WO2016140168A1 - Composite film and method for manufacturing same - Google Patents

Composite film and method for manufacturing same Download PDF

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Publication number
WO2016140168A1
WO2016140168A1 PCT/JP2016/055888 JP2016055888W WO2016140168A1 WO 2016140168 A1 WO2016140168 A1 WO 2016140168A1 JP 2016055888 W JP2016055888 W JP 2016055888W WO 2016140168 A1 WO2016140168 A1 WO 2016140168A1
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Prior art keywords
film
composite film
filamentous carbon
cnt
carbon
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PCT/JP2016/055888
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French (fr)
Japanese (ja)
Inventor
野田　優
慈喜 青井
裕介 森川
陽一郎 本田
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Ｊｘエネルギー株式会社
学校法人早稲田大学
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Publication of WO2016140168A1 publication Critical patent/WO2016140168A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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 composite film, a manufacturing method thereof, and an electrode and an electricity storage device using the composite film.
  • Energy storage devices such as secondary batteries such as lithium-ion batteries and electric double layer capacitors are used as power sources for mobile devices such as personal computers and mobile phones.
  • mobile devices such as personal computers and mobile phones.
  • electric vehicles In recent years, not only mobile devices but also electric vehicles and It is also used as a power source for automobiles that can reduce the environmental load of CO 2 such as hybrid cars.
  • CO 2 such as hybrid cars.
  • it is necessary to increase the weight and capacity per volume of a lithium ion battery and to enable long-distance movement by electric vehicles.
  • the electrode of the lithium ion battery includes an active material that occludes and releases lithium ions during charging and discharging.
  • the active material lithium metal oxide is generally used for the positive electrode, and graphite is used for the negative electrode.
  • an active material powder is generally mixed with a binder made of a non-conductive polymer such as polyvinylidene fluoride and a conductor made of carbon fiber (CF), carbon black, or the like. It is manufactured by applying a paste to an aluminum (Al) foil or a copper (Cu) foil as a current collector and baking it.
  • the binder is used for the purpose of fixing the active material on the current collector, and the conductor is used for the purpose of electrically connecting the current collector and the active material.
  • a layer in which the active material 130, the conductor 140, and the nonconductive binder 150 are mixed is formed on the current collector 180.
  • Patent Document 1 describes an electrode in which a columnar structure 132 made of Si is directly formed on a current collector 180 as shown in FIG.
  • the interface between the active material 130 and the current collector 180 is two-dimensional and the contact area is small, and further, the two-dimensional interface is non-conductive. Therefore, the resistance between the active material 130 and the current collector 180 is large. Therefore, it is impeded to increase the capacity of the lithium ion battery. Further, there is a problem that the active material 130 is peeled off from the current collector 180 due to deterioration of the binder 150 during use of the lithium ion battery.
  • an object of the present invention is to provide a composite film that can be used as an electrode of an electricity storage device having a high capacity and excellent cycle characteristics, and a method and an apparatus for manufacturing the composite film.
  • Another object of the present invention is to provide a self-supporting film having an aggregate of filamentous carbon having a novel structure, and a manufacturing method and manufacturing apparatus therefor. It is a further object of the present invention to provide a functional composite film that can be used for various applications and is self-supporting, as well as a manufacturing method and a manufacturing apparatus thereof.
  • a filamentous carbon layer composed of filamentous carbon It consists only of a metal layer composed of metal, A self-supporting composite film is provided in which a part or all of the metal layer overlaps with a part of the filamentous carbon layer to have a coexistence region where the filamentous carbon and the metal coexist.
  • a part of the metal layer may overlap with a part of the filamentous carbon layer.
  • the filamentous carbon layer has a network structure
  • the metal may enter the mesh of the mesh structure.
  • the filamentous carbon layer has a vertical alignment structure in which the filamentous carbon is aligned in a thickness direction of the filamentous carbon layer, and in the coexistence region, the filamentous carbon layer has a vertical alignment structure.
  • the metal may enter the gap.
  • the filamentous carbon may be bundled to form an upright wall in the thickness direction of the filamentous carbon layer.
  • the second aspect of the present invention consists only of a metal layer composed of metal and an aggregate of filamentous carbon, A part of the aggregate of filamentous carbon is included in the metal layer, A self-supporting composite film is provided in which the other part of the aggregate of filamentous carbon is exposed on the metal layer.
  • the filamentous carbon may include carbon nanotubes.
  • the metal may be Cu, Al, or Ni.
  • the self-supporting composite membrane of the first aspect or the second aspect A functional composite film having an active material attached to the filamentous carbon is provided.
  • a step of producing a filamentous carbon film composed of filