WO2004097962A1 - リチウム二次電池用負極、その負極を用いたリチウム二次電池、その負極形成に用いる成膜用材料及びその負極の製造方法 - Google Patents
リチウム二次電池用負極、その負極を用いたリチウム二次電池、その負極形成に用いる成膜用材料及びその負極の製造方法 Download PDFInfo
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- WO2004097962A1 WO2004097962A1 PCT/JP2004/005527 JP2004005527W WO2004097962A1 WO 2004097962 A1 WO2004097962 A1 WO 2004097962A1 JP 2004005527 W JP2004005527 W JP 2004005527W WO 2004097962 A1 WO2004097962 A1 WO 2004097962A1
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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
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- 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
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
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- 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
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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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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 negative electrode used for a lithium secondary battery, a lithium secondary battery using the negative electrode, a film forming material used for forming the negative electrode, and a method for producing the negative electrode.
- Lithium rechargeable batteries which charge and discharge by inserting and extracting lithium ions, have the characteristics of high capacity, high voltage, and high energy density, making them suitable for OA equipment, especially mobile information devices such as mobile phones and personal computers. It is used very often as a power source. In this lithium secondary battery, lithium ions move from the positive electrode to the negative electrode during charging, and lithium ions stored in the negative electrode move to the positive electrode during discharging.
- Carbon powder is frequently used as a negative electrode active material for forming a negative electrode of a lithium secondary battery. As will be described in detail later, this is because the comprehensive evaluation of various characteristics such as the capacity, initial efficiency, and cycle life of the carbon anode is high.
- the carbon powder is mixed with a binder solution to form a slurry.
- the slurry is applied to the surface of a current collector plate, dried, and then pressed to form a negative electrode sheet by a powder kneading application drying method.
- a transition metal oxide containing lithium mainly etc. L i C 0_Rei two is used as the cathode active material constituting the positive electrode.
- the capacity of lithium secondary batteries which are frequently used as power sources for portable information devices, is required to be further increased. From this viewpoint, the development of negative electrode active materials that have larger capacities than carbon powder is under way.
- One such negative electrode active material is S i 0, and the theoretical capacity of S i 0 reaches several times that of carbon. Nevertheless, the Sio negative electrode has not been put to practical use. The biggest reason is that the initial efficiency of the S i 0 negative pole is extremely low.
- the initial efficiency is the ratio of the initial discharge capacity to the initial charge capacity, and is one of the important battery design factors.
- the fact that this is low means that lithium ions injected into the negative electrode during the initial charge are not sufficiently released during the initial discharge, and if this initial efficiency is low, it is difficult to commercialize it even if the theoretical capacity is large. .
- various measures have been taken to increase the initial efficiency of the S i 0 negative electrode, one of which is described in Japanese Patent No. 29977471, in which lithium is contained in S i 0 in advance. It is a way to make it.
- the desired initial efficiency is 75% or more.
- the Sio negative electrode is prepared by mixing a fine powder of Si0 with a binder solution to form a slurry, applying the slurry to the surface of a current collector plate, drying, and then pressing and kneading the powder. It is produced by a method.
- the negative electrode is also produced by laminating powder on the surface of a current collector plate using the same powder kneading coating and drying method.
- the lithium-containing Si ⁇ negative electrode thus produced is effective in increasing the initial efficiency of the lithium secondary battery.
- the method in which lithium is preliminarily contained in the Si reduces the initial charge capacity due to the inclusion, and substantially impairs the high theoretical capacity, which is an excellent characteristic of Si0. Will do. For this reason, there is a need for measures to increase the initial efficiency without reducing the initial charge capacity of the Si-negative electrode.
- lithium secondary batteries are required to be further miniaturized.
- the Sio negative electrode manufactured by the powder kneading coating and drying method the Sio layer is a low-density porous body.
- miniaturization is difficult regardless of the presence or absence of lithium.
- a first object of the present invention is to significantly reduce the disadvantage of low initial efficiency, which is a disadvantage of a lithium secondary battery using Si ⁇ as a negative electrode, without impairing the initial charge capacity characteristic of a lithium secondary battery. To improve.
- a second object of the present invention is to reduce the size of a negative electrode using Sio.
- a third object of the present invention is to improve the cycle characteristics as well as the initial efficiency. Disclosure of the invention
- the present inventor has changed the idea and planned to form a dense Sio layer on the surface of the current collector by vacuum evaporation.
- the capacity per unit volume increase compared with the conventional Si layer formed by the powder kneading coating and drying method but also the low initial efficiency, which has been a problem in the Si layer, is reduced.
- the thin film formed by the ion plating method has a particularly high performance, the effect similar to the vacuum deposition film can be obtained even with the sputtering ring film, and the method is used for the vacuum deposition.
- the S i 0 powder is produced, for example, as follows. By heating the mixture of S i powder and S i ⁇ 2 powder in vacuo First, to generate S i 0 gas to obtain S i 0 deposit with which precipitated at a low temperature deposition section. The molar ratio of 0 to Si of the Si 0 precipitate obtained by this method is almost 1. This S i 0 precipitate is pulverized to obtain S i 0 powder.However, since the powder has a large surface area, it is oxidized by oxygen in the atmosphere during pulverization and use of the powder. The molar ratio of ⁇ to Si in the i 0 molded body exceeds 1.
- the S i 0 powder when the S i 0 powder is laminated by the powder kneading coating and drying method, oxidation proceeds because of the large surface area of the S i ⁇ powder.
- the molar ratio of ⁇ to Si becomes higher in the dry layer of the powder mixture of S ⁇ . If the molar ratio of 0 to the Si of the Si kneaded powder in the powder kneaded and dried layer is high, the lithium ions absorbed at the time of initial charging become difficult to be released at the time of discharging, and the initial efficiency decreases. .
