JP3913439B2 - lithium secondary battery - Google Patents

lithium secondary battery Download PDF

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Publication number
JP3913439B2
JP3913439B2 JP2000100407A JP2000100407A JP3913439B2 JP 3913439 B2 JP3913439 B2 JP 3913439B2 JP 2000100407 A JP2000100407 A JP 2000100407A JP 2000100407 A JP2000100407 A JP 2000100407A JP 3913439 B2 JP3913439 B2 JP 3913439B2
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Japan
Prior art keywords
active material
thin film
secondary battery
lithium secondary
current collector
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Expired - Fee Related
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JP2000100407A
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Japanese (ja)
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JP2001283834A (en
Inventor
博昭 池田
正久 藤本
伸 藤谷
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三洋電機株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to lithium secondary batteries.
[0002]
[Prior art]
A lithium secondary battery using lithium metal as a negative electrode has attracted attention as a next-generation secondary battery because of its high energy density. However, since lithium metal is used for the negative electrode, lithium metal dissolves and precipitates with charge and discharge, and dendrites are generated and the electrode is deformed. For this reason, cycle performance is inferior, and what can endure practical use has not been made. As a solution to such a problem, a Li alloy negative electrode using a metal alloying with Li and a carbon negative electrode using a carbon material such as graphite have been proposed. It has been put into practical use.
[0003]
However, since the theoretical capacity of the carbon negative electrode is as low as 372 mAh / g, there is a drawback that the energy density is greatly reduced as compared with the case where metallic lithium is used for the negative electrode. Further, when a Li alloy negative electrode is used, volume expansion and contraction are repeated with charge / discharge, so that the active material particles are pulverized as the charge / discharge cycle progresses, resulting in poor cycle performance.
[0004]
On the other hand, in application equipment using a lithium secondary battery, further improvement in energy density is required, and cycle performance equal to or higher than that of a lithium secondary battery using a graphite negative electrode and higher energy density are required. There is a need for a lithium secondary battery.
[0005]
Therefore, a negative electrode in which silicon powder having a very large capacity compared with graphite is mixed with graphite powder has been proposed. The purpose of this is to combine the large capacity of silicon powder with the excellent cycle performance of graphite.
[0006]
[Problems to be solved by the invention]
However, since silicon powder is an active material that absorbs and releases lithium by alloying with lithium as described above, even when mixed with graphite powder, pulverization proceeds with charge / discharge cycles. Since the active material was peeled from the current collector, the cycle performance of the entire electrode was inferior and was not practical.
[0007]
The objective of this invention is providing the lithium secondary battery which can prevent the fall of the cycling characteristics by the expansion / contraction of the active material at the time of charging / discharging.
[0008]
[Means for Solving the Problems]
The lithium secondary battery of the present invention, Ri Do from Li not alloyed with material on the current collector having a surface roughness Ra of 0.01 to 1 [mu] m, thickness made of a metal or semiconductor which Li alloyed 0 A first active material layer having a thickness of 1 to 5.0 μm is provided, and a second active material layer having a thickness of 20.2 to 85.1 μm made of carbon is provided on the first active material layer. The active material layer is an active material thin film formed by being deposited on the current collector by a CVD method, a sputtering method, or a vapor deposition method , and the surface of the active material thin film has unevenness on the surface of the current collector. Corresponding irregularities are formed, and due to the expansion and contraction of the active material thin film due to charge / discharge reaction, a cut is formed in the thickness direction from the irregular valleys of the active material thin film toward the current collector, The active material thin film is separated into columns by the cuts, and the An electrode in which the bottom of the columnar portion is in close contact with the current collector is used .
[0009]
In the electrode of the present invention, a first active material layer may be further provided on the second active material layer. That is, an active material layer having a three-layer structure of first active material layer / second active material layer / first active material layer may be provided on the current collector. Furthermore, in the electrode of the present invention, the first active material layer and the second active material layer may be alternately and repeatedly laminated in this order on the second active material layer. That is, on the current collector, the first active material layer and the second active material layer are formed as follows: first active material layer / second active material layer / first active material layer / second active material layer. A repetitive laminated structure composed of material layers may be formed.
[0010]
The active material used for the first active material layer of the present invention is not particularly limited as long as it is formed from a metal or semiconductor alloyed with Li, but from the viewpoint of obtaining a large electrode capacity, Si, Ge, Sn, Al, and In are preferably used. Among these, Si (silicon) and Ge (germanium) are particularly preferably used because they have a particularly high capacity and can occlude Li up to the composition of Li 4.4 Si and Li 4.4 Ge. Si-Ge (silicon germanium) alloy also has a high capacity and is preferably used in the same manner.
