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WO2001097304A1 - Multi-layered lithium electrode, its preparation and lithium batteries comprising it - Google Patents

Multi-layered lithium electrode, its preparation and lithium batteries comprising it Download PDF

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Publication number
WO2001097304A1
WO2001097304A1 PCT/KR2000/000616 KR0000616W WO0197304A1 WO 2001097304 A1 WO2001097304 A1 WO 2001097304A1 KR 0000616 W KR0000616 W KR 0000616W WO 0197304 A1 WO0197304 A1 WO 0197304A1
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Prior art keywords
lithium
layer
porous
alloy layer
porous metal
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French (fr)
Inventor
Kyungsuk Yun
Byungwon Cho
Wonil Cho
Hyungsun Kim
Youngsoo Yoon
Unseok Kim
Sangcheol Nam
Youngchang Lim
Changhoon Choi
Hoyoung Park
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Korea Institute of Science and Technology KIST
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Korea Institute of Science and Technology KIST
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Priority to PCT/KR2000/000616 priority Critical patent/WO2001097304A1/en
Publication of WO2001097304A1 publication Critical patent/WO2001097304A1/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
    • H01M4/13—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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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

  • lithium or lithium alloy layer and a 1A - 10 ⁇ m thick porous metal or porous
  • lithium electrode which is fabricated by in the order
  • lithium or a lithium alloy on a Cu- or Ni-current collector forming a 1A - 10 ⁇ m thick porous metal or porous carbon layer by coating a porous metal or porous carbon on the lithium or lithium alloy layer, and coating consecutively a lithium or lithium alloy layer and a porous metal or porous carbon layer on the resulting current collector, and to lithium batteries comprising it.
  • 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 occurrs due to local dissolution of a lithium electrode, resulting in degradation in the utilization of the electrode.
  • Figure 1 is a cross-sectional view of a multi-layered lithium electrode of the present invention.
  • Figure 2 is a graph illustrating the test results of the capacity and cycle characteristics of an electrode using lithium batteries obtained in Examples 1 - 5 and Comparative Example 1.
  • Figure 3 is a graph illustrating the test results of the high-rate charge characteristic of an electrode using lithium batteries obtained in Example 3 and Comparative Example 1.
  • the present invention relates to a multi-layered lithium electrode
  • a lithium electrode which is fabricated by forming a
  • FIG. 1 illustrates a cross-sectional view of a multi-layered lithium electrode of the present invention.
  • a lithium or lithium alloy layer 101a is coated on a current collector 103, and the lithium or lithium alloy layer 101 a is in turn coated with a porous metal or porous carbon layer 102a.
  • This porous metal or porous carbon layer 102a is coated with a lithium or lithium alloy layer 101 b, and the lithium or lithium alloy layer 101 b is coated with a porous metal or porous carbon layer 102b.
  • a multi-layered lithium electrode is formed by sequential stacks of lithium or lithium alloy layers 101 c....101 n and porous metal or porous carbon layers 102c .... 102n.
  • 101 c...101 n are stacked at a thickness of 1A - 10 ⁇ m, but they are not limited
  • lithium or lithium alloy layers 101 a, 101 b,....101 n become thiner, the number thereof to be coated becomes larger. In this case, the performance of the battery can be improved.
  • mtals used for forming a lithium alloy in combination with metallic lithium include Al, Sn, Bi, Si, Sb, B and alloys thereof.
  • the porous metal or porous carbon layers 102a, 102b, 102c....102n are coated at a thickness of 1A - 10 ⁇ m, but they are not limited thereto.
  • metals used for the porous metal layers include Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Si, Sb and alloys thereof.
  • carbon group materials used for the porous carbon layers includes graphite, cokes, hard carbon, acetylene black, carbon black, and activated carbon.
  • the electrical conductivity of the electrode is improved, and accordingly current and potential distribution is made constant, resulting in the suppression of local overcharging.
  • the utilization and cycle life of the electrode are increased, and because of their porosity, the porous metal layers do not reduce the transport rate of lithium, in particular, in large-sized batteries.