- the film deposition method and the sputtering method since the film is formed in a vacuum, the increase in the oxygen molar ratio is suppressed, and as a result, the decrease in the initial efficiency is suppressed.
- thin films formed by vacuum evaporation or sputtering are dense.
- the powder kneaded and dried layer is merely a powder aggregate obtained by merely compacting the powder, and has a low S i ⁇ filling rate. Since the initial charge capacity is the charge per unit volume of the negative electrode active material layer, a dense thin film has a higher initial charge capacity, and has a higher charge capacity after the second cycle.
- the reason why the thin film formed by the ion plating method has a particularly high performance is that even when a Si ⁇ having a molar ratio of 0 to Si of 1: 1 is used, the Si0 The oxygen tends to decrease It is thought that it is affecting. In other words, it is desirable that the oxygen in Si ⁇ be as small as possible because of its strong bond with lithium ions.However, by using the ion plating method, the molar ratio of 0 to Si in the Si 0 film is maximum. It drops to about 0.5. Incidentally, the reason why the oxygen molar ratio is reduced by the ion plating method is unknown at present.
- an evaporation source that is, a film-forming material is heated and melted in a vacuum by resistance heating, induction heating, electron beam irradiation, or the like, and the vapor is adhered to the surface of the substrate.
- the film-forming material in the case, for example, mixed sintered body of S i powder and S I_ ⁇ 2 powder is used. Further, the above-mentioned Sio precipitates and Si0 sintered bodies produced from powders, granules, and lump of Sio obtained by pulverizing the precipitates are used.
- the use of the Sio film-forming material can increase the film-forming speed of the thin film.
- the evaporation characteristics of the film-forming material consisting of Si ⁇ produced by sintering depend on various conditions such as the particle size of the Si ⁇ powder used in the production and the production method. Compared with Si ⁇ , the evaporation rate of the film-forming material after sintering is lower, and it is not expected to improve the productivity of the thin film by using the film-forming material consisting of Si ⁇ .
- the present inventors have studied an Sio sintered body capable of maintaining a high evaporation rate even when sintered, and a method of manufacturing the same. As a result, the following findings were obtained.
- Si 2 is a material that is more energy stable than Si 0, and the evaporation rate of Si 2 is lower than the evaporation rate of Si 0. Therefore, even when producing a film-forming material S I ⁇ , for its part S i 0 is locally oxidized to change to the S i 0 2, inferred that the decrease in the evaporation rate occurs Is done.
- Oxidation of Si • can occur during natural oxidation when left in the air or during sintering in an oxygen atmosphere. Therefore, natural oxidation is prevented by using Sio powder having a small surface area, and sintering such Sio powder in a non-oxidizing atmosphere minimizes oxidation of Sio. Can be.
- the thus-produced silicon powder sintered body has a high evaporation rate, and the evaporation residue when thermogravimetric measurement is performed is extremely small.
- the initial efficiency in the lithium secondary battery is improved because the molar ratio of 0 to Si becomes low.
- the Sio sintered body requires sintering of the Si0 precipitate, the production cost essentially increases. For this reason, from an economic point of view, there is a demand to use relatively inexpensive S i 0 precipitates.
- the S i ⁇ precipitate has a problem of deteriorating the cycle characteristics as compared with the S i 0 sintered body.
- the cycle characteristic refers to the characteristic of decreasing the discharge amount when charging and discharging are repeated, and is an important battery factor along with the initial efficiency and the initial filling capacity.
- the initial efficiency is improved, but the cycle characteristics are degraded and the charge is discharged each time charge and discharge are repeated. Electricity tends to decrease. This tendency is more remarkable when the Sio precipitate is used than when the Sio sintered body is used as the material for film formation.
- the present inventor has found the following countermeasures against such a decrease in the cycle characteristics when the S i 0 precipitate is used.
- the present inventor has set forth a deposition film used as a packaging material for foods, pharmaceuticals, and the like, and in particular, Si 0 used as a deposition source for the deposition.
- Si 0 used as a deposition source for the deposition.
- the present inventors have found that the use of Si0 precipitates with a weight loss rate (Latra value) of 1.0% or less in the Ratra test as an evaporation source suppresses the splash phenomenon during deposition film formation. And presented it (International Publication No. 0 3/0 2 5 2 4 6 pamphlet).
- a film-forming material evaporation source
- a film-forming material evaporation source
- the vapor is adhered to the surface of the substrate.
- a material for film formation for example, a mixture of S i powder and S i O 2 powder was heated in a vacuum to generate S i O gas, which was deposited at a low temperature deposition part. Sio precipitates are used.
- the present inventor focused on the physical properties of the material for film formation and made various studies on the relationship between the physical properties and the splash phenomenon. As a result, it is used in the evaluation of compacts as a basis for evaluating that the brittleness of the film-forming material itself has a large effect on the splash phenomenon and that the material is less likely to cause the splash phenomenon. It was found that the weight loss rate (Lattola rate) in the rattle test was effective.
- the Si ⁇ precipitate has a lower density than the Sio sintered body and is liable to crack or chip.
- this S i 0 precipitate is used for forming a S i ⁇ film in a negative electrode for a lithium secondary battery, the amount of discharge tends to decrease with each repetition of charging and discharging. This tendency is hardly observed when the Sio sintered body is used.
- a Si ⁇ precipitate with a weight loss rate (Latra value) of less than 1.0% in the rattra test is used, the cycle characteristic, which is an inherent phenomenon when such a Si ⁇ precipitate is used, is obtained. The decline is effectively suppressed.