[0011]
The first active material layer in the present invention, Ru thin film of active material der formed by depositing on the current collector. These thin films can be formed by thin film forming methods such as CVD, sputtering, and vapor deposition.
[0012]
The silicon thin film is preferably a microcrystalline silicon thin film or an amorphous silicon thin film. The microcrystalline silicon thin film is a silicon thin film in which both a peak near 520 cm −1 corresponding to a crystalline region and a peak near 480 cm −1 corresponding to an amorphous region are substantially detected in Raman spectroscopic analysis. . Further, in the amorphous silicon thin film, the peak near 520 cm −1 corresponding to the crystalline region is not substantially detected in the Raman spectroscopic analysis, and the peak at 480 cm −1 corresponding to the amorphous region is substantially detected. It is a silicon thin film.
The germanium thin film is preferably an amorphous thin film.
[0013]
As the current collector in the present invention, for example, a metal foil can be used. The metal foil is preferably a metal foil made of a metal that can be alloyed with the active material thin film from the viewpoint of improving the adhesion with the active material thin film. When the silicon thin film and the germanium thin film are formed as an active material thin film, the current collector is particularly preferably a copper foil. Moreover, as copper foil, the electrolytic copper foil which is copper foil with large surface roughness Ra is preferable.
[0014]
In the present invention, the surface roughness Ra of the current collector surface is preferably 0.01 to 1 μm, respectively. Moreover, it is preferable that the surface roughness Ra and the average interval S between the local peaks have a relationship of 100Ra ≧ S.
[0015]
The surface roughness Ra and the average interval S between the local peaks are defined in Japanese Industrial Standards (JIS B 0601-1994), and can be measured by, for example, a surface roughness meter.
[0016]
In Japanese Patent Application No. 2000-47675, which is not yet known, the present applicant forms a cut in the thickness direction in the active material thin film formed on the current collector, the thin film is separated into columns, and the bottom of the columnar portion. Has been found to be able to relieve the stress associated with the expansion and contraction of the active material during charging and discharging, and to obtain excellent cycle performance. The active material thin film in the present invention preferably has such a stress relaxation structure. Therefore, in the secondary battery of a preferred embodiment according to the present invention, the active material thin film is separated into columns by the cuts formed in the thickness direction, and the bottom of the columnar part is in close contact with the current collector. It is characterized by that.
[0017]
Since a gap is formed around the columnar part, even if the expansion and contraction of the active material is repeated by the charge / discharge reaction, such expansion and contraction can be absorbed by the gap formed around the columnar part. it can. Therefore, the charge / discharge reaction can be repeated without causing the active material thin film to be detached from the current collector and peeled off.
[0018]
Further, in the thickness direction of the active material thin film, it is preferable that at least a part of at least 1/2 of the thickness is separated into a columnar shape by the cut.
The cut is preferably formed by expansion and contraction of the active material thin film.
Moreover, the said cut | interruption may be formed by the charging / discharging reaction after assembling a battery, and may be formed by the charging / discharging reaction before assembling a battery.
[0019]
In the present invention, it is preferable that irregularities are formed on the surface of the active material thin film. Moreover, it is preferable that the said cut | interruption is formed in the thickness direction toward the electrical power collector from the uneven | corrugated trough part of this thin film surface.
[0020]
The unevenness on the surface of the thin film is preferably formed corresponding to the unevenness on the surface of the current collector. Moreover, it is preferable that the uneven | corrugated convex part of the collector surface is a cone shape.
Furthermore, it is preferable that the upper part of the columnar part of the active material thin film has a rounded shape.
[0021]
The present applicant has found in Japanese Patent Application No. 2000-47675, which is not yet known, that the cut is formed along a low-density region formed in the active material thin film. It has been found that the active material thin film is formed so as to be continuous in a network shape in the surface direction and to extend in the thickness direction toward the current collector. Similarly, in the active material thin film of the present invention, a low density region may be formed, and the cut may be formed along the low density region. Therefore, in a preferred embodiment according to the present invention, the active material thin film before the cut is formed is formed with a low density region which is continuous in a mesh shape in the plane direction and extends in the thickness direction toward the current collector. And the said cut | interruption may be formed in the thickness direction along this low density area | region.
[0022]
In addition, when the present applicant uses a copper foil as a current collector, the copper element from the copper foil is diffused and distributed in the silicon thin film, and the copper element decreases as the current comes away from the current collector. It has been found that it is diffused by the concentration distribution. Moreover, it has been found that the active material thin film adheres well to the current collector due to the diffusion distribution of the copper element. Therefore, also in the present invention, it is preferable that the copper element from the copper foil is diffusely distributed in the first active material layer, and this concentration distribution is such that the copper element decreases as the distance from the current collector increases. A distribution is preferred.
