WO2002061864A1 - A lithium electrode comprising surface-treated lithium particles, its fabrication method and lithium battery comprising the same - Google Patents

A lithium electrode comprising surface-treated lithium particles, its fabrication method and lithium battery comprising the same Download PDF

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Publication number
WO2002061864A1
WO2002061864A1 PCT/KR2001/000134 KR0100134W WO02061864A1 WO 2002061864 A1 WO2002061864 A1 WO 2002061864A1 KR 0100134 W KR0100134 W KR 0100134W WO 02061864 A1 WO02061864 A1 WO 02061864A1
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lithium
electrode
metal
battery
particles
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PCT/KR2001/000134
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French (fr)
Korean (ko)
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Byung-Won Cho
Won-Il Cho
Hyung-Sun Kim
Un-Sek Kim
Sang-Cheol Nam
Young-Chang Lim
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Korea Institute Of Science And Technology
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Priority to PCT/KR2001/000134 priority Critical patent/WO2002061864A1/en
Publication of WO2002061864A1 publication Critical patent/WO2002061864A1/en

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Abstract

The present invention relates to a lithium electrode comprising surface-treated lithium or lithium alloy particles, its fabrication and lithium battery comprising the same. More specifically, the present invention relates to a lithium electrode comprising lithium particles or lithium particles coated with metal or metal oxide.