  • the multi-layered lithium electrode of this invention is fabricated by thin film fabrication techniques and certain pressing techniques commonly employed in an electrode fabrication process.
  • thin film fabrication techniques refers to techniques for physical deposition under a non-aqueous atmosphere. These thin film fabrication techniques include thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition, laser ablation deposition methods, and the like. These deposition methods are advantageous in that a desired single metal or alloy can be freely coated, a pure porous metal or porous carbon can be coated without external contamination, the uniformity of coatings can be achieved, and the deposition thickness and time can be controlled by adjusting the rate of deposition freely.
  • the lithium or lithium alloy layers and porous metal or porous carbon layers which form the lithium electrode are pressed.
  • pressing refers to densification of the layers by applying pressure.
  • Means for pressing includes a roll press and plate press. The pressure applied at this time is usually 10kg/cm 2 - 100 ton/cm 2 .
  • the method of preparing a multi-layered lithium electrode according to the present invention will now be described more specifically.
  • the multi- layered lithium electrode is fabricated as follows: a) Coating lithium or a lithium alloy on a copper or nickel current
  • lithium or lithium alloys used for fabricating the above-described lithium or lithium alloy layer include a thin plate made of lithium or a lithium alloy and fine particles thereof.
  • the multi- layered lithium electrode fabricated with sequential stacks of a lithium or lithium alloy layer and a porous metal or porous carbon layer, increases the utilization and cycle life of the lithium electrode and improves the high-rate charge and discharge characteristics by increasing the conductivity of the lithium electrode and by keeping potential distribution constant on the surface of the electrode.
  • the multi-layered lithium electrode of the present invention can be widely used to fabricate a variety of lithium batteries including lithium primary batteries and lithium secondary batteries.
  • lithium primary batteries using the lithium electrode of the present invention and MnO 2 , (DF) n or SOCI 2 as a cathode
  • lithium secondary batteries using the lithium electrode of the present invention and LiCoO 2 , LiNiO 2l LiNiCoO 2 , LiMn2O 4 , V 2 O 5 , or V 6 O 13 as a cathode.
  • the lithium electrode of the present invention is advantageous in that it can be used as an anode material of a lithium ion battery using a separator such as PP (polypropylene), PE (polyethylene), etc., a lithium polymer battery using a polymer electrolyte, and a complete solid-type lithium battery using a solid electrolyte, among the lithium secondary batteries.
  • a separator such as PP (polypropylene), PE (polyethylene), etc.
  • Example 1 1 -1 Preparation of a multi-layered lithium anode used for lithium batteries.
  • lithium anode with a thickness of 80 ⁇ m.
  • LiCoO 2 cathode After mixing a composition of 5.7g of LiCoO 2 , 0.6g of AB (acetylene black), and 0.4g of PVdF(polyvinylidenefluoride) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO 2 cathode.
  • LiCoO 2 cathode After mixing a composition of 5.7g of LiCoO 2 , 0.6g of AB (acetylene black), and 4.0g of PVdF (polyvinylidenefluohde) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO 2 cathode.
  • AB acetylene black
  • PVdF polyvinylidenefluohde
  • Example 2-1 After stacking the multi-layered lithium anode obtained in Example 2-1 , a PP separator, and the LiCoO 2 cathode obtained in Example 2-2, injected 1 M UPF 6 solution in PC:EMC, and then sealed to prepare a lithium battery.
  • resulting plate at a thickness of 1000A by a vacuum deposition method.
  • a further 15 layers were coated to prepare a multi-layered lithium anode of about 80 ⁇ m thick.
  • LiCoO 2 cathode After mixing a composition of 5.7g of LiCoO 2 , 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluohde) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO 2 cathode.
  • AB acetylene black
  • PVdF polyvinylidenefluohde
  • Example 3-1 After stacking the multi-layered lithium anode obtained in Example 3-1 , a PP separator, and the LiCoO 2 cathode obtained in Example 3-2, injected 1 M LiPF 6 solution in PC:EMC, and then sealed to prepare a lithium battery.