- the present inventors have also paid attention to the adhesiveness of the Si • film to the negative electrode current collector as one of the causes of the poor cycle characteristics of the Sio film type negative electrode. That is, since Si ⁇ has a relatively large expansion at the time of charging, it was thought that the peeling of the Sio film from the current collector during repeated charging / discharging might cause the cycle characteristics to deteriorate. As a cause of lowering the adhesion of the SiO film, various experimental studies were conducted, focusing on the cleaning treatment performed on the current collector before film formation. As a result, the following facts became clear.
- a cleaning process is generally performed on the base material before the film formation. Specifically, washing and drying are performed in the atmosphere.
- the present inventor believes that such a cleaning treatment may not be sufficient for the production of a Si film-type negative electrode, and purifies the negative electrode current collector as a base material in a non-atmospheric atmosphere. After that, a film was formed on the surface of the base material without being continuously exposed to the air atmosphere. As a result, it is not clear whether or not the improvement in adhesion was affected. It was confirmed that the cycle characteristics were improved.
- the present invention has been developed based on such knowledge, and has the following negative electrode for a lithium secondary battery, a lithium secondary battery, a material for film formation, and a method for manufacturing a lithium secondary battery.
- a negative electrode for a lithium secondary battery which is a membrane type negative electrode and has a cycle retention characteristic of a capacity retention ratio of 98% or more in the 10th discharge.
- (4-1) A method for producing a negative electrode for a lithium secondary battery, wherein a silicon oxide thin film is formed on the surface of a current collector by vacuum evaporation or sputtering.
- the molar ratio of 0 to Si in the silicon oxide forming the negative electrode active material layer is preferably 0.5 to 1.2, and more than 0.5 to 1 Less than is particularly preferred. That is, in the present invention, the molar ratio of 0 to Si in the silicon oxide forming the negative electrode active material layer can be lower than that in the case of the powder kneaded and coated dry layer. Specifically, it can be reduced to less than 1 and can be increased on purpose.
- This molar ratio is preferably 0.5 to 1.2, which is sufficiently lower than that of the powder kneaded and dried layer, particularly preferably 0.5 or more and less than 1.
- the silicon oxide SiOx (0.5 ⁇ x ⁇ 1.2) is preferable, and SiOx (0.5 ⁇ x ⁇ 1) is particularly preferable. That is, from the viewpoint of suppressing the phenomenon that lithium ions are combined with oxygen at the negative electrode, the molar ratio is preferably 1.2 or less, and particularly preferably less than 1. On the other hand, if it is less than 0.5, the volume expansion during occlusion of lithium ions becomes remarkable, and the negative electrode active material layer may be broken.
- the Ratra test is a method of Ratra test of metal compacts by the Japan Powder Metallurgy Association (JPMA). Standard 4 _ 69 ”.
- This test method is a test method for evaluating the abrasion resistance and the tip stability of a pressed metal compact. In the present invention, this is used for evaluating the physical properties of the Si • precipitate. Specifically, test specimens of the same size and shape as those used for the rattle test are collected from the Si ⁇ precipitate by mechanical machining, etc., and the test pieces are subjected to the test in the same manner as the rattra test, before and after the test. Calculate the weight loss rate (Ratra value) of In the original test, the compressibility and moldability of the metal powder were evaluated. i) The denseness and uniformity of the precipitate are evaluated.
- a laminated structure is composed of an anode current collector, an anode active material layer, an electrolyte, a separator, an anode active material layer, and an anode current collector.
- the negative electrode active material layer has locally non-uniform portions or irregularities, it is conceivable that the destruction of the laminated structure proceeds from that portion, leading to a decrease in cycle characteristics. Therefore, it is considered that homogenizing the negative electrode active material layer is effective for improving the cycle characteristics.
- the Sio precipitate which is a material for film formation, is dense and uniform. This is considered to be the reason why the S i 0 precipitate with a small Ratra value is effective for improving the cycle characteristics.
- examples of the cleaning treatment in a vacuum or an inert atmosphere include a surface treatment bombard by a DC magnetron discharge in a vacuum chamber. it can .
- the film forming method examples include a vacuum evaporation method and a sputtering method, and among them, the ion plating method is particularly preferable. If the cleaning process is performed in a vacuum, it is reasonable to perform both processes in the same atmosphere, such as performing the film formation in a vacuum, but the cleaning process should be performed in an inert atmosphere. It is also possible to carry out both processes in different atmospheres, such as performing film formation in a vacuum. In short, from the current collector cleaning process The film formation process is performed in a vacuum or in an inert atmosphere, and during this time, the surface of the current collector need not be exposed to the atmosphere.
- a Si 0 precipitate or a Si ⁇ sintered body can be used as a material for film formation.
- the use of a dense and hard Si 0 sintered body provides better cycle characteristics.
- the production cost is lower for the S i 0 precipitate.
- One of the important values of the production method (4-2) is that good cycle characteristics can be ensured even when inexpensive S i 0 precipitates are used.
- the thickness of the silicon oxide thin film is preferably from 0.1 to 50 m. If it is less than 0.1 m, the capacity per unit volume increases, but the capacity per unit area decreases. On the other hand, since this thin film is an insulating film, if the thickness exceeds 50 111, the current collection efficiency from the thin film to the current collector may be reduced.
- a particularly preferred film thickness ranges from 0.1 to 20111.
- the ion plating method is preferable. The reason is as described above.
- a thin metal plate is preferable as the current collector.
- the metal Cu, A 1 or the like can be used.
- the plate thickness is preferably from 1 to 50 m. If it is too thin, it will be difficult to manufacture, and the decrease in mechanical strength will also be a problem. On the other hand, if the thickness is too large, miniaturization of the negative electrode is hindered.
