WO2002061863A1 - A lithium electrode dispersed in porous 3-dimensional current collector, its fabrication method and lithium battery comprising the same - Google Patents

A lithium electrode dispersed in porous 3-dimensional current collector, its fabrication method and lithium battery comprising the same Download PDF

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Publication number
WO2002061863A1
WO2002061863A1 PCT/KR2001/000132 KR0100132W WO02061863A1 WO 2002061863 A1 WO2002061863 A1 WO 2002061863A1 KR 0100132 W KR0100132 W KR 0100132W WO 02061863 A1 WO02061863 A1 WO 02061863A1
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lithium
current collector
porous
group
lithium electrode
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PCT/KR2001/000132
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French (fr)
Inventor
Byung-Won Cho
Won-Il Cho
Hyung-Sun Kim
Un-Sek Kim
Sang-Cheol Nam
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Korea Institute Of Science And Technology
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Priority to PCT/KR2001/000132 priority Critical patent/WO2002061863A1/en
Publication of WO2002061863A1 publication Critical patent/WO2002061863A1/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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • 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
    • H01M4/36—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

  • the present invention relates to a lithium electrode using a porous 3-dimensional current collector, its fabrication method and a lithium battery comprising the same.
  • the present invention relates to a lithium electrode in which lithium or a lithium alloy is dispersed in pores of a porous 3-dimensional current collector, its fabrication method and a lithium battery comprising the same.
  • 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 an anode material, and Li-MnO 2 , Li-(CF) n , Li-SOCI 2 , etc. are used as a cathode 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 O 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
  • an object of the present invention is to provide a lithium electrode by which the utilization and cycle life of the electrode are increased and the high-rate charge and discharge characteristics are improved.
  • Another object of the present invention is to provide a novel lithium electrode in which lithium or a lithium alloy is dispersed in pores of a porous current collector.
  • Still another object of the present invention is to provide a fabrication method of the above lithium electrode.
  • Still another object of the present invention is to provide a lithium battery comprising the above lithium electrode.
  • Figure 1 is a cross-sectional view showing a lithium electrode according to the present invention.
  • Figure 2 is a graph showing test results of electrode capacities and cycle performance of the lithium batteries obtained in Examples 1 - 5 of the present invention and obtained in Comparative Example 1.
  • Figure 3 is a graph showing test results of high-rate discharge characteristics of the lithium secondary batteries obtained in Example 1 and Comparative Example 1.
  • Figure 4 is a graph showing test results of high-rate discharge characteristics of the lithium primary batteries obtained in Example 6 of the present invention and obtained in Comparative Example 2.
  • the present invention relates to an lithium electrode using a porous
  • Lithium or a lithium alloy is uniformly filled into pores of the current collector with a method of an electroplating, a melting, a thin film fabrication technique or a particle paste packing, and then optionally pressed, to obtain the lithium electrode in which lithium or a lithium alloy is uniformly dispersed into the pores of 3-dimensional current collector.
  • the present invention can provide a lithium electrode by which a conductivity of the lithium electrode can be increased and potential distribution on the surface of the electrode can be maintained constant, and accordingly, the utilization of lithium and the cycle life can be increased and the high-rate charge/discharge characteristics can be improved.
  • FIG 1 is a cross-sectional view showing the lithium electrode 100 of the present invention.
  • the Lithium or lithium alloy 101 is uniformly distributed in the pores of the porous current collector 102.
  • Examples of a material of the porous current collector which can be used may 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, but not limited thereto on condition that it is capable of maintaining porosity.
  • Another metal besides the lithium or lithium alloy 101 can be further included in the porous current collector, and examples may 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.
  • Lithium or lithium alloy is uniformly filled into the pores of a porous current collector with an electroplating, melting or thin film fabrication technique, or lithium particles are uniformly filled into the pores of a current collector with a paste casting method.
  • thin film fabrication technique means a technique to deposit physically under an anhydrous atmosphere. Examples of such thin film fabrication technique include a thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition and laser ablation.
  • a paste of lithium or a lithium alloy with a solvent is made and then cast, or lithium or a lithium alloy, a binder such as PVdF and a solvent are mixed in order to form a paste and then cast.
  • pressing can be carried out to obtain a lithium electrode having a high density.
  • the term "pressing" means that an application of pressure to make a material have a high density.
  • Means for pressing may include a roll press and a plate press. It is preferred that the pressure applied is usually in the range of 10 kg/cm 2 - 100 ton/cm 2 .
  • another metal may be formed simultaneously. Examples of such 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.
  • the present invention has advantages that the desired metal or alloy can be freely coated or filled into the pores of the porous 3-dimensional current collector, pure lithium and/or metal composite can be coated or filled without an outer contamination, and the composition of lithium-metal,
  • coating thickness and coating time can be controlled by adjusting the coating speed.
  • the conductivity of the electrode of the present invention is improved to make the current and potential distribution constant, and thereby, a partial overcharge reaction can be prevented. Accordingly, the utilization and the cycle life of the electrode are increased, the moving rate of the lithium is not decreased because the electrode layer is porous, and such effect is enlarged in large batteries.
  • the lithium electrode of the present invention can be used for fabricating various 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
  • a lithium secondary battery can also be made using the lithium electrode of the present invention and LiCoO 2 , LiNiO 2 , LiNiCoO 2 , LiMn 2 O 4 , V 2 O 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 fabricated by coating lithium at a thickness of 20 ⁇ m with an electroplating method into the pores of a porous copper current collector which was fabricated by an electroplating method.
  • a cathode was obtained by adding 5.7g of LiCoO 2 , 0.6g of acetylene black (AB) and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and then drying and rolling the obtained plate.
  • the lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF 6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
  • Example 2 A lithium electrode was fabricated by coating lithium at a thickness of
  • a cathode was obtained by adding 5Jg of LiCoO 2 , 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate.
  • the lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF 6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
  • a lithium electrode was fabricated by making a paste after mixing
  • a cathode was obtained by adding 5.7g of LiCoO 2 , 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate.
  • the lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF 6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
  • a lithium electrode was fabricated by coating lithium at a thickness of
  • a cathode was obtained by adding 5.7g of LiCoO 2 , 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate.
  • the lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1M LiPF 6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
  • a lithium electrode was fabricated by coating lithium at a thickness of
  • a cathode was obtained by adding 5Jg of LiCoO 2 , 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate.
  • the lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1M LiPF 6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
  • Example 6 A lithium electrode was fabricated by coating lithium at a thickness of
  • a cathode was obtained by adding 5.7g of MnO 2 , 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate.
  • the lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF 6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
  • a lithium anode was fabricated by pressing a lithium thin plate of
  • a lithium anode was fabricated by pressing a lithium thin plate at a
  • Electrode capacities and cycle life characteristics of the lithium secondary batteries obtained in Examples 1 - 5 and in Comparative Example 1 were measured (at a charge/discharge rate C/2), and the results are shown in Figure 2.
  • the lithium batteries comprising the lithium electrode of the present invention exhibited stable discharge capacities regardless the repeated charging/discharging.
  • the lithium batteries of the present invention exhibited improved cycle life characteristics.