Description

A LITHIUM ELECTRODE COMPRISING SURFACE-TREATED LITHIUM PARTICLES. ITS FABRICATION METHOD AND LITHIUM BATTERY COMPRISING THE SAME
TECHNICAL FIELD
The present invention relates to a lithium electrode comprising surface- treated lithium particles, its fabrication method and a lithium battery using the same. In particular, the present invention relates to a lithium electrode using lithium particles of which surfaces are coated with a metal or metal oxide, its fabrication method, and a lithium battery using 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 comprising surface-treated lithium or lithium alloy particles, its fabrication method and a lithium battery using the same.
Another object of the present invention is to provide a lithium electrode comprising lithium or lithium alloy particles having a surface coated with a metal or metal oxide thereon, its fabrication method and a lithium battery using the same.
Still another object of the present invention is to provide a lithium electrode in which lithium or lithium alloy particles coated with a metal or
metal oxide at a thickness of from several hundreds A to a few μm using a physical vapor deposition (PVD), a chemical vapor deposition (CVD), an electroplating or eiectroless plating are pressed onto a current collector such as copper, nickel, silver or the like, and a lithium battery using the same.
Still another object of the present invention is to provide a lithium electrode in which lithium or lithium alloy particles coated with a metal or
metal oxide at a thickness of from several hundreds A to a few μm using a
physical vapor deposition (PVD), a chemical vapor deposition (CVD), an electroplating or eiectroless plating are mixed with a binder such as PVdF and then pressed onto a current collector such as copper, nickel, silver or the like, and a lithium battery using the same.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a cross-sectional view showing a lithium electrode in which a metal or metal oxide is coated on the surfaces of lithium or lithium alloy particles. Figure 2 is a graph showing test results of electrode capacity and life of lithium secondary batteries according to the present invention prepared in Examples 1 - 5 and those of a battery prepared in Comparative Example 1. Figure 3 is a graph comparing a high-rate discharge characteristic of the lithium secondary battery according to the present invention prepared in Example 1 to that of the battery prepared in Comparative Example 1.
Figure 4 is a graph showing discharge characteristics of the lithium primary battery prepared in the Example 6 and those of the battery prepared 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 a lithium electrode comprising surface- treated lithium particles, its fabrication method and a lithium battery using the same. The lithium electrode comprises lithium or lithium alloy particles of which surfaces are coated with a metal or metal oxide. Figure 1 is a cross- sectional view showing the lithium electrode of the present invention. As shown in Figure 1 , in the lithium electrode 1 of the present invention, the lithium or lithium alloy particles 11 are coated with the metal or metal oxide 12 and stacked on a current collector 13. Coating of the lithium or lithium alloy particles 11 with the metal or metal oxide 12 can be performed by various methods including a physical vapor deposition (PVD), a chemical vapor deposition (CVD), an electroplating, an eiectroless plating, etc.
It is preferred that the metal or metal oxide used for coating the lithium or lithium alloy particles is selected from the group consisting of Ni, Cu, Ti, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Al, Sn, Bi, Sb and alloys thereof.
In addition, it is preferred that 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.
According to the preferred embodiment of the present invention, an electric conductivity of the lithium electrode of the present invention is improved than that of the conventional electrode, a utilization of lithium and cycle life are also improved by maintaining a potential distribution on the surface of the electrode, and high-rate charge/discharge characteristics are also improved.
The lithium electrode of the present invention can be fabricated through the following steps: a) a step of coating a metal or metal oxide on the surfaces of lithium or lithium alloy particles; and b) a step of pressing the surface-coated lithium or lithium alloy particles onto a current collector directly, or casting the surface-coated lithium or lithium alloy particles after making paste it with an organic solvent and/or a binder onto the current collector, drying and then pressing.
Coating of lithium or lithium alloy particles using a metal or metal oxide can be performed with various methods including PVD, CVD, an electroplating and an eiectroless plating, and the coating thickness can be
adjusted in the range of several hundreds A - a few μm. A preferable coating
method is the PVD, and examples include a thermal deposition, an electron beam deposition, an ion beam deposition, a laser ablation, etc.
Example of the current collector include one made of copper, nickel or silver as used widely, but it is not limited thereto. In addition, the binder is not limited if it is widely used in the field of battery fabrication, such as PVdF. The pressing step for making the lithium electrode have high density is performed with a press at a pressure of 10 kg/cm2- 100 ton/cm2.
The present invention has an advantage that the composition of coating, homogeneity of coating, deposition thickness and deposition time can be controlled by adjusting the kinds of desired metal, or alloys or oxides thereof. In addition, according to the lithium electrode of the present invention, the conductivity of the electrode is improved to make the current and potential distribution constant, and thereby, a partial overcharge reaction can be prevented. Therefore, 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 this 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. Example
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
1-a) Preparation of a lithium electrode
Silver was uniformly coated onto the surface of lithium particles with
a diameter of a few μm at a thickness of several hundreds of A with an
electroplating. 6.0g of lithium particles on which silver was coated was mixed with 0.3g of a binder, polyvinylidene fluoride (PVdF), and then resulting mixture was added to N-methyl-2-pyrolidone (NMP). The obtained slurry was cast onto a copper thin plate, and then dried and rolled, to prepare a lithium electrode.
1-b) Preparation of a lithium secondary battery 5.7g of LiCoO2, 0.6g of acetylene black (AB) and 0.4g of PVdF were added in a mixture of NMP and acetone. When an appropriate viscosity was obtained, the resultant was cast onto an aluminum thin plate, and then dried and rolled, to obtain a cathode. A lithium secondary battery was obtained by stacking the lithium electrode obtained in Example 1-a), a PP separating film and a LiCoO2 cathode, and then injecting 1M LiPF6 solution in PC/EMC.
Example 2 Silver was uniformly coated onto the surface of lithium particles with a diameter of a few μm at a thickness of several hundreds of A with a vacuum
deposition. 6.0g of lithium particles of which the surface was coated with silver was mixed with 0.3g of a binder, PVdF, and then the resultant was added to NMP. The obtained slurry was cast onto a copper thin plate, and then dried and rolled, to prepare a lithium electrode. A lithium battery was fabricated by the same method as in Example 1-b) with the obtained lithium electrode.
Example 3 Silver was uniformly coated onto the surface of lithium particles with
a diameter of a few μm at a thickness of several hundreds of A with a CVD
method. 0.6g of lithium particles of which the surface was coated with silver was mixed with 0.3g of a binder, PVdF, and then the resulting mixture was add to NMP. The obtained slurry was cast onto a copper thin plate, and then dried and rolled, to prepare a lithium electrode. A lithium battery was fabricated by the same method as in Example 1-b) using the obtained lithium electrode.
Example 4 Silver was uniformly coated onto the surface of lithium particles with
a diameter of a few μm at a thickness of several hundreds of A with an eiectroless plating. 0.6g of lithium particles of which the surface was coated with silver was mixed with 0.3g of a binder, PVdF, and then the resulting mixture was add to NMP. The obtained slurry was cast onto a copper thin plate, and then dried and rolled, to prepare a lithium electrode. A lithium battery was fabricated by the same method as in Example 1-b) using the obtained lithium electrode.
Example 5
Nickel was uniformly coated onto the surface of lithium particles with
a diameter of a few μm at a thickness of several hundreds of A with an
eiectroless plating. 0.6g of lithium particles on which nickel was coated was mixed with 0.3g of a binder, PVdF, and then the resulting mixture was add to NMP. The obtained slurry was cast onto a copper thin plate, and then dried and rolled, to prepare a lithium electrode. A lithium battery was fabricated by the same method as in example 1-b) using the obtained lithium electrode.
Example 6
6-a) Preparation of a lithium electrode
Silver was uniformly coated onto the surface of lithium particles with
a diameter of a few μm at a thickness of several hundreds of A with an
electroplating. 0.6g of lithium particles of which the surface was coated with silver was mixed with 0.3g of a binder, PVdF, and then the resulting mixture was add to NMP. The obtained slurry was cast onto a copper thin plate, and then dried and rolled, to prepare a lithium electrode. 6-b) Preparation of a lithium primary battery 5.7g of MnO2, 0.6g of AB, 0.4g of PVdF were added to a mixture of NMP and acetone, and the resulting mixture was cast onto an aluminum thin plate, and then dried and rolled, to obtain a MnO2 electrode, when an appropriate viscosity is obtained. A lithium primary battery was obtained by stacking the lithium electrode obtained in Example 6-a), a PP separator and the above obtained MnO2 cathode, and then injecting 1 M LiPF6 solution in PC/EMC.
Comparative Example 1
A lithium thin plate having a thickness of 100μm was pressed onto an
extended copper thin plate to be a thickness of 80μm, to obtain a lithium
anode. 5.7g of MnO2, 0.6g of AB, 0.4g of PVdF were added to a mixture of NMP and acetone. When an appropriate viscosity is obtained, the resulting mixture was cast onto an aluminum thin plate, and then dried and rolled, to obtain a cathode. A lithium secondary battery was obtained by stacking the obtained lithium electrode, a PP separator and the above obtained MnO2 cathode, and then injecting 1M LiPF6 solution in PC/EMC.
Comparative Example 2 A lithium anode was fabricated by pressing a lithium thin plate to be
a thickness of 50μm onto a copper thin plate. A lithium primary battery was
fabricated by the same method as in Example 6-b) using the obtained lithium anode. Example 7
Electrode capacities and cycle life characteristics of the lithium secondary batteries obtained in Examples 1 - 5 and Comparative Example 1 were measured (charge/discharge rate C/2), and the results are shown in Figure 2. As shown in Figure 2, the lithium batteries comprising the lithium electrodes of the present invention show stable discharge capacities regardless of repeated charging and 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 is 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 (see Figure 4). The lithium primary battery comprising the lithium electrode of the present invention is remarkably superior in discharge characteristic to that of the conventional lithium primary battery obtained in Comparative Example 2.