- the positive electrode has a structure in which a positive electrode active material layer is formed on the surface of a current collector.
- the positive electrode active material L i C 0_Rei 2, L i N i 0 2 , L i M n 2 0 4 transition metal oxide containing Lithium such is mainly used.
- a method for preparing a positive electrode a powder kneading coating and drying method is known in which a fine powder of an oxide is mixed with a binder solution to form a slurry, the slurry is applied to the surface of a current collector plate, dried, and then pressurized. However, it can also be formed by the same film formation as the negative electrode.
- the electrolytic solution for example, a non-aqueous electrolyte containing ethylene carbonate or the like can be used.
- the film forming material of (3) is particularly effective for vacuum deposition, but is also effective for sputtering.
- the bulk density of the sintered body of silicon monoxide is not particularly limited, but is preferably 80% or more from the viewpoint of effectively suppressing splash and preventing cracking during handling. 5% or more is more preferable.
- FIG. 1 is a longitudinal sectional view of a lithium secondary battery showing an embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing a configuration of a thermogravimeter used for thermogravimetry.
- FIG. 3 is a graph showing a change in mass of a measurement sample when thermogravimetry is performed.
- the lithium secondary battery of the present embodiment is a so-called button battery, and includes a circular flat case 10 forming a positive electrode surface.
- the case 10 is made of a metal, and accommodates therein a disk-shaped positive electrode 20 and a negative electrode 30 which are stacked in order from the bottom.
- the positive electrode 20 is composed of a current collector 21 made of a circular thin metal plate and a positive electrode active material layer 2 formed on the surface thereof.
- the negative electrode 30 includes a current collector 31 made of a circular thin metal plate and a negative electrode active material layer 32 formed on the surface thereof. The two electrodes are stacked with the respective active material layers facing each other, with the separator 40 sandwiched between the facing surfaces, and housed in the case 10.
- the case 10 also contains an electrolytic solution together with the positive electrode 20 and the negative electrode 30. Then, the opening of the case 10 is covered via the sealing member 50. The contents are sealed in the case 10 by sealing with 60.
- the cover 60 also serves as a member forming the negative electrode surface, and is in contact with the current collector 31 of the negative electrode 30.
- the negative electrode active material layer 32 in the negative electrode 30 is formed by vacuum evaporation or sputtering on the current collector 31 using Si as a raw material, preferably It consists of a dense thin film of silicon oxide formed by ion plating, which is a kind of vacuum deposition.
- Si silicon oxide
- the silicon oxide can be controlled to Si On (0.5 ⁇ n ⁇ 1.2) by controlling the oxygen concentration in the atmosphere.
- the appropriate thickness of the thin film is 0.1 to 50 im.
- the positive electrode active material layer 2 of the positive electrode 0 is formed into a slurry by mixing powder of a transition metal oxide containing lithium such as LiC 0 ⁇ 2 with a binder solution as in the past, and the slurry is formed. It is formed by a powder kneading coating and drying method in which the powder is applied to the surface of the current collector plate 21, dried, and then pressurized.
- the negative electrode active material layer 32 is made of silicon oxide, the theoretical capacity is much larger than that of the carbon powder layer.
- the silicon oxide is a thin film formed by vacuum evaporation or sputtering, and has a low molar ratio of ⁇ to Si and is dense, so that the initial efficiency is reduced without reducing the initial charge capacity. Can be higher.
- the material for forming a film for forming the negative electrode active material layer 32 in the secondary battery negative electrode 30 is as follows.
- a material suitable for the film formation is a precipitate of Si i or a sintered body produced from the precipitate.
- the heating temperature is 130 ° C and the pressure is 10 ° C.
- the thermogravimetric measurement of the sintered body sample was performed in a vacuum atmosphere of Pa or less, the evaporation residue was 4% or less of the mass of the sample before measurement.
- thermogravimeter of Fig. 2 is used for thermogravimetry of the sintered body. Specifically, the measurement sample 3 is charged into a crucible 2 suspended on one side of the balance 1. On the other hand, a weight 4 having a mass that balances with the measurement sample 3 is arranged on the other side of the balance 1.
- the thermogravimeter is provided with a heating furnace 5, a gas inlet 6, a gas outlet 7, and the like, and these are used to adjust the temperature and atmosphere of the measurement sample 3.
- the temperature of the measurement sample 3 is set to 1300 ° C, and the thermogravimetric measurement is performed in a vacuum atmosphere of 10 Pa or less. At this time, in the thermogravimetric measurement, a slight change in the temperature of the measurement sample 3 is inevitable, but a slight change in the temperature within the range of 130 ⁇ 50 ° C is permissible. When thermogravimetry is performed under these conditions, the mass of the sintered body decreases as silicon monoxide evaporates.
- FIG. 3 shows the change in the mass of the sample at this time, with the mass of the measurement sample before measurement being 100%, and the change in the amount of evaporation residue with the lapse of measurement time. In the measurement shown in the figure, the temperature of the measurement sample was increased from room temperature to 130 ° C.
- a preferred film-forming material is a sintered body of S i 0 in which the mass of the evaporation residue of the sintered body at this time, that is, the mass of the constant weight residue is 4% or less of the mass before measurement.
- the evaporation rate of Si 0 is high, and the productivity of the silicon oxide thin film by evaporation by evaporation can be improved.
- the thin film has a low molar ratio of 0 to Si, so that the initial efficiency can be increased without reducing the initial charge capacity.
- Such a sintered body of S i 0 can be manufactured by sintering a S i 0 powder having a particle diameter of 250 Um or more in a non-oxidizing atmosphere after press molding or while pressing. .
- the use of S i ⁇ powder having an average particle size of 250 or more is because the S i ⁇ powder having a particle size of less than 250 m has a surface area of S i ⁇ powder. This is because silicon dioxide is formed on the particle surface due to large natural oxidation, and this silicon dioxide is reflected on the sintered body, resulting in a decrease in the evaporation rate and a decrease in the initial efficiency.
- the upper limit of the particle size is preferably 20000 wm or less. If it exceeds 200 m, press formability and sinterability will be reduced.
- the average particle diameter of the Sio powder need not be the same as long as the average is 250 m or more.
- the density of the sintered body can be increased. If the density of the sintered body is about 95% or less, the particle size of the Si ⁇ powder in the sintered body can be investigated by observing the cross section with an optical microscope, and the average particle size as a raw material of the sintered body is 250 111 It can be confirmed whether or not the above 3i ⁇ powder was used.
- Such Sio powder is sintered in a non-oxidizing atmosphere after press-forming into an arbitrary shape or during press-forming.
- the press molding method is particularly suitable if the desired shape can be formed by pressing. It doesn't matter. If the bonding property between the S i ⁇ particles is poor, a small amount of water may be added to the S i0 powder, and after press molding, water may be removed by a dehydration treatment. By applying a load of about 300 to 1500 kg per 1 cm 2, the Sio powder can be formed into an arbitrary shape.
- Sintering is desirably performed in a non-oxidizing atmosphere.
- the non-oxidizing atmosphere is an atmosphere containing no oxygen, for example, a vacuum atmosphere or an inert atmosphere such as an argon gas.
- a vacuum atmosphere the evaporation rate of the sintered Si Si powder is not different from the evaporation rate of the Si powder before sintering. It is preferred to do so.
- an oxygen-containing atmosphere the Si powder is combined and the evaporation rate is reduced.
- the sintering temperature is not particularly limited as long as the Si • particles are bonded to each other and their shapes can be maintained. Sintering at 1200-135 ° C for 1 hour or more is sufficient.
- the configuration of the negative electrode was changed in various ways as follows.
- Examples include a current collector made of a copper foil having a thickness of 10 A ⁇ m, a negative electrode active material layer, an ion plating method, a normal vapor deposition method (resistance heating), a sputtering method, and powder kneading.
- a silicon oxide thin film was formed by a coating and drying method.
- a S0 powder sinter (tablet) is used as a material for film formation (evaporation source), and an EB gun is used as a heating source to achieve a predetermined vacuum.
- the above-mentioned S i 0 precipitate that is, a mixture of S i powder and S i 0 2 powder is heated in a vacuum, A crushed lump of S i 0 precipitate, a mixed sintered body of S i 0 powder and S i 0 2 powder, and a silicon lump obtained by generating i 0 gas and depositing it at a low temperature precipitation part were used. .
- the Sio powder sintered body three kinds of powder having an average particle diameter of 250 um, 100 Owm, and 10 m were used.
- the one with a thickness of 250 ⁇ m is sintered (at 1200 ° C X 1.5 hours in a vacuum) while pressing with a load of 100 kg / cm 2 , and l OOO zm in those performed sintered (1 2 0 0 ° CX 1. 5 hours in a vacuum) while applying press-in load 1 0 0 kg / cm z, 1 0 load 2 0 things 0 kg / cm 2 Sintering was performed under pressure (120 ° C in vacuum for 1.5 hours).
- thermogravimetric measurement of the sintered sample was performed in a vacuum atmosphere with a heating temperature of 1300 ° (pressure of 10 Pa or less, the evaporation residue rates were 4%, 3%, and 8%, respectively.
- the thermogravimeter was measured using the measuring device shown in Fig. 2.
- the heating temperature of 1300 ° C was measured at a distance of about 1 mm from the measurement sample with a thermocouple 8 and was substantially It is probable that the measurement sample is heated to this temperature before the measurement.
- the data obtained by thermogravimetry are organized, and the mass when the mass change of the measurement sample is substantially eliminated is regarded as the mass of the evaporation residue before the measurement.
- We calculated the ratio (evaporation residue ratio) to the mass of the water see Fig. 3).
- the two types of samples shown in FIG. 3 are two of the above three types of Sio powder sinters. Specifically, the two types of Si0 powder having an average particle size of 250 0 Sintered powder (solid line: Example 3) and powder having an average particle size of 1 um This is a S i 0 powder sintered body (dotted line: Example 10). The former has an evaporation residue ratio of 4%, while the latter has an evaporation residue ratio of 8%.
- the fabricated various negative electrodes were combined with the positive electrode, and sealed in a case together with the electrolyte to complete the lithium secondary battery.
- the initial charge capacity, initial discharge capacity, and initial efficiency of the completed batteries were measured.
- the positive electrode is LiC0
- a fine powder of No. 2 was used, and a non-aqueous electrolyte containing ethylene carbonate was used as the electrolyte.
- Table 1 shows the initial charge capacity and the initial efficiency calculated from the initial charge capacity and the initial discharge capacity.
- the initial charging capacity was evaluated based on the amount of current per unit volume, and is expressed as a ratio when the data in Example 3 was set to 1.
- Example 6 when the thickness of the thin film was 1 m, oxygen was added to the film forming atmosphere to intentionally increase the molar ratio of Si to 0 in the silicon oxide.
- Example 7 a thin film of silicon oxide having a thickness of 1 m was formed on the surface of the current collector by ordinary vacuum deposition (resistance heating) and sputtering.
- the molar ratio of 0 to S i in the layer was increased to 1.4.
- the initial efficiency is as low as 46% because the initial discharge capacity is smaller than the initial charge capacity (conventional example 1).
- the initial efficiency is increased to 84% by incorporating lithium into S i 0 in advance, but this is because the initial charge capacity is reduced and the excellent theoretical capacity of S i 0 is hindered. (Conventional example 2).