[0023]
The carbon material used for the second active material layer in the present invention is not particularly limited as long as it is a carbon material that can be used as a negative electrode in a lithium secondary battery. For example, natural graphite, artificial graphite, carbon black, Examples thereof include activated carbon, carbon fiber, coke, carbon synthesized by heat treatment of an organic precursor in an inert atmosphere, diamond-like carbon (DLC), and the like. As the graphite, graphite having an interlayer distance d of 3.37 mm or less and a crystallite size Lc in the stacking direction of 300 mm or more is preferably used.
[0024]
In the present invention, the electrode may be used as a negative electrode or a positive electrode, but is generally used as a negative electrode.
Although it does not restrict | limit especially as a positive electrode in this case, The thing conventionally used as a positive electrode of a lithium secondary battery can be used. Examples of such positive electrode active materials include lithium-containing transition metal oxides such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiCo 0.5 Ni 0.5 O 2 , LiNi 0.7 Co 0.2 Mn 0.1 O 2 , and MnO 2. Examples thereof include metal oxides not containing lithium. In addition, any substance that electrochemically inserts and desorbs lithium can be used without limitation.
[0025]
The electrolyte solvent used in the secondary battery of the present invention is not particularly limited, but cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate, and chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate. And a mixed solvent. Further, mixed solvents of the cyclic carbonate and ether solvents such as 1,2-dimethoxyethane and 1,2-diethoxyethane are also exemplified. As electrolyte solutes, LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 and the like and mixtures thereof. Further, examples of the electrolyte include gel polymer electrolytes in which a polymer electrolyte such as polyethylene oxide and polyacrylonitrile is impregnated with an electrolytic solution, and inorganic solid electrolytes such as LiI and Li 3 N. The electrolyte of the secondary battery of the present invention can be used without restriction unless the Li compound as a solvent that develops ionic conductivity and the solvent that dissolves and retains it are decomposed by the voltage at the time of charging, discharging, or storage of the battery. be able to.
[0026]
(Function and effect)
According to the present invention, the second active material layer made of carbon is provided on the first active material layer made of metal or semiconductor alloyed with Li. Therefore, the first active material layer is provided between the current collector and the second active material layer, and the first active material layer is not only the current collector but also the second active material. The layer exists in an electrically conductive state. For this reason, even if the first active material layer is separated from the current collector due to expansion and contraction during charge and discharge, current can be collected through the second active material layer.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples, and can be implemented with appropriate modifications within a range not changing the gist thereof. Is.
[0029]
(Preparation of batteries A to F of the present invention)
[Preparation of negative electrode first active material layer]
A silicon thin film as a first active material layer is formed on the electrolytic copper foil (thickness 17 μm, surface roughness Ra = 0.188 μm, average distance S between local peaks S = 11 μm) as a current collector by plasma CVD. Formed. SiH 4 gas was used as the source gas, and H 2 gas was used as the carrier gas. The thin film formation conditions were as follows: source gas flow rate: 10 sccm, carrier gas flow rate: 200 sccm, substrate temperature: 180 ° C., reaction pressure: 40 Pa, and high-frequency power 555 W. The formed silicon thin film was confirmed to be a microcrystalline silicon thin film by Raman spectroscopic analysis. Regarding the thickness of the silicon thin film, six types of 0.1 μm, 0.3 μm, 0.5 μm, 1 μm, 2 μm, and 5 μm were prepared.
[0030]
In the above embodiment, the silicon thin film is formed by the CVD method, but may be formed by other thin film forming methods such as a sputtering method and a vapor deposition method .
[0031]
[Preparation of negative electrode second active material layer]
A first active material layer was prepared using graphite (d <3.37Å, Lc> 300Å) as an active material of the second active material layer of the negative electrode and using a fluororesin (PVdF) as a binder. Graphite was added to the N-methylpyrrolidone solution in which the fluororesin was dissolved so that the concentration of the fluororesin was 5% by weight of the total of the graphite + fluororesin, and the slurry was prepared with a milling machine for 30 minutes. . This slurry was applied onto the first active material layer by a doctor blade method and dried to form a second active material layer. The coating amount was changed to a thickness as shown in Table 1 according to the thickness of the silicon thin film of the first active material layer. In Table 1, the Si film thickness indicates the thickness of the silicon thin film that is the first active material layer, and the graphite layer thickness indicates the thickness of the second active material layer.
[0032]
[Production of positive electrode]
A positive electrode was produced using LiCoO 2 as a positive electrode active material and a fluororesin (PVdF) as a binder. Specifically, 100 g of LiCoO 2 powder was mixed with an N-methylpyrrolidone solution in which the fluororesin was dissolved at 5% by weight, and the mixture was broken with a cracking machine for 30 minutes to prepare a slurry. This slurry was applied onto an aluminum foil having a thickness of 20 μm by a doctor blade method and dried to obtain a positive electrode.