  • Example 5 After stacking the multi-layered lithium anode obtained in Example 4-1 , a PP separator, and the LiCoO 2 cathode obtained in Example 4-2, injected 1 M LiPF 6 solution in PC:EMC, and then sealed to prepare a lithium battery.
  • Example 5 After stacking the multi-layered lithium anode obtained in Example 4-1 , a PP separator, and the LiCoO 2 cathode obtained in Example 4-2, injected 1 M LiPF 6 solution in PC:EMC, and then sealed to prepare a lithium battery.
  • lithium anode of about 80 ⁇ m thick.
  • LiCoO 2 cathode After mixing a composition of 5.7g of LiCoO 2 , 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1 -methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO 2 cathode.
  • AB acetylene black
  • PVdF polyvinylidenefluoride
  • LiCoO 2 cathode After mixing a composition of 5.7g of LiCoO 2 , 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO 2 cathode.
  • AB acetylene black
  • PVdF polyvinylidenefluoride
  • Example 6-1 After stacking the multi-layered lithium anode obtained in Example 6-1, a PP separator, and the LiCoO 2 cathode obtained in Example 6-2, injected 1 M LiPF 6 solution in PC:EMC, and then sealed to prepare a lithium battery.
  • LiCoO 2 cathode After mixing a composition of 5.7g of LiCoO 2 , 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO 2 cathode.
  • AB acetylene black
  • PVdF polyvinylidenefluoride
  • Example 7-1 After stacking the multi-layered lithium anode obtained in Example 7-1 , a PP separator, and the LiCoO 2 cathode obtained in Example 7-2, injected 1 M LiPF 6 solution in PC:EMC, and then sealed to prepare a lithium battery.
  • a high-rate discharge characteristic was tested using the lithium battery obtained in Example 3 and the lithium battery obtained in Comparative Example 1. The results thereof are illustrated in Figure 3. As illustrated therein, it is shown that the lithium battery obtained in Example 3 has a more excellent high-rate charge and discharge characteristic than the lithium battery obtained in Comparative Example 1.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention provides a multi-layered lithium electrode formed on a current collector with sequential stacks of 10 Å - 100νm thick lithium or lithium alloy layer and 1 Å - 10νm thick-porous metal or porous carbon layer, its fabrication method, and lithium batteries comprising it. More particularly, it provides to the lithium electrode which is fabricated by sequentially forming 10 Å - 100 νm thick lithium or lithium alloy layer on a Cu- or Ni-current collector, and 1 Å - 10νm thick porous metal or porous carbon layer, and lithium batteries comprising it.

Description

MULTI-LAYERED LITHUM ELECTRODE. ITS PREPARATION AND LITHIUM BATTERIES COMPRISING IT
TECHNICAL FIELD The present invention relates to a multi-layered lithium electrode
formed on a current collector with sequential stacks of a 10A - 100μm thick
lithium or lithium alloy layer and a 1A - 10μm thick porous metal or porous
carbon layer, its fabrication method, and lithium batteries comprising it. More particularly, it relates to a lithium electrode which is fabricated by in the order
of forming a 10A - 10Oμm thick lithium or lithium alloy layer by coating metallic
lithium or a lithium alloy on a Cu- or Ni-current collector, forming a 1A - 10μm thick porous metal or porous carbon layer by coating a porous metal or porous carbon on the lithium or lithium alloy layer, and coating consecutively a lithium or lithium alloy layer and a porous metal or porous carbon layer on the resulting current collector, and to lithium batteries comprising it.
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 occurrs 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 LiMn2O4 are presently commercialized, many studies of lithium anodes for increasing the energy density of cells have been made. (D. Linden, Handbook of Batteries, McGraw-HHI 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 disclosed 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 multi-layered lithium electrode with sequential stacks of a lithium or lithium alloy layer, and a porous metal or porous carbon layer.