- a negative electrode active material Si ⁇ was formed by an ion plating method.
- the molar ratio of 0 to Si in the thin film is 0.5 Dropped. The initial efficiency was improved while the initial charge capacity was large.
- Example 5 having a large film thickness, the initial charge capacity and the initial efficiency were slightly reduced.
- Example 6 in which the molar ratio of Si to Si in the thin film was increased to 0.99, the initial efficiency was somewhat low, but still at a high level, and the initial charging capacity was large.
- Example 7 and 8 in which a thin film was formed by ordinary vacuum deposition and sputtering, the molar ratio of ⁇ to Si in the thin film exceeded 1. Although the initial efficiency is slightly lower than that of ion plating, it is still at a high level, and the initial charging capacity is also at a high level. The deposition rate is lower in normal vacuum deposition than in the ion plating method, and further lower in spattering. On the other hand, in Examples 9 to 13, the ion-plating method was used as the film-forming method, and the material for film-forming was variously changed. The film thickness was 1 ⁇ .
- Example 9 the material for film formation was a Si i powder sintered body (vacuum sintered product) having an average powder particle diameter of 1000 / m.
- Example 10 a Si powder sintered body (vacuum sintered product) having an average powder particle diameter of 10 m was used.
- the evaporation residue rates are 3% and 8%, respectively.
- the average particle diameter of the powder in the Sio powder sintered body is preferably 250 Um or more.
- Example 11 a crushed lump of Si 0 precipitate (average particle size of about 5 cm) was used. Compared with Example 3 having the same film thickness of 1 win, even the precipitate can obtain the same initial efficiency and initial charge capacity as the powder sintered body.
- the sintered body since the splash during the film formation is smaller than that of the precipitate, the film formation rate (evaporation rate) can be further increased. For this reason, a sintered body is more preferable in terms of productivity.
- the sintered body provides a continuous supply of raw materials to the film forming apparatus. There is also an easy advantage. The reason why the splash during the film formation of the Sio sintered compact is small may be that the Sio, which is a material for film formation, is bonded more firmly than the Sio precipitate.
- Example 12 a mixed sintered body of Si powder and Sio 2 powder was used. Although this film-forming material can provide an effect on battery performance, the film-forming rate is considerably slow.
- Si ⁇ precipitates and Si ⁇ sintered bodies film formation is possible only by raising the heating temperature by one sublimation temperature of S i ⁇ , but mixed sintering of S i powder and S i ⁇ 2 powder in the body, it is necessary to generate a S i 0 by reacting with each other first with S i and S i 0 2 of the contact portion of the sintered body. For this reason, the mixed sintered body has a lower Sio generation rate than the Sio precipitate and the Sio sintered body. If a large amount of heat is applied, the generation rate increases, but this increases the splash at the time of film formation, and consequently there is a restriction that the film formation rate must be reduced.
- Example 13 a film is formed in an oxidizing atmosphere using a silicon lump cut out of a silicon ingot manufactured by a casting method as a material.
- the same battery performance as that of the mixed sintered body of Example 12 can be obtained.
- the oxidizing atmosphere was formed by introducing oxygen gas. In this case, since the Si atoms need to be diffused from the material surface, splash is more likely to occur than in the mixed sintered body. For this reason, the deposition rate is even lower.
- the negative electrode active material layer 32 in the negative electrode 30 is formed by vacuum deposition or sputtering, preferably vacuum deposition, using the S i 0 precipitate as a film forming material.
- This is a point composed of a dense Sio thin film formed on the current collector 31 by ion plating, which is one type of the above.
- the negative electrode active material layer 32 in the negative electrode 30 is This is a thin film using a precipitate with a weight loss rate (Ratra value) of 1.0% or less in the Ratra test.
- the appropriate thickness of the thin film is 0.1 to 50 wm.
- the positive electrode active material layer 2 2 in the positive electrode 2 conventionally, a powder of an oxide of a transition metal containing lithium, such as L i C 0 ⁇ 2, mixed with a binder solution was slurried its The slurry is formed by a powder kneading coating and drying method in which the slurry is applied to the surface of the current collector plate 21, dried, and then pressurized.
- Other configurations are the same as those in the first embodiment.
- the features of the lithium secondary battery of the present embodiment are as follows.
- the negative electrode active material layer 32 is made of Sio, the theoretical capacity is much larger than that of the carbon powder layer.
- the Si ⁇ is a thin film formed by vacuum evaporation or sputtering, the initial efficiency can be increased without reducing the initial charge capacity.
- the capacity per unit volume of the thin film is large, miniaturization is easy.
- the cycle characteristics are excellent because a Si0 precipitate having a weight loss rate (Latra value) of 1.0% or less in a Ratra test is used as a material for film formation. Specifically, the cycle characteristics are better than the Sio layer formed by the powder kneading coating and drying method, and it is equivalent to a thin film formed using a Si ⁇ sintered body.
- a Si ⁇ precipitate was produced as a material for film formation. Specifically, by heating the mixture of S i powder and S I_ ⁇ 2 powder in a vacuum, by raised calling the S i 0 gas to precipitate it in the low temperature deposition section, S I_ ⁇ precipitation Manufactured body. At that time, the physical properties of the Si0 precipitates were changed by changing the manufacturing conditions and the precipitation conditions such as the structure of the precipitation part (International Publication No. 03/0225246). See brochure).
- a rattra test was performed on each of the manufactured Si ⁇ precipitates, and a rattra value was examined.
- a negative electrode active material layer was formed on the surface of a current collector made of copper foil having a thickness of 10 m by ion plating.
- i ⁇ A film was formed.