Abstract

The present invention relates to a lithium electrode, its fabrication method, and lithium battery comprising the same, wherein the lithium electrode comprises lithium or lithium alloy dispersed in a porous 3-dimensional current collector.

Description

A LITHIUM ELECTRODE DISPERSED IN POROUS 3-DIMENSIONAL CURRENT COLLECTOR. ITS FABRICATION METHOD AND LITHIUM BATTERY COMPRISING THE SAME
TECHNICAL FIELD
The present invention relates to a lithium electrode using a porous 3-dimensional current collector, its fabrication method and a lithium battery comprising the same. In particular, the present invention relates to a lithium electrode in which lithium or a lithium alloy is dispersed in pores of a porous 3-dimensional current collector, its fabrication method and a lithium battery comprising the same.
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 an anode material, and Li-MnO2, Li-(CF)n, Li-SOCI2, etc. are used as a cathode 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 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-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 suggested yet.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a lithium electrode by which the utilization and cycle life of the electrode are increased and the high-rate charge and discharge characteristics are improved.
Another object of the present invention is to provide a novel lithium electrode in which lithium or a lithium alloy is dispersed in pores of a porous current collector.
Still another object of the present invention is to provide a fabrication method of the above lithium electrode.
Still another object of the present invention is 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 electrode according to the present invention. Figure 2 is a graph showing test results of electrode capacities and cycle performance of the lithium batteries obtained in Examples 1 - 5 of the present invention and obtained in Comparative Example 1.
Figure 3 is a graph showing test results of high-rate discharge characteristics of the lithium secondary batteries obtained in Example 1 and Comparative Example 1.
Figure 4 is a graph showing test results of high-rate discharge characteristics of the lithium primary batteries obtained in Example 6 of the present invention and obtained in Comparative Example 2.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described in detail with reference to accompanying drawings.
The present invention relates to an lithium electrode using a porous
3-dimensional current collector, its fabrication method and a lithium battery using the same. Lithium or a lithium alloy is uniformly filled into pores of the current collector with a method of an electroplating, a melting, a thin film fabrication technique or a particle paste packing, and then optionally pressed, to obtain the lithium electrode in which lithium or a lithium alloy is uniformly dispersed into the pores of 3-dimensional current collector. The present invention can provide a lithium electrode by which a conductivity of the lithium electrode can be increased and potential distribution on the surface of the electrode can be maintained constant, and accordingly, the utilization of lithium and the cycle life can be increased and the high-rate charge/discharge characteristics can be improved.
The present invention will be described in more detail. Figure 1 is a cross-sectional view showing the lithium electrode 100 of the present invention. The Lithium or lithium alloy 101 is uniformly distributed in the pores of the porous current collector 102. Examples of a material of the porous current collector which can be used may 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, but not limited thereto on condition that it is capable of maintaining porosity. Another metal besides the lithium or lithium alloy 101 can be further included in the porous current collector, and examples may 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.
The fabrication method of the lithium electrode of the present invention will be described in more detail. Lithium or lithium alloy is uniformly filled into the pores of a porous current collector with an electroplating, melting or thin film fabrication technique, or lithium particles are uniformly filled into the pores of a current collector with a paste casting method. Herein, the term "thin film fabrication technique" means a technique to deposit physically under an anhydrous atmosphere. Examples of such thin film fabrication technique include a thermal deposition, electron beam deposition, ion beam deposition, sputtering, arc deposition and laser ablation. In casting method, a paste of lithium or a lithium alloy with a solvent is made and then cast, or lithium or a lithium alloy, a binder such as PVdF and a solvent are mixed in order to form a paste and then cast. Also, if it is necessary, pressing can be carried out to obtain a lithium electrode having a high density. Herein, the term "pressing" means that an application of pressure to make a material have a high density. Means for pressing may include a roll press and a plate press. It is preferred that the pressure applied is usually in the range of 10 kg/cm2 - 100 ton/cm2. When lithium or a lithium alloy is cast, another metal may be formed simultaneously. Examples of such 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.
The present invention has advantages that the desired metal or alloy can be freely coated or filled into the pores of the porous 3-dimensional current collector, pure lithium and/or metal composite can be coated or filled without an outer contamination, and the composition of lithium-metal,