It is another object of the present invention to provide a method of preparing the above multi-layered lithium electrode.
It is another object of the present invention to provide a lithium battery comprising the above multi-layered lithium electrode.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 is a cross-sectional view of a multi-layered lithium electrode of the present invention. Figure 2 is a graph illustrating the test results of the capacity and cycle characteristics of an electrode using lithium batteries obtained in Examples 1 - 5 and Comparative Example 1.
Figure 3 is a graph illustrating the test results of the high-rate charge characteristic of an electrode using lithium batteries obtained in Example 3 and Comparative Example 1.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a multi-layered lithium electrode
formed on a current collector with sequential stacks of a 10A - 100μm thick lithium or lithium alloy layer and a 1A - 10μm thick porous metal or porous carbon layer, its fabrication method, and lithium batteries comprising it. More particularly, it relates to a lithium electrode which is fabricated by forming a
1θA - 100μm thick lithium or lithium alloy layer on a Cu- or Ni-current collector
and then coating a 1A - 10μm thick porous metal or porous carbon layer consecutively, and lithium batteries comprising it.
Figure 1 illustrates a cross-sectional view of a multi-layered lithium electrode of the present invention. As illustrated therein, in the lithium electrode 100 of the invention, a lithium or lithium alloy layer 101a is coated on a current collector 103, and the lithium or lithium alloy layer 101 a is in turn coated with a porous metal or porous carbon layer 102a. This porous metal or porous carbon layer 102a is coated with a lithium or lithium alloy layer 101 b, and the lithium or lithium alloy layer 101 b is coated with a porous metal or porous carbon layer 102b. In this manner, a multi-layered lithium electrode is formed by sequential stacks of lithium or lithium alloy layers 101 c....101 n and porous metal or porous carbon layers 102c .... 102n.
It is preferable that the lithium or lithium alloy layers 101a, 101b,
101 c...101 n are stacked at a thickness of 1A - 10μm, but they are not limited
thereto. As the lithium or lithium alloy layers 101 a, 101 b,....101 n become thiner, the number thereof to be coated becomes larger. In this case, the performance of the battery can be improved. Examples of mtals used for forming a lithium alloy in combination with metallic lithium include Al, Sn, Bi, Si, Sb, B and alloys thereof.
It is preferable that the porous metal or porous carbon layers 102a, 102b, 102c....102n are coated at a thickness of 1A - 10μm, but they are not limited thereto. Examples of metals used for the porous metal layers include Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Si, Sb and alloys thereof. Examples of carbon group materials used for the porous carbon layers includes graphite, cokes, hard carbon, acetylene black, carbon black, and activated carbon.
In the multi-layered lithium electrode of the present invention, the electrical conductivity of the electrode is improved, and accordingly current and potential distribution is made constant, resulting in the suppression of local overcharging. Thus, the utilization and cycle life of the electrode are increased, and because of their porosity, the porous metal layers do not reduce the transport rate of lithium, in particular, in large-sized batteries.
The multi-layered lithium electrode of this invention is fabricated by thin film fabrication techniques and certain pressing techniques commonly employed in an electrode fabrication process. In this specification, the term "thin film fabrication techniques" refers to techniques for physical deposition under a non-aqueous atmosphere. These thin film fabrication techniques include thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition, laser ablation deposition methods, and the like. These deposition methods are advantageous in that a desired single metal or alloy can be freely coated, a pure porous metal or porous carbon can be coated without external contamination, the uniformity of coatings can be achieved, and the deposition thickness and time can be controlled by adjusting the rate of deposition freely. It is preferable that the lithium or lithium alloy layers and porous metal or porous carbon layers which form the lithium electrode are pressed. In this specification, "pressing" refers to densification of the layers by applying pressure. Means for pressing includes a roll press and plate press. The pressure applied at this time is usually 10kg/cm2 - 100 ton/cm2.
