisting of Al, Sn, Bi, Si, Sb, B and alloys thereof. The lithium electrode according to the present invention is advantageous in that it can increase utilization and cycle life of the electrode because current and electrical potential can be maintained by improving electrical conductivity of the electrode, thereby to inhibit partial over-charge, and does not lower the delivery speed of lithium because the electrode layer has a porosity. In particular, the above effect is enlarged in large-size batteries.
The lithium electrode according to the present invention is prepared with a thin film fabrication technique that is conventionally applied in a preparation process of an electrode, and then optionally with a pressing technology. The "thin film fabrication technique" means a technology for physically depositing under a vacuum and an anhydrous condition. Examples of such thin film fabrication technique may include a thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition, laser ablation deposition and the like. The thin film fabrication technique including the above deposition methods is advantageous in that it can freely coat a desired metal or metal alloy, coat a pure porous metal or porous carbon without external contamination and obtain a uniformly coated film. Further, by using the above deposition technique, the thickness of film and time for deposition can be adjusted by freely adjusting the deposition speed. It is preferred that lithium or a lithium alloy and metal deposited on the collector by the thin film fabrication technique is pressed. Herein, the "pressing" means to make a film have a high density by applying pressure. Examples of means for pressing may include a roll press or plate press. The applied pressure is typically in the range of 10 kg/cm2 - 100 ton/cm2.
In more detail, the lithium electrode of the present invention can be prepared through the following steps: a) forming a film of lithium or a lithium alloy and a metal simultaneously
onto a current collector at a thickness of several μm to several hundreds μm
using a thin film fabrication technique including thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition, ablation deposition and the like; and b) pressing, if it is necessary, the obtained current collector in step a) with a roll press or plate press under a pressure of 10 kg/cm2 - 100 ton/cm2, thereby to obtain the lithium electrode.
According to one embodiment of the present invention, the lithium electrode can increase electrical conductivity of the lithium electrode and maintain a constant electrical potential distribution on the surface of the electrode, and accordingly, increase utilization of the lithium electrode and cycle life and improve high-rate charge and discharge characteristics.
The lithium electrode of the present invention can be applied to various types of lithium batteries, including lithium primary and secondary batteries. For instance, a lithium primary battery can be made using the lithium electrode of the present invention and MnO2, (CF)n or SOCI2 as a cathode, secondary battery can also be made using the lithium electrode of the present invention and LiCoO2, LiNi02, LiNiCoO2, LiMn2O4, V205 or V6O13 as a cathode. Also, the lithium electrode of the present invention can be used as an anode of lithium ion batteries using polypropylene, polyethylene or the like as a separator film, lithium polymer batteries using polymer electrolyte and complete solid type lithium batteries using solid electrolyte among the lithium secondary batteries.
EXAMPLES The preparation methods of the lithium electrode and lithium batteries using the same and advantages of the lithium batteries will now be described in more detail by way of the following examples, to which the present invention is not limited.
Example 1
1-a) Preparation of a lithium electrode
A lithium electrode was made by coating lithium and metallic silver at
a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50 μm
using a vacuum sputtering deposition method, and followed by pressing the obtained foil with a roll press under a pressure of 100 kg/cm2 - 300 kg/m2. 1-b) Preparation of a lithium secondary battery An cathode was obtained by adding 5.7g of LiCoO2, 0.6g of acetylene black (AB) and 0.4g of PVdF into a mixture of NMP and acetone, casting the resultant onto an aluminum foil when an appropriate viscosity was obtained, and then drying and rolling the foil. A lithium secondary battery was made by stacking the lithium electrode obtained in the above 1-a), PP separator film and the LiCoO2 cathode obtained above and then injecting a 1 M LiPF6 solution in PC/EMC.
Example 2
A lithium electrode was prepared by coating lithium and metallic gold at a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50
μm using a vacuum sputtering deposition method, and followed by pressing
the obtained foil with a plate press under an appropriate pressure. A lithium battery was prepared in the same manner as in Example 1-b) using the obtained lithium-metal composite electrode.
Example 3 A lithium electrode was prepared by coating lithium and metallic titanium at a ratio of 2:1 by weight onto an extended copper foil at a thickness
of 50 μm using a vacuum sputtering deposition method, and followed by
pressing the obtained foil with a plate press under an appropriate pressure. A lithium battery was prepared in the same manner as in Example 1-b) using
the obtained lithium-metal composite electrode.
Example 4
A lithium electrode was prepared by coating a lithium-aluminum alloy at a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50 μm using a vacuum sputtering deposition method, and followed by pressing
the obtained foil with a roll press under an appropriate pressure. A lithium battery was prepared in the same manner as in Example 1-b) using the obtained lithium-metal composite electrode.
Example 5
A lithium electrode was prepared by coating a lithium and metallic tin at a ratio of 2:1 by weight onto an extended copper foil at a thickness of 50
μm using a vacuum sputtering deposition method, and followed by pressing
the obtained foil with a roll press under an appropriate pressure. A lithium battery was prepared in the same manner as in Example 1-b) using the obtained lithium-metal composite electrode.
Comparative Example 1 A lithium anode was prepared by pressing a lithium foil having a
thickness of 100 μm onto an extended copper foil to be 80 μm thick. A
cathode was obtained by adding 5.7g of LiCo02, 0.6g of acetylene black (AB) and 0.4g of PVdF into a mixture of NMP and acetone, casting the resultant onto an aluminum foil when an appropriate viscosity was obtained, and drying and rolling the obtained foil. A lithium secondary battery was made by stacking the lithium electrode obtained, PP separator film and LiCoO2 cathode, and then injecting 1 M LiPF6 solution in PC/EMC.
Example 6 Electrode capacities and cycle life characteristics of the lithium secondary batteries obtained in Examples 1 to 5 and Comparative Example were examined (at a charge and discharge ratio of C/2), and the results were shown in Figure 2. As shown in Figure 2, the lithium batteries comprising the lithium electrode according to the present invention showed stable discharge capacities in spite of continuous charge and discharge and improved cycle life characteristics compared to the conventional lithium battery.
Example 7 High-rate discharge characteristics of the lithium secondary batteries prepared in Example 1 and Comparative Example were measured, and the results were shown in Figure 3. Figure 3 shows that the lithium battery comprising the lithium electrode according to the present invention exhibited remarkably better high-rate discharge characteristic than the lithium battery obtained in Comparative Example.

