WO2011071154A1 - Film de silicium et cellule secondaire au lithium - Google Patents

Film de silicium et cellule secondaire au lithium Download PDF

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Publication number
WO2011071154A1
WO2011071154A1 PCT/JP2010/072255 JP2010072255W WO2011071154A1 WO 2011071154 A1 WO2011071154 A1 WO 2011071154A1 JP 2010072255 W JP2010072255 W JP 2010072255W WO 2011071154 A1 WO2011071154 A1 WO 2011071154A1
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Prior art keywords
silicon film
substrate
columnar
deposition source
film according
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PCT/JP2010/072255
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English (en)
Japanese (ja)
Inventor
優 野田
慎吾 諸隈
武継 山本
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住友化学株式会社
国立大学法人東京大学
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Application filed by 住友化学株式会社, 国立大学法人東京大学 filed Critical 住友化学株式会社
Priority to CN201080056160.8A priority Critical patent/CN102652183B/zh
Priority to US13/514,893 priority patent/US20120244441A1/en
Publication of WO2011071154A1 publication Critical patent/WO2011071154A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/541—Heating or cooling of the substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

  • the present invention relates to a silicon film and a lithium secondary battery. Specifically, the present invention relates to a lithium secondary battery using a silicon film obtained by vapor deposition and an electrode having the silicon film as a negative electrode.
  • Lithium secondary batteries are used as a power source for mobile devices such as personal computers and mobile phones. In recent years, not only for these mobile devices, but also for reducing the environmental burden of CO 2 such as electric vehicles and hybrid vehicles. Application has also been attempted as a power source for automobiles.
  • a silicon (Si) material has been studied as a material constituting a negative electrode capable of inserting and extracting lithium ions.
  • a carbon electrode is mainly used as the negative electrode, but the theoretical discharge capacity of the Si negative electrode is as large as about 4200 mAh / g, which can be more than 10 times the theoretical discharge capacity of the carbon negative electrode.
  • Patent Document 1 an electrode in which a silicon raw material is put into thermal plasma and a silicon film made of a silicon nanowire network is arranged on a substrate is used as a negative electrode of a lithium secondary battery.
  • the space between the wires in the silicon film acts as a space for relaxing expansion during charging of the lithium secondary battery, that is, storage of lithium ions, thereby reducing the expansion / contraction rate of the Si negative electrode.
  • an electrode formed by etching a silicon substrate to form a silicon columnar structure is used as a negative electrode of a lithium secondary battery.
  • the gap between the silicon columnar structures acts as a space for relaxing the expansion.
  • Patent Document 3 a flat film of silicon is used in advance as a negative electrode of a lithium secondary battery, and charging / discharging of the secondary battery is repeated to form a break, that is, a gap in the flat film. In this case, the cut acts as a space for relaxing the expansion.
  • Patent Document 1 when nanowire-shaped silicon is used, the film thickness can be increased, which is effective in reducing the expansion / contraction rate during charge / discharge. Since the gap between the wires occupies most of the silicon film, the density of the Si material in the electrode is low, and it is difficult to increase the capacity of the secondary battery. Moreover, since this silicon nanowire grows at random, it becomes difficult to control the air gap.
  • Patent Document 2 when an electrode formed by etching a silicon substrate to form a silicon columnar structure is used as a negative electrode, since silicon is also a substrate, a lithium secondary battery is obtained. It ’s hard to wind. As a result, there are structural limitations such as difficulty in obtaining a large-capacity secondary battery.
  • Patent Document 3 it is difficult to control the air gap with high accuracy and to obtain a large capacity secondary battery because the silicon flat film is cut by charging and discharging the secondary battery.
  • An object of the present invention is to provide a silicon film capable of providing an electrode suitable for a large capacity lithium secondary battery and a simple manufacturing method thereof.
  • the present invention provides the following inventions.
  • a silicon film having a columnar assembly which is an assembly of columnar structures made of Si or Si compounds.
  • ⁇ 2> The silicon film according to ⁇ 1>, wherein side surfaces of the columnar structures are in contact with each other to form a columnar aggregate.
  • ⁇ 3> The silicon film according to ⁇ 1> or ⁇ 2>, wherein the columnar structure is grown in a film thickness direction of the silicon film.