The method of preparing a multi-layered lithium electrode according to the present invention will now be described more specifically. The multi- layered lithium electrode is fabricated as follows: a) Coating lithium or a lithium alloy on a copper or nickel current
collector at a thickness of 10A - 10μm by a thin film fabrication technique and certain pressing technique to obtain a lithium or lithium alloy layer on the current collector; b) Pressing the lithium or lithium alloy layer by using a certain roll press to density the layer; c) Coating porous metal or porous carbon on the lithium or lithium alloy
layer at a thickness of 1 A - 10μm by a thin film fabrication technique to obtain a porous metal or porous carbon layer on the lithium or lithium alloy layer; d) Pressing the lithium or lithium alloy layer by using a certain roll press to density the layer; and e) Sequentially repeating coating of a lithium or lithium alloy layer on the porous metal or porous carbon layer, certain pressing, coating of a porous metal or porous carbon layer on the lithium layer or lithium alloy, and certain pressing, thereby fabricating a multi-layered lithium electrode.
In addition, examples of lithium or lithium alloys used for fabricating the above-described lithium or lithium alloy layer include a thin plate made of lithium or a lithium alloy and fine particles thereof.
According to the embodiments of the present invention, the multi- layered lithium electrode, fabricated with sequential stacks of a lithium or lithium alloy layer and a porous metal or porous carbon layer, increases the utilization and cycle life of the lithium electrode and improves the high-rate charge and discharge characteristics by increasing the conductivity of the lithium electrode and by keeping potential distribution constant on the surface of the electrode. The multi-layered lithium electrode of the present invention can be widely used to fabricate a variety of lithium batteries including lithium primary batteries and lithium secondary batteries. For example, there are lithium primary batteries using the lithium electrode of the present invention and MnO2, (DF)n or SOCI2as a cathode, and lithium secondary batteries using the lithium electrode of the present invention and LiCoO2, LiNiO2l LiNiCoO2, LiMn2O4, V2O5, or V6O13as a cathode. In addition, the lithium electrode of the present invention is advantageous in that it can be used as an anode material of a lithium ion battery using a separator such as PP (polypropylene), PE (polyethylene), etc., a lithium polymer battery using a polymer electrolyte, and a complete solid-type lithium battery using a solid electrolyte, among the lithium secondary batteries.
EXAMPLES
The fabrication of the multi-layered lithium electrode of the present invention, fabrication of lithium batteries comprising it, and the superiority thereof will be described in more detail by way of the following Examples, to which the invention is not limited.
Example 1 1 -1 ) Preparation of a multi-layered lithium anode used for lithium batteries.
After pressing a 50μm thick lithium thin plate to a thickness of 40μm using a roll press (pressure: 1 ton/cm2), the same was coated on an expanded copper thin plate, and metallic silver was coated on the resulting plate at a thickness of 2000A by a vacuum deposition method. By the same way as described above, a further layer was coated to prepare a multi-layered
lithium anode with a thickness of 80μm.
1 -2) Preparation of a cathode used for lithium batteries
After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 0.4g of PVdF(polyvinylidenefluoride) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode.
1-3) Preparation of a lithium battery. After stacking the multi-layered lithium anode obtained in Example 1-1 , a PP separator and the LiCoO2 cathode obtained in Example 1-2, injected a 1 M LiPF6 solution in PC:EMC, and then sealed to prepare a lithium battery.
Example 2
2-1 ) Preparation of a multi-layered lithium anode used for lithium batteries
After a 5μm thick lithium thin plate was coated on a copper thin plate
by pressing it to a thickness of 4μm, metallic silver was coated on the
resulting plate at a thickness of 1000A by a vacuum deposition method. By the same way as described above, a further 15 layers were coated to prepare
a multi-layered lithium anode of about 80μm thick.
2-2) Preparation of a cathode used for lithium batteries
After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 4.0g of PVdF (polyvinylidenefluohde) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode.
2-3) Preparation of a lithium battery.
After stacking the multi-layered lithium anode obtained in Example 2-1 , a PP separator, and the LiCoO2 cathode obtained in Example 2-2, injected 1 M UPF6 solution in PC:EMC, and then sealed to prepare a lithium battery.