Claims

1. A lithium-metal composite electrode which particles of lithium or a lithium alloy are mixed with a metal.
2. The lithium-metal composite electrode according to claim 1 , wherein the metal is selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Si, Sb and alloys thereof.
3. The lithium-metal composite electrode according to claim 1 , wherein the lithium alloy is an alloy of lithium with a metal selected from the group consisting of Al, Sn, Bi, Si, Sb, B and alloys thereof.
4. A preparation method of the lithium-metal composite electrode according to claim 1 , comprising steps of depositing lithium or a lithium alloy and metal simultaneously onto a current collector using a thin film fabrication technique; and pressing the obtained current collector.
5. The method according to claim 4, wherein the thin film fabrication technique is selected from the group consisting of thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition and ablation deposition.
6. The method according to claim 5, the pressing is performed by applying a pressure of 10 kg/cm2 - 100 ton/cm2 with a roll press or plate press.
7. A lithium battery comprising a cathode, an anode and electrolyte, characterized in that the anode is the lithium-metal composite electrode according to claim 1.
8. The lithium battery according to claim 7, wherein the cathode is selected from the group consisting of MnO2, (CF)n and SOCI2.
9. The lithium battery according to claim 7, wherein the cathode is selected from the group consisting of LiCoO2, LiNi02, LiNiCoO2, LiMn204, V205 and V6O13.
PCT/KR2001/000131 2001-01-31 2001-01-31 A lithium-metal composite electrode, its preparation method and lithium secondary battery WO2002061862A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113991059A (en) * 2021-11-09 2022-01-28 河南电池研究院有限公司 Lithium ion battery negative pole piece and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0652888B2 (en) * 1984-03-17 1994-07-06 ソニー株式会社 Driving circuit for light emitting diode for optical communication

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0652888B2 (en) * 1984-03-17 1994-07-06 ソニー株式会社 Driving circuit for light emitting diode for optical communication

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113991059A (en) * 2021-11-09 2022-01-28 河南电池研究院有限公司 Lithium ion battery negative pole piece and preparation method thereof

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