- the various negative electrodes produced in this way were combined with the positive electrode, and sealed in a case together with the electrolytic solution to complete a lithium secondary battery (size diameter 15 mm, thickness 3 mm).
- the cycle characteristics of various completed batteries were measured.
- the cycle characteristics were evaluated by the ratio (capacity retention ratio) of the 10th discharge amount to the 1st discharge amount. Note that the positive electrode using a fine powder of L i C 00 2, the electrolytic solution using nonaqueous electrolyte containing ethylene carbonate.
- Table 2 shows the relationship between the measured capacity retention rate and the rattra value. As can be seen from Table 2, the lower the Ratra value of the Sio precipitate, which is a material for film formation, the higher the capacity retention ratio, and a capacity of 98% or more is maintained at a Ratra value of 1.0% or less. The rate is secured.
- Comparative Example 2 1.4 8 3.6
- the initial efficiency is 50% or less for the SiO layer formed by the powder kneading coating and drying method.
- the initial efficiency rises to 80% or more by preliminarily including lithium in S i 0, but this is because the initial charge capacity is reduced, and the excellent theoretical capacity of S i 0 is hindered. It will be.
- the initial efficiency is improved to 80% or more while the initial charge capacity is large.
- the negative electrode active material layer 32 in the negative electrode 30 is formed by vacuum evaporation or sputtering, preferably vacuum evaporation, using a Si ⁇ precipitate as a film forming material. This is a point composed of a dense S i 0 thin film formed on the current collector 31 by a kind of ion plating.
- the surface of the current collector 31 is cleaned by a surface treatment bombardment using a DC magnetron discharge in a vacuum chamber.
- an Sio film is formed on the surface of the current collector 31 by an ion plating method or the like without exposing to the atmosphere in the vacuum chamber.
- the appropriate thickness of the 310 film is 0.1 to 50 ⁇ m.
- the positive electrode active material layer 1 2 in the positive electrode 1 0 conventionally, a powder of an oxide of a transition metal containing lithium, such as L i C 0 0 2, is mixed with a binder solution was slurried its The slurry is formed by a powder kneading coating and drying method in which the slurry is applied to the surface of the current collector plate 21, dried, and then pressurized.
- Other configurations are the same as those of the first embodiment and the second embodiment.
- the features of the lithium secondary battery of the present embodiment are as follows.
- the negative electrode active material layer 32 is composed of Si0, it is compared with the carbon powder layer. The theoretical capacity is much larger.
- the Si ⁇ is a thin film formed by vacuum evaporation or sputtering, the initial efficiency can be increased without reducing the initial charge capacity.
- the capacity per unit volume of the thin film is large, miniaturization is easy.
- the surface of the current collector 31 is cleaned in a vacuum, and the film is continuously formed in a vacuum without being exposed to an air atmosphere. Excellent cycle characteristics can also be obtained when the Sio precipitate is used as a material for use.
- a S i O film was formed as a negative electrode active material layer on the surface of a current collector made of a copper foil having a thickness of 10 ⁇ by an ion plating method.
- a predetermined vacuum atmosphere EB gun as a heat source 3 was formed 1_Rei film (thickness 5 m) in [1 0-3 3 (1 0 5 1 0 1> 1].
- the surface of the current collector was washed in the air and dried, and then a film was formed in one vacuum chamber. Further, as an example of the present invention, after the surface of the current collector was cleaned by bombardment treatment in the vacuum chamber, a film was formed in the vacuum chamber and then in the bow I.
- the two types of manufactured negative electrode were combined with the positive electrode, and sealed in a case together with the electrolyte to complete a lithium secondary battery (size diameter 15 mm, thickness 3 mm).
- the cycle characteristics of various completed batteries were measured.
- the cycle characteristics were evaluated by the ratio of the 10th discharge amount to the 1st discharge amount (capacity maintenance rate). Note that the positive electrode using a fine powder of L i C 00 2, the electrolytic solution using nonaqueous electrolyte containing E Ji Ren carbonate.
- the cycle characteristics were 85% in the comparative example, but improved to 98% in the example of the present invention. That is, in the embodiment of the present invention, the cleaning process of the current collector is started. By isolating the surface of the current collector from the atmosphere
- the cycle characteristics when the same pretreatment as in the comparative example was performed were 90%. By performing the same pretreatment as in the example, the cycle characteristics were improved to 99%.
- the present invention is also effective when using a Sio sintered body as a material for film formation.
- the initial efficiency is 50% or less for the SiO layer formed by the powder kneading coating and drying method.
- the initial efficiency is increased to 80% or more by preliminarily including lithium in Si ⁇ , but this is because the initial charge capacity is reduced, and the excellent theoretical capacity of Si0 is hindered. become .
- the initial efficiency is improved to 80% or more while the initial charge capacity is large.
- the button battery is used as the battery type.
- the negative electrode is thin, the capacity can be easily increased by stacking.
- the present invention is particularly suitable for a stacked battery, and has a feature in that a small-sized and large-capacity battery can be provided at low cost by applying to the stacked battery. Then, in the case of a stacked type battery, it is possible to form a thin film by forming a film on the positive electrode active material layer, the current collector, the separator, and the like, similarly to the negative electrode active material layer.
- the negative electrode for a lithium secondary battery of the present invention has a structure in which a silicon oxide thin film formed by vacuum evaporation or sputtering is provided on the surface of a current collector, and thus a lithium secondary battery using Si
- the disadvantage of low initial efficiency, which is a disadvantage of the battery, is not significantly affected by the initial charge capacity of the battery. It has a significant effect on improving the performance and reducing the size of lithium secondary batteries.
- the negative electrode for a lithium secondary battery of the present invention is also a Sio film type negative electrode in which a silicon oxide film is formed as a negative electrode active material on the surface of a current collector, and has a tenth cycle characteristic.