Example 3
3-1 ) Preparation of a multi-layered lithium anode used for lithium batteries After coating metallic lithium on a copper thin plate at a thickness of
5μm by a vacuum deposition method, metallic silver was coated on the
resulting plate at a thickness of 1000A by a vacuum deposition method. By the same way as described above, a further 15 layers were coated to prepare a multi-layered lithium anode of about 80μm thick.
3-2) Preparation of a cathode used for lithium batteries
After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluohde) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode.
3-3) Preparation of a lithium battery
After stacking the multi-layered lithium anode obtained in Example 3-1 , a PP separator, and the LiCoO2 cathode obtained in Example 3-2, injected 1 M LiPF6 solution in PC:EMC, and then sealed to prepare a lithium battery.
Example 4
4-1 ) Preparation of a multi-layered anode used for lithium batteries
After coating a 50μm thick lithium plate on an expanded copper thin
plate by pressing it to a thickness of 40μm, metallic platinum was coated on the resulting plate at a thickness of 2000A by a sputtering method. By the same way as described above, a further layer was coated to prepare a multi-
layered lithium anode of about 80μm thick.
4-2) Preparation of a cathode used for lithium batteries After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1 -methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode. 4-3) Preparing of a lithium battery
After stacking the multi-layered lithium anode obtained in Example 4-1 , a PP separator, and the LiCoO2 cathode obtained in Example 4-2, injected 1 M LiPF6 solution in PC:EMC, and then sealed to prepare a lithium battery. Example 5
5-1 ) Preparation of a multi-layered lithium anode used for lithium batteries
After coating lithium on a copper thin plate at a thickness of 5μm by a vacuum deposition method, gold was coated on the resulting plate at a thickness of 1000A by a vacuum deposition method. By the same way as described above, a further 15 layers were coated to prepare a multi-layered
lithium anode of about 80μm thick.
5-2) Preparation of a cathode used for lithium batteries
After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1 -methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode.
5-3) Preparation of a lithium battery After stacking the multi-layered lithium anode obtained in Example 5-1 , a PP separator, and the LiCoO2 cathode obtained in Example 5-2, injected 1 M LiPF6 solution in PC:EMC, and then sealed to prepare a lithium battery.
Example 6
6-1 ) Preparation of a multi-layered anode used for lithium batteries After coating a 50μm thick lithium plate on an expanded copper thin
plate by pressing it to a thickness of 40μm, graphite was coated on the resulting plate at a thickness of 2000A by an arc deposition method. By the same way as described above, a further layer was coated to prepare a multi-
layered lithium anode of about 80μm thick.
6-2) Preparation of a cathode used for lithium batteries
After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode.
6-3) Preparation of a lithium battery
After stacking the multi-layered lithium anode obtained in Example 6-1, a PP separator, and the LiCoO2 cathode obtained in Example 6-2, injected 1 M LiPF6 solution in PC:EMC, and then sealed to prepare a lithium battery.
Example 7
7-1 ) Preparation of a multi-layered lithium anode used for lithium batteries
After coating an alloy of lithium and aluminum on a copper thin plate
at a thickness of 5μm by a vacuum deposition method, metallic silver was
coated on the resulting plate at a thickness of 1000A by a vacuum deposition method. By the same way as described above, a further 15 layers were
coated to prepare a multi-layered lithium anode of about 80μm thick. 7-2) Preparation of a cathode used for lithium batteries
After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black), and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1-methyl-2-pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode.
7-3) Preparing of a lithium battery
After stacking the multi-layered lithium anode obtained in Example 7-1 , a PP separator, and the LiCoO2 cathode obtained in Example 7-2, injected 1 M LiPF6 solution in PC:EMC, and then sealed to prepare a lithium battery.