homogeneity of coating, coating thickness and coating time can be controlled by adjusting the coating speed.
In addition, the conductivity of the electrode of the present invention is improved to make the current and potential distribution constant, and thereby, a partial overcharge reaction can be prevented. Accordingly, the utilization and the cycle life of the electrode are increased, the moving rate of the lithium is not decreased because the electrode layer is porous, and such effect is enlarged in large batteries.
The lithium electrode of the present invention can be used for fabricating various lithium batteries including lithium primary and secondary batteries. For example, a lithium primary battery can be made using the lithium electrode of the present invention and MnO2, (CF)n or SOCI2 as a cathode, and a lithium secondary battery can also be made using the lithium electrode of the present invention and LiCoO2, LiNiO2, LiNiCoO2, LiMn2O4, V2O5 or V6O13 as a cathode. Also, it is advantageous in that 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 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
A lithium electrode was fabricated by coating lithium at a thickness of 20μm with an electroplating method into the pores of a porous copper current collector which was fabricated by an electroplating method. A cathode was obtained by adding 5.7g of LiCoO2, 0.6g of acetylene black (AB) and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and then drying and rolling the obtained plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
Example 2 A lithium electrode was fabricated by coating lithium at a thickness of
20μm with an electroplating method into the pores of a porous 3-dimensional
nickel current collector which was fabricated by an electroplating method. A cathode was obtained by adding 5Jg of LiCoO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
Example 3
A lithium electrode was fabricated by making a paste after mixing
lithium particles of a few μm with a solution of a binder PVdF in NMP, packing
by casting the paste onto a porous 3-dimensional silver current collector fabricated by an electroplating method and then drying and rolling the resulting current collector. A cathode was obtained by adding 5.7g of LiCoO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
Example 4
A lithium electrode was fabricated by coating lithium at a thickness of
20μm with a vacuum deposition method into the pores of a porous 3-
dimensional copper current collector which was fabricated by an electroless plating method. A cathode was obtained by adding 5.7g of LiCoO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
Example 5
A lithium electrode was fabricated by coating lithium at a thickness of
20μm with a melting method into the pores of a porous 3-dimensional copper current collector which was fabricated by an electroplating method. A cathode was obtained by adding 5Jg of LiCoO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
Example 6 A lithium electrode was fabricated by coating lithium at a thickness of
20μm with an electroplating method into the pores of a porous 3-dimensional
copper current collector which was fabricated by an electroplating method. A cathode was obtained by adding 5.7g of MnO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium battery.
Comparative Example 1
A lithium anode was fabricated by pressing a lithium thin plate of
100μm to be 80μm onto an extended copper thin plate. A cathode was
obtained by adding 5.7g of LiCoO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a secondary lithium battery.
Comparative Example 2
A lithium anode was fabricated by pressing a lithium thin plate at a
thickness of 50μm onto a copper thin plate. A cathode was obtained by
adding 5.7g of LiCoO2, 0.6g of AB and 0.4g of PVdF to a mixture of NMP and acetone, casting the obtained mixture onto an aluminum thin plate when an appropriate viscosity was obtained, and drying and rolling the resulting plate. The lithium electrode, a PP separator and the cathode were stacked sequentially, and then 1 M LiPF6 solution in PC/EMC was injected thereto, thereby to fabricate a lithium primary battery.
Example 7
Electrode capacities and cycle life characteristics of the lithium secondary batteries obtained in Examples 1 - 5 and in Comparative Example 1 were measured (at a charge/discharge rate C/2), and the results are shown in Figure 2. As shown in Figure 2, the lithium batteries comprising the lithium electrode of the present invention exhibited stable discharge capacities regardless the repeated charging/discharging. In addition, the lithium batteries of the present invention exhibited improved cycle life characteristics. Example 8
High-rate discharge characteristics of the lithium secondary batteries obtained in Example 1 and Comparative Example 1 were measured, and the results are shown in Figure 3. As shown in Figure 3, the lithium battery comprising the lithium electrode of the present invention was remarkably superior in high-rate discharge characteristic to that of the lithium battery obtained in Comparative Example 1.
Example 9
High-rate discharge characteristics of the lithium primary batteries obtained in Example 6 and Comparative Example 2 were measured (Figure 4). The results shows that the lithium primary battery comprising the lithium electrode of the present invention was remarkably superior in discharge characteristic to that of the conventional lithium primary battery obtained in Comparative Example 2.