Claims

1. A lithium electrode comprising lithium or lithium alloy particles which are coated with a metal or metal oxide.
2. The lithium electrode according to claim 1 , wherein the metal or metal oxide 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, Sb, alloys thereof and oxides 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 , wherein the coating is achieved by using a physical vapor deposition (PVD), a chemical vapor deposition (CVD), an electroplating or an eiectroless plating.
5. A preparation method of a lithium electrode comprising: a) a step of coating metal or metal oxide onto the surface of lithium or lithium alloy particles; and b) a step of directly pressing the surface-coated lithium or lithium alloy particles onto a current collector, or casting the lithium or lithium alloy particles onto the current collector after making paste it with an organic solvent and/or a binder, and then drying and pressing.
6. The method according to claim 5, wherein the coating is performed by using a physical vapor deposition (PVD), a chemical vapor deposition (CVD), an electroplating or an eiectroless plating.
7. The method according to claim 6, wherein the physical vapor deposition includes a thermal deposition, an electron beam deposition, an ion beam deposition, a sputtering and a laser ablation deposition.
8. The method according to claim 5, wherein the pressing is achieved under a pressure of 10kg/cm2 - 10Oton/cm2.
9. A lithium battery comprising a cathode, an anode and an electrolyte, wherein the anode is the lithium electrode according to claim 1.
10. The lithium battery according to claim 9, wherein the cathode is selected from the group consisting of MnO2, (CF)n and SOCI2.
11. The lithium battery according to claim 9, wherein the cathode is selected from the group consisting of LiCoO2, LiNiO2, LiNiCoO2, LiMn2O4,
V2O5 and V6O13.
PCT/KR2001/000134 2001-01-31 2001-01-31 A lithium electrode comprising surface-treated lithium particles, its fabrication method and lithium battery comprising the same WO2002061864A1 (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8110305B2 (en) 2007-02-15 2012-02-07 Samsung Sdi Co., Ltd. Rechargeable lithium battery
US8115282B2 (en) 2006-07-25 2012-02-14 Adesto Technology Corporation Memory cell device and method of manufacture
US8367248B2 (en) * 2006-11-22 2013-02-05 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, method of preparing thereof, and rechargeable lithium battery including the same
DE102011120893B3 (en) * 2011-10-29 2013-03-07 Karlsruher Institut für Technologie Electrode material for lithium-ion batteries and method for its production
US8623552B2 (en) 2007-06-07 2014-01-07 Samsung Sdi Co., Ltd. Negative active material for lithium secondary battery, and lithium secondary battery including same
US8685567B2 (en) 2007-09-12 2014-04-01 Samsung Sdi Co., Ltd. Rechargeable lithium battery
US8835049B2 (en) 2006-11-22 2014-09-16 Samsung Sdi Co., Ltd. Negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery including the same
EP3093909A4 (en) * 2014-01-06 2017-08-02 Kabushiki Kaisha Toshiba Electrode and nonaqueous electrolyte battery
CN109103428A (en) * 2018-08-02 2018-12-28 武汉艾特米克超能新材料科技有限公司 A kind of alkali metal battery cathode and preparation method thereof and battery
EP3547411A4 (en) * 2017-04-25 2020-02-19 LG Chem, Ltd. Negative electrode for lithium secondary battery, method for manufacturing same, and lithium secondary battery comprising same
CN111224068A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Metal lithium cathode for lithium battery and lithium battery

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

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US8115282B2 (en) 2006-07-25 2012-02-14 Adesto Technology Corporation Memory cell device and method of manufacture
US8835049B2 (en) 2006-11-22 2014-09-16 Samsung Sdi Co., Ltd. Negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery including the same
US8367248B2 (en) * 2006-11-22 2013-02-05 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, method of preparing thereof, and rechargeable lithium battery including the same
US8110305B2 (en) 2007-02-15 2012-02-07 Samsung Sdi Co., Ltd. Rechargeable lithium battery
US8623552B2 (en) 2007-06-07 2014-01-07 Samsung Sdi Co., Ltd. Negative active material for lithium secondary battery, and lithium secondary battery including same
US8685567B2 (en) 2007-09-12 2014-04-01 Samsung Sdi Co., Ltd. Rechargeable lithium battery
DE102011120893B3 (en) * 2011-10-29 2013-03-07 Karlsruher Institut für Technologie Electrode material for lithium-ion batteries and method for its production
EP3093909A4 (en) * 2014-01-06 2017-08-02 Kabushiki Kaisha Toshiba Electrode and nonaqueous electrolyte battery
US10003073B2 (en) 2014-01-06 2018-06-19 Kabushiki Kaisha Toshiba Electrode and nonaqueous electrolyte battery
EP3419086A1 (en) * 2014-01-06 2018-12-26 Kabushiki Kaisha Toshiba Electrode and nonaqueous electrolyte battery
EP3547411A4 (en) * 2017-04-25 2020-02-19 LG Chem, Ltd. Negative electrode for lithium secondary battery, method for manufacturing same, and lithium secondary battery comprising same
CN109103428A (en) * 2018-08-02 2018-12-28 武汉艾特米克超能新材料科技有限公司 A kind of alkali metal battery cathode and preparation method thereof and battery
CN111224068A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Metal lithium cathode for lithium battery and lithium battery

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