  • ⁇ 4> The silicon film according to any one of ⁇ 1> to ⁇ 3>, wherein the columnar structure has an aspect ratio of 20 or more.
  • ⁇ 5> The silicon film according to any one of ⁇ 1> to ⁇ 4>, wherein the silicon film has a plurality of columnar assemblies.
  • ⁇ 6> The silicon film according to any one of ⁇ 1> to ⁇ 5>, wherein the columnar structure has a diameter of 1 to 100 nm and a film thickness of 0.2 to 100 ⁇ m.
  • ⁇ 7> The silicon film according to any one of ⁇ 1> to ⁇ 6>, wherein there is a gap of 0.3 to 10 nm in a direction parallel to the columnar assemblies between the columnar assemblies.
  • ⁇ 11> The silicon film according to ⁇ 10>, wherein the particle has a diameter of 1 to 1000 nm.
  • ⁇ 12> The silicon film according to ⁇ 10> or ⁇ 11>, which includes a plurality of columnar aggregates.
  • ⁇ 13> The silicon film according to any one of ⁇ 1> to ⁇ 12>, which is formed in contact with a substrate.
  • ⁇ 14> The silicon according to ⁇ 13>, wherein the material of the substrate contains one or more elements selected from the group consisting of copper, nickel, iron, cobalt, chromium, manganese, molybdenum, niobium, tungsten, titanium, and tantalum. film.
  • a silicon film manufacturing method in which a silicon film is deposited on a substrate using a deposition source made of Si or a Si compound, wherein the temperature of the deposition source is 1700 K or higher and the substrate temperature is lower than the temperature of the deposition source.
  • a method for producing a silicon film wherein the difference between the temperature of the vapor deposition source and the substrate temperature is 700K or more.
  • ⁇ 17> The method for producing a silicon film according to ⁇ 15> or ⁇ 16>, wherein an average free path ( ⁇ ) of Si atoms is smaller than a deposition source-substrate distance (D).
  • ⁇ 18> The method for producing a silicon film according to any one of ⁇ 15> to ⁇ 17>, wherein an average free path ( ⁇ ) of Si atoms is 1/10 or less of a deposition source-substrate distance (D) .
  • ⁇ 19> The method for producing a silicon film according to any one of ⁇ 15> to ⁇ 18>, wherein the film forming speed is from 0.1 ⁇ m / min to 200 ⁇ m / min.
  • the substrate material includes one or more selected from the group consisting of copper, nickel, iron, cobalt, chromium, manganese, molybdenum, niobium, tungsten, titanium, and tantalum.
  • the manufacturing method of the silicon film in any one.
  • a silicon film deposition apparatus for depositing a silicon film on a substrate using a deposition source composed of Si or a Si compound, A means for heating the vapor deposition source so that the temperature of the vapor deposition source is 1700 K or higher, and a means for cooling the substrate so that the substrate temperature is lower than the temperature of the vapor deposition source, and the temperature of the vapor deposition source and the substrate temperature A silicon film deposition apparatus in which these temperatures can be set so that the difference between them is 700K or more.
  • a minimum diameter (P) of the substrate viewed from the vertical direction of the substrate can be set larger than a deposition source-substrate distance (D).
  • ⁇ 23> The above-mentioned ⁇ 21> or ⁇ 22>, provided with a carrier gas supply means and capable of vapor deposition under a condition that the mean free path ( ⁇ ) of Si atoms is smaller than the deposition source-substrate distance (D).
  • ⁇ 24> The silicon film deposition apparatus according to any one of ⁇ 21> to ⁇ 23>, wherein the film forming speed can be set to 0.1 ⁇ m / min to 200 ⁇ m / min.
  • ⁇ 26> The electrode according to ⁇ 25>, wherein the silicon film is formed in contact with the metal substrate.
  • the present invention it is possible to provide a silicon film that can provide an electrode suitable for a large-capacity lithium secondary battery and a simple manufacturing method thereof.