- a silicon oxide film is formed as a negative electrode active material on the surface of a current collector, and has a tenth cycle characteristic.
- the capacity retention ratio in discharging is 98% or more, the initial efficiency and the initial charge capacity are large, and the cycle characteristics are good.
- the use of the negative electrodes of the lithium secondary batteries of the present invention does not impair the initial charge capacity characteristic of lithium secondary batteries using Si i This greatly improves the battery performance, and also improves the cycle characteristics. This has a significant effect on improving battery performance and miniaturization.
- the film-forming material of the present invention comprises a precipitate of S i 0 or a sintered body produced from the precipitate, it is used for forming a silicon oxide thin film in a negative electrode for a lithium secondary battery.
- the disadvantage of low initial efficiency which is a disadvantage of lithium secondary batteries that use ⁇ as the negative electrode, can be significantly improved without impairing the initial charge capacity characteristic of lithium secondary batteries.
- the evaporation rate is high, and the film formation rate can be improved.
- the film-forming material of the present invention is also a Si • precipitate, and the decrease in the initial charge capacity is accompanied by a weight reduction rate (Ratra value) of 1.0% or less in a Ratra test.
- the initial efficiency can be improved without any problems, and the cycle characteristics can also be improved.
- the method for producing a negative electrode for a lithium secondary battery according to the present invention is characterized by forming a silicon oxide thin film on the surface of the current collector by vacuum evaporation or sputtering to form a lithium secondary battery using Sio as a negative electrode.
- the drawback of low initial efficiency is greatly reduced without impeding the initial charge capacity.
- a negative electrode having excellent characteristics that can be improved can be provided, which has a great effect on improving the performance and reducing the size of the lithium secondary battery.
- the method for producing a negative electrode for a lithium secondary battery according to the present invention also reduces the initial charge capacity by using a Si0 precipitate having a weight reduction rate (Ratra value) of 1.0% or less in a Ratra test. Without this, the initial efficiency can be improved, and the cycle characteristics can be improved accordingly.
- the method for producing a negative electrode for a lithium secondary battery according to the present invention also includes the steps of: forming a silicon oxide film as a negative electrode active material on the surface of the negative electrode current collector, in a vacuum or in an inert atmosphere; After cleaning, the silicon oxide film is formed on the surface of the current collector without exposing the surface of the current collector to the air atmosphere. Good cycle characteristics can be ensured even when using i 0 precipitates. In addition, the use of these film forming materials can improve the initial efficiency without lowering the initial charge capacity.
Abstract
Description
Claims
Priority Applications (3)
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KR1020107027027A KR101118933B1 (ko) | 2003-04-28 | 2004-04-16 | 리튬 2차 전지용 음극, 당해 음극을 사용하는 리튬 2차 전지, 당해 음극 형성에 사용하는 막 형성용 재료 및 당해 음극의 제조방법 |
US10/554,397 US20070059601A1 (en) | 2003-04-28 | 2004-04-16 | Negative electrode for lithium secondary cell, lithium secondary cell employing the negative electrode, film deposition material b used for forming negative electrode, and process for producing negative electrode |
EP04728063A EP1622215A4 (en) | 2003-04-28 | 2004-04-16 | NEGATIVE ELECTRODE FOR LITHIUM ACCUMULATOR, LITHIUM ACCUMULATOR HAVING THIS NEGATIVE ELECTRODE, FILM DEPOSITION MATERIAL FOR MAKING A NEGATIVE ELECTRODE, AND METHOD FOR MANUFACTURING NEGATIVE ELECTRODE |
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JP2003295363A JP3999175B2 (ja) | 2003-04-28 | 2003-08-19 | リチウム二次電池用負極、その負極を用いたリチウム二次電池、その負極形成に用いる成膜用材料及びその負極の製造方法 |
JP2003-295363 | 2003-08-19 | ||
JP2003297443A JP3984937B2 (ja) | 2003-04-28 | 2003-08-21 | リチウム二次電池用負極の製造に用いる成膜用材料、リチウム二次電池用負極の製造方法及びリチウム二次電池用負極 |
JP2003-297443 | 2003-08-21 | ||
JP2003299701A JP3927527B2 (ja) | 2003-08-25 | 2003-08-25 | リチウム二次電池用負極の製造方法 |
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US (1) | US20070059601A1 (ja) |
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CN113241426B (zh) * | 2021-04-01 | 2022-09-27 | 长沙矿冶研究院有限责任公司 | 碳复合包覆氧化亚硅负极材料、其制备方法及锂离子电池 |
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- 2004-04-16 WO PCT/JP2004/005527 patent/WO2004097962A1/ja active Application Filing
- 2004-04-16 KR KR1020097013899A patent/KR20090081438A/ko not_active Application Discontinuation
- 2004-04-16 KR KR1020107027027A patent/KR101118933B1/ko not_active IP Right Cessation
- 2004-04-16 US US10/554,397 patent/US20070059601A1/en not_active Abandoned
- 2004-04-16 KR KR1020057020430A patent/KR20050119214A/ko not_active Application Discontinuation
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WO2006046353A1 (ja) * | 2004-10-25 | 2006-05-04 | Sumitomo Titanium Corporation | リチウム二次電池用負極の製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
US20070059601A1 (en) | 2007-03-15 |
EP1622215A4 (en) | 2009-07-22 |
EP1622215A1 (en) | 2006-02-01 |
KR101118933B1 (ko) | 2012-03-13 |
KR20050119214A (ko) | 2005-12-20 |
KR20110002495A (ko) | 2011-01-07 |
KR20090081438A (ko) | 2009-07-28 |
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