Comparative Example 1
A 10Oμm thick lithium thin plate was pressed on an expanded copper
thin plate to a thickness of 80μm to prepare a lithium anode. After mixing a composition of 5.7g of LiCoO2, 0.6g of AB (acetylene black) and 0.4g of PVdF (polyvinylidenefluoride) with an appropriate amount of NMP (1 -methyl-2- pyrrolidon) and acetone, the mixture was cast onto an aluminum thin plate when an appropriate viscosity was obtained and then dried, and thereafter rolled to prepare a LiCoO2 cathode. After stacking the multi-layered lithium anode obtained, a PP separator, and a LiCoO2 cathode, injected 1 M LiPF6 solution in PC: EMC, and then sealed to prepare a lithium battery.
Example 8
The capacities (based on LiCoO2 cathode active material) and cycle properties of the electrodes were tested at a charging and discharging rate of C/2 using the lithium batteries obtained in Examples 1-7 and the lithium battery obtained in Comparative Example 1. The results thereof are illustrated in Figure 2. As illustrated therein, it is shown that the lithium batteries obtained in Examples 1-7 have excellent electrode capacities and cycle life characteristics, while the lithium battery obtained in Comparative Example 1 has a poor electrode capacity and cycle life. Example 9
A high-rate discharge characteristic was tested using the lithium battery obtained in Example 3 and the lithium battery obtained in Comparative Example 1. The results thereof are illustrated in Figure 3. As illustrated therein, it is shown that the lithium battery obtained in Example 3 has a more excellent high-rate charge and discharge characteristic than the lithium battery obtained in Comparative Example 1.

Claims

1. A multi-layered lithium electrode having sequential stacks of 10A -
100μm thick lithium or lithium alloy layers and 1A - 10μm thick porous metal or porous carbon layers.
2. The lithium electrode according to claim 1 , wherein said lithium alloy layer comprises an alloy of lithium and a metal selected from the group consisting of Al, Sn, Bi, Si, Sb, B and alloys thereof.
3. The lithium electrode according to claim 1 , wherein the metal forming said porous metal layer is Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Si, Sb, or alloys thereof.
4. The lithium electrode according to claim 1 , wherein the carbon forming said porous carbon layer is selected from the group consisting of graphite, cokes, hard carbon, acetylene black, carbon black, activated carbon, and mixtures thereof.
5. A method of preparing the multi-layered lithium electrode according to claim 1 , comprising the steps of a) forming a lithium or lithium alloy layer on a current collector by coating lithium or a lithium alloy on the current collector at a thickness of 10A
- 100μm by a thin film fabrication technique;
b) forming a porous metal or porous carbon layer on the lithium or lithium alloy layer by coating a porous metal or porous carbon on the lithium or lithium alloy layer formed in step a) at a thickness of 1A - 10μm by a thin
film fabrication technique; and c) consecutively repeating the formation of a lithium or lithium alloy layer on the porous metal or porous carbon layer and the formation of a porous metal or porous carbon layer on the lithium or lithium alloy layer by a thin film fabrication technique.
6. The method according to claim 5, wherein said thin film fabrication technique is a thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition, laser ablation deposition method, or a combination thereof.
7. The method according to claim 5, further comprising a step of pressing after forming the lithium or lithium alloy layer, and/or after forming the porous metal or porous carbon layer.
8. The method according to claim 7, wherein said pressing is achieved by densification of the layers under a pressure of 10kg/cm2 - 100 ton/cm2 using a roll press or plate press.
9. The method according to claim 5, wherein the lithium or lithium alloy used for forming said lithium or lithium alloy layer is a thin plate made of metallic lithium or a lithium alloy, or fine particles thereof.
10. A lithium battery comprising the lithium electrode according to claim 1.
11. A lithium primary battery comprising the lithium electrode according to claim 1 as an anode material and one element selected from the group consisting of MnO2, (CF)n and Li-SOCI2 as a cathode material.
12. A lithium secondary battery comprising the lithium electrode according to claim 1 as an anode material and one element selected from the group consisting of LiCoO2, LiNiO2, LiNiCoO2, LiMn2O4, V2O5, and V6O13 as a cathode material.
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