  • the silicon film of the present invention includes a gap between columnar structures, a gap between columnar aggregates that are aggregates of columnar structures, and / or secondary columnar aggregates that are aggregates of columnar aggregates. Due to the gap between them, the expansion and contraction of the silicon film during charging and discharging of the lithium secondary battery can be alleviated. Therefore, the silicon film of the present invention can suppress the deterioration of the silicon film as the negative electrode during repeated charging and discharging of the lithium secondary battery. That is, according to the silicon film of the present invention, a lithium secondary battery having good cycle characteristics can be provided.
  • Such a silicon film of the present invention can be applied not only to a lithium secondary battery but also to electrodes of other electrochemical storage devices such as a lithium ion capacitor.
  • a silicon film having a practically useful thickness can be produced in a short time, and since a vapor deposition method that does not necessarily require high vacuum is used, The manufacturing cost of the device is also low. Furthermore, according to the method for producing a silicon film of the present invention, the generation of by-products during film formation is also suppressed, so the environmental load is small. Therefore, the industrial value of the method for producing a silicon film of the present invention is extremely high.
  • the present invention provides a silicon film having a columnar aggregate which is an aggregate of columnar structures made of Si or Si compounds.
  • the columnar structure is made of Si or a Si compound.
  • the aspect ratio of the columnar structure is preferably 2 or more, 5 or more, 10 or more, 20 or more, 50 or more, or 100 or more. The upper limit of the aspect ratio is usually about 5000.
  • the side surfaces of the columnar structures are aggregated in contact with each other.
  • the silicon film of the present invention preferably has a plurality of columnar assemblies.
  • the columnar structure has a diameter of 10 to 100 nm or 1 to 100 nm and a film thickness of 0.2 to 100 ⁇ m in order to further increase the capacity of the obtained lithium secondary battery.
  • the columnar structure has a diameter of 15 nm or more, 20 nm or more, or 30 nm or more, and may be 90 nm or less, 80 nm or less, or 70 nm or less.
  • cracks having a width of 0.01 to 3 ⁇ m in the direction parallel to the columnar aggregates are present between the secondary columnar aggregates that are aggregates of the columnar aggregates, and the interval between the cracks is 1 to 100 ⁇ m. Is preferable in order to further improve the cycle characteristics of the obtained lithium secondary battery.
  • the diameter or width of the columnar aggregate is preferably 10 to 100 ⁇ m.
  • the columnar structure in the present invention is preferably polycrystalline or amorphous.
  • the present invention provides a silicon film having a columnar aggregate which is an aggregate of columnar structures made of Si or Si compounds, and the columnar structure has a structure in which particles are connected in a columnar shape.
  • the silicon film of the present invention preferably has a plurality of columnar assemblies.
  • the particles constituting the columnar structure preferably have a diameter of 10 to 1000 nm or 1 to 1000 nm in order to increase the capacity of the obtained lithium secondary battery.
  • the particle may have a diameter of 15 nm or more, 20 nm or more, or 30 nm or more, and may be 100 nm or less, 90 nm or less, 80 nm or less, or 70 nm or less.
  • the silicon film of the present invention is preferably formed in contact with the substrate.
  • the material of the substrate include metals, and among these, one or more elements selected from the group consisting of copper, nickel, iron, cobalt, chromium, manganese, molybdenum, niobium, tungsten, titanium, and tantalum are included. It is preferably one or more, more preferably one or more selected from the group consisting of copper, nickel and iron, and even more preferably copper.
  • Stainless steel is also a preferred material.
  • the substrate is preferably thin, preferably a metal foil, more preferably a copper foil.
  • a copper foil whose surface is roughened is preferable.
  • Examples of such copper foil include electrolytic copper foil.
  • an electrolytic copper foil is prepared by immersing a metal drum in an electrolytic solution in which copper ions are dissolved, and flowing current while rotating the copper drum, thereby depositing copper on the surface of the drum and peeling it off. It is the obtained copper foil.
  • One side or both sides of the electrolytic copper foil may be further subjected to roughening treatment or surface treatment.
  • the copper foil which precipitated copper on the surface of the rolled copper foil by the electrolytic method, and roughened the surface may be sufficient.
  • the columnar structure is made of Si or a Si compound.
  • the Si compound include a Si—Ge alloy.
  • the Si or Si compound in the present invention may be doped with impurities.
  • impurities include elements such as nitrogen, phosphorus, aluminum, arsenic, boron, gallium, indium, and oxygen.
  • the silicon film manufacturing method of the present invention is a silicon film manufacturing method in which a silicon film is deposited on a substrate using a deposition source made of Si or a Si compound, and the temperature of the deposition source is 1700 K or more. The temperature is lower than the temperature of the vapor deposition source, and the difference between the temperature of the vapor deposition source and the substrate temperature is 700K or more. According to this method, a high vacuum is not necessarily required, and a silicon film can be manufactured at normal pressure. By the silicon film manufacturing method of the present invention, the diffusion of Si atoms in the parallel direction of the substrate is suppressed, and the silicon film of the present invention can be manufactured.
  • the temperature of the vapor deposition source is preferably 1800K or higher.
  • the silicon film obtained by the method for producing a silicon film of the present invention has the same effect as the silicon film of the present invention.
  • the upper limit of the temperature of the vapor deposition source is usually about 2300K.
  • the distance (D) between the evaporation source and the substrate is smaller than the minimum diameter (P) of the substrate viewed from the vertical direction of the substrate.
  • the film growth rate that is, the film formation rate can be further increased.
  • a silicon film having a columnar structure can be obtained even when the vapor deposition source and the substrate are arranged in parallel and Si atoms fly from various directions. .
  • the mean free path ( ⁇ ) of Si atoms represented by the following formula is preferably smaller than the deposition source-substrate distance (D).
  • D deposition source-substrate distance
  • the resulting silicon film has columnar structures of particles, particularly 10 to 1000 nm. It has a structure in which particles with a diameter are connected in a columnar shape.
  • the film forming speed is preferably 0.1 ⁇ m / min to 200 ⁇ m / min. Further, even if the deposition time is 0.1 to 10 minutes, a silicon film having a thickness useful for practical use can be produced.
  • the substrate is the same as that described above, and the description thereof is omitted here.
  • the silicon film deposition apparatus of the present invention is a silicon film deposition apparatus for depositing a silicon film on a substrate using a deposition source made of Si or a Si compound so that the temperature of the deposition source is 1700K or higher.
  • the temperature can be set. With this apparatus, the silicon film of the present invention can be manufactured.
  • the minimum diameter (P) of the substrate viewed from the vertical direction of the substrate can be set larger than the distance (D) between the deposition source and the substrate.
  • a carrier gas supply means is provided so that vapor deposition can be performed under the condition that the mean free path ( ⁇ ) of Si atoms is smaller than the deposition source-substrate distance (D).
  • Argon is mentioned as carrier gas.
  • the film forming speed can be set to 0.1 ⁇ m / min to 200 ⁇ m / min.
  • the vapor deposition time can be set to 0.1 to 10 minutes.
  • Electrode with silicon film can be suitably used as an electrode in an electrochemical storage device such as a lithium secondary battery.
  • the electrode having the silicon film of the present invention can be used very suitably as a negative electrode in a lithium secondary battery.
  • the substrate can also function as a current collector in the electrode.
  • Lithium secondary battery As a representative example of the lithium secondary battery in the present invention, a copper foil is used as a substrate, and an electrode having a silicon film formed on the copper foil is used as a negative electrode of the lithium secondary battery. The case of manufacturing will be described.
  • an electrode group obtained by laminating or laminating or winding a separator, the above-described negative electrode, separator and positive electrode is housed in a battery case such as a battery can, and then impregnated with an electrolytic solution. Can be manufactured.
  • the shape of the electrode group for example, a shape in which the cross section when the electrode group is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, a rectangle with rounded corners, etc. Can be mentioned.
  • examples of the shape of the battery include a paper shape, a coin shape, a cylindrical shape, and a square shape.
  • the positive electrode only needs to be able to dope / dedope lithium ions at a higher potential than the negative electrode, and may be manufactured by a known method.
  • the positive electrode is manufactured by supporting a positive electrode mixture containing a positive electrode active material, a conductive material, and a binder on a positive electrode current collector.
  • a carbon material or the like can be used as the conductive material, and a thermoplastic resin can be used as the binder.
  • An example of the positive electrode current collector is Al.