Claims

1. A lithium electrode comprising a porous 3-dimensional current collector and lithium or a lithium alloy which is dispersed into the pores of the porous 3-dimensional current collector.
2. The lithium electrode according to claim 1 , wherein a material of the porous current collector 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 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. The lithium electrode according to claim 1 , further comprising a metal in the pores of the porous 3-dimensional current collector.
5. The lithium electrode according to claim 4, 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.
6. A fabrication method of a lithium electrode according to claim 1 , comprising a step of uniformly distributing lithium or a lithium alloy and a metal in a porous 3-dimensional current collector with a method selected from the group consisting of an electroplating, melting, thin film fabrication technique and a paste casting.
7. The method according to claim 6, further comprising a step of pressing.
8. The method according to claim 7, wherein the pressing is performed by applying a pressure of 10kg/cm2 - 100ton/cm2 with a roll press or a plate press.
9. The method according to claim 6, 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 laser ablation deposition.
10. The method according to claim 6, wherein the paste casting method comprises casting a paste made with lithium or lithium alloy particles and a solvent, or obtained by mixing lithium or lithium alloy particles, a binder and a solvent.
11. A lithium battery comprising a cathode, an anode and an electrolyte, wherein the anode is the lithium electrode according to claim 1.
12. The lithium battery according to claim 11 , wherein the cathode is selected from the group consisting of MnO2, (CF)π and SOCI2.
13. The lithium battery according to claim 11 , wherein the cathode is selected from the group consisting of LiCoO2, LiNiO2, LiNiCoO2, LiMn2O4, V2O5 and V6O13.
PCT/KR2001/000132 2001-01-31 2001-01-31 A lithium electrode dispersed in porous 3-dimensional current collector, its fabrication method and lithium battery comprising the same WO2002061863A1 (en)

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