[0033]
[Production of battery]
After laminating | stacking the said negative electrode and the said positive electrode through the separators made from a polypropylene, the electrode group was produced by winding up. After this electrode group was inserted into the battery can, the electrolyte solution was injected and sealed to produce the batteries A to F of the present invention shown in Table 1. As the electrolytic solution, an equal volume mixed solvent of ethylene carbonate and diethyl carbonate was used as the LiPF 6 was dissolved 1 mol / liter.
[0034]
[Table 1]
[0035]
(Production of comparative battery)
Graphite powder and silicon powder were mixed at a weight ratio of 84: 4.6 and slurried using the same fluororesin as above as a binder, and then applied onto an electrolytic copper foil to produce a negative electrode. . A comparative battery was produced in the same manner as the battery of the present invention except that this negative electrode was used.
[0036]
(Charge / discharge cycle test)
A charge / discharge cycle test was performed on the battery E of the present invention and the comparative battery. Charging is performed up to a battery voltage of 4.2 V, discharging is performed up to a battery voltage of 2.75 V, charging / discharging current is set to 100 mA, and discharging is performed in the first cycle, the second cycle, the fifth cycle, and the tenth cycle. Capacity and charge / discharge efficiency were measured. The measurement results are shown in Table 2.
[0037]
[Table 2]
[0038]
As shown in Table 2, the battery E of the present invention shows higher discharge capacity and charge / discharge efficiency than the comparative battery.
When each battery was disassembled after 10 cycles, no part of the negative electrode active material of the battery E of the present invention was peeled off from the copper foil as the current collector, and the negative electrode active material itself maintained its shape. On the other hand, in the comparative battery, it was confirmed that most of the negative electrode active material was peeled off from the current collector, and silver-white fine powder that seemed to be silicon powder was dispersed in the electrolytic solution.
[0039]
Next, also about this invention battery other than this invention battery E, the charge / discharge cycle test was done on the same conditions as the above. Table 3 shows the discharge capacity and charge / discharge efficiency of the first cycle. In Table 3, the measurement result of the battery E of the present invention is also shown.
[0040]
[Table 3]
[0041]
As shown in Table 3, all of the batteries of the present invention exhibit high discharge capacity and charge / discharge efficiency.
As described above, it can be seen that the batteries A to F of the present invention do not cause pulverization even in the charge / discharge cycle test and exhibit excellent cycle characteristics.
[0042]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the fall of the cycle characteristic by the expansion / contraction of the active material at the time of charging / discharging can be prevented.

Claims (9)

  1. Ri Do from Li not alloyed with material on the current collector having a surface roughness Ra of 0.01 to 1 [mu] m, the of 0.1~5.0μm thickness made of a metal or semiconductor which Li alloyed 1 And a second active material layer made of carbon having a thickness of 20.2 to 85.1 μm is provided on the first active material layer, and the first active material layer is formed by a CVD method, An active material thin film formed by being deposited on the current collector by a sputtering method or a vapor deposition method , and the surface of the active material thin film is formed with unevenness corresponding to the unevenness of the current collector surface, Due to the expansion and contraction of the active material thin film due to the charge / discharge reaction, a cut is formed in the thickness direction from the concave and convex valleys of the active material thin film toward the current collector, and the active material thin film is columnar by the cut. And the bottom of the columnar portion is separated from the current collector. A lithium secondary battery using an electrode that is in close contact.
  2.   The lithium secondary battery according to claim 1, wherein the first active material layer is made of silicon, germanium, or a silicon germanium alloy.
  3.   The lithium secondary battery according to claim 1, wherein the active material thin film is a silicon thin film or a germanium thin film.
  4.   The lithium secondary battery according to claim 3, wherein the silicon thin film is a microcrystalline silicon thin film or an amorphous silicon thin film.
  5.   The lithium secondary battery according to claim 1, wherein the current collector is a copper foil.
  6.   The lithium secondary battery according to claim 5, wherein the copper foil is an electrolytic copper foil.
  7.   The lithium secondary battery according to claim 5, wherein a copper element from a copper foil is diffused and distributed in the first active material layer.
  8.   The lithium secondary battery according to claim 7, wherein the copper element has a concentration distribution that decreases as the copper element moves away from the current collector.
  9.   9. The graphite according to claim 1, wherein graphite having an interlayer distance d of 3.37 mm or less and a crystallite size Lc in the stacking direction of 300 mm or more is used as carbon of the second active material layer. The lithium secondary battery as described.
JP2000100407A 2000-04-03 2000-04-03 lithium secondary battery Expired - Fee Related JP3913439B2 (en)

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