  • ⁇ Lithium secondary battery-separator> As the separator, known separators may be used. For example, a porous film made of a material such as a polyolefin resin such as polyethylene or polypropylene, a fluororesin, or a film having a form such as a nonwoven fabric or a woven fabric can be used. .
  • the electrolyte usually contains an electrolyte and an organic solvent, and uses an electrolyte made of a lithium salt such as LiPF 6 and this is used as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate. What is obtained by dissolving in an organic solvent such as (EMC) may be used as the electrolytic solution.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC organic solvent
  • Example 1 Manufacture of silicon film
  • An 80 ⁇ 6 mm tungsten board was placed in the chamber, and a silicon piece (purity 99.99% or more) treated with HF using a 5 to 10% HF solution was placed on the tungsten board. It was. Since the silicon pieces are melted by heating and spread on the board, the size of the vapor deposition source is 80 ⁇ 6 mm.
  • Stainless steel foil (SUS304, size 30 mm ⁇ ) was placed on the upper side of the tungsten board, and this was used as a substrate (current collector). The stainless steel foil was made to face the silicon plate in parallel. At this time, the distance between the deposition source and the substrate was set to 25 mm, which was shorter than the minimum substrate diameter of 30 mm. The stainless steel foil was fixed in close contact with the surface of a cooling block that can be cooled with a water-cooled tube.
  • a vacuum was applied to 10 ⁇ 5 Pa with a turbo pump, and then 10 sccm of argon gas was introduced, and the pressure in the furnace was set to 13.3 Pa (0.1 Torr).
  • Boltzmann constant k 1.38 ⁇ 10 ⁇ 23 J / K
  • temperature T 300 K
  • pressure p 13.3 Pa
  • collision cross-sectional area ⁇ ⁇ d 2 . Therefore, when the collision diameter d between Si and Ar is 0.35 nm, the mean free path ⁇ is calculated as 0.57 mm.
  • FIG. 1 shows a cross-sectional SEM photograph and FIG. 2 shows a surface SEM photograph of the obtained silicon film.
  • FIG. 1 shows that the film of the present invention has a columnar structure (1).
  • a columnar structure (1) is shown. 1 and 2, the columnar structure (1) grows in the film thickness direction, has an aspect ratio of 5 or more, and a portion of 20 or more can also be confirmed.
  • the silicon film formed on the substrate was cut to 1 ⁇ 1 cm to obtain a negative electrode AE1.
  • the negative electrode AE1 was dried in a vacuum oven at 120 ° C. for 6 hours. After drying, it is transferred into a glove box substituted with argon gas and immersed in an electrolytic solution (1M LiPF 6 / EC + EMC (weight ratio of EC and EMC 3: 7)).
  • a lithium secondary battery TC1 is assembled by disposing the silicon deposition surface of the battery facing the separator.
  • FIGS. show that when the silicon film of the present invention is used as a negative electrode of a lithium secondary battery, the secondary battery characteristics such as cycle characteristics are excellent.
  • Example 2 Manufacture of silicon film
  • a silicon film having a film thickness of 0.8 ⁇ m was obtained in the same manner as in Example 1 except for the silicon filling amount.
  • a lithium secondary battery TC2 was produced in the same manner as in Example 1 except that this silicon film was used, and charge / discharge tests were performed by repeating charge / discharge.
  • FIG. 5 shows that when the silicon film of the present invention is used as a negative electrode of a lithium secondary battery, the secondary battery characteristics such as cycle characteristics are excellent.
  • Example 3 Manufacture of silicon film
  • a film thickness of 0.4 ⁇ m was obtained in the same manner as in Example 1 except that the pressure in the chamber during vapor deposition was 133 Pa (1 Torr, and the mean free path ⁇ of Si atoms was calculated to be 0.057 mm).
  • a silicon film was obtained.
  • a lithium secondary battery TC3 was produced in the same manner as in Example 1 except that this silicon film was used, and charge / discharge tests were performed by repeating charge / discharge.
  • FIG. 6 shows that when the silicon film of the present invention is used as a negative electrode of a lithium secondary battery, the secondary battery characteristics such as cycle characteristics are excellent.
  • Example 4 Manufacture of silicon film
  • a silicon film having a thickness of 2.0 ⁇ m was obtained in the same manner as in Example 3 except for the silicon filling amount.
  • a lithium secondary battery TC4 was produced in the same manner as in Example 3 except that this silicon film was used, and charge / discharge tests were performed by repeating charge / discharge.
  • Example 5 Manufacture of silicon film
  • the film thickness was reduced to 0,72 in the same manner as in Example 1 except that the pressure in the chamber during vapor deposition was set to 732 Pa (5.5 Torr, and the mean free path ⁇ of Si atoms was calculated to be 0.010 mm).
  • a silicon film of 25 ⁇ m was obtained.
  • a lithium secondary battery TC5 was produced in the same manner as in Example 1 except that this silicon film was used, and charge / discharge tests were performed by repeating charge / discharge.
  • FIGS. show that when the silicon film of the present invention is used as a negative electrode of a lithium secondary battery, the secondary battery characteristics such as cycle characteristics are excellent.
  • Example 6 Manufacture of silicon film
  • a silicon film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the filling amount of silicon and the Cu foil was used as the substrate.
  • a lithium secondary battery TC6 was produced in the same manner as in Example 1 except that this silicon film was used, and charge / discharge tests were performed by repeating charge / discharge.
  • Example 7 Manufacture of silicon film
  • a silicon film having a thickness of 3.7 ⁇ m was formed in the same manner as in Example 6 except for the silicon filling amount, and this was annealed at 600 ° C. for 10 minutes in an atmospheric pressure argon gas atmosphere to obtain a silicon thin film.
  • FIG. 9 shows a low-magnification surface SEM photograph and FIG. 10 shows a high-magnification surface SEM photograph of the obtained silicon film.
  • FIG. 9 shows that cracks (11) following the irregularities on the surface of the Cu foil are formed at intervals of 1 to 3 ⁇ m between the columnar aggregates (10), which are aggregates of columnar structures.
  • FIG. 10 shows that the silicon film is formed of a columnar structure (1) having a diameter of 30 to 200 nm.
  • FIG. 10 also shows that the width of the crack (11) between the columnar assemblies (10), which is an assembly of the columnar structures (1), is about 30 nm.
  • a lithium secondary battery TC7 was produced in the same manner as in Example 1 except that this silicon film was used, and charge / discharge tests were performed by repeating charge / discharge.

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention concerne un film de silicium capable de donner une électrode convenant pour un usage dans des cellules secondaires au lithium de grande capacité, ainsi qu'un procédé permettant de produire aisément le film de silicium. Le film de silicium est agencé en structures en colonnes, qui sont constituées de Si ou d'un composé de Si. Le film de silicium peut être un film dans lequel les structures en colonnes ont un diamètre de 10 à 100 nm et dans lequel le film a une épaisseur de 0,2 à 100 µm. Le procédé de production du film de silicium comprend l'utilisation d'une source de dépôt comprenant du Si ou un composé de Si afin de déposer en phase vapeur un film de silicium sur un substrat ; la source de dépôt affiche une température supérieure ou égale à 1 700 K et le substrat présente une température inférieure à celle de la source de dépôt, la différence de température entre la source de dépôt et le substrat étant supérieure ou égale à 700 K. Le procédé de production du film de silicium peut être un procédé au cours duquel la distance (D) entre la source de dépôt et le substrat est inférieure à la longueur de l'axe minimum (P) du substrat, vu depuis une direction perpendiculaire au substrat. L'invention concerne également une électrode disposant du film de silicium et une cellule secondaire au lithium ayant l'électrode en guise de cathode.
PCT/JP2010/072255 2009-12-10 2010-12-10 Film de silicium et cellule secondaire au lithium WO2011071154A1 (fr)

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JP7064709B2 (ja) * 2018-02-28 2022-05-11 Tdk株式会社 リチウムイオン二次電池用負極及びリチウムイオン二次電池
CN116134637A (zh) * 2020-09-08 2023-05-16 学校法人冲绳科学技术大学院大学学园 复合纳米架构单元、多层复合物和复合纳米架构单元的制造方法
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JP2011122200A (ja) 2011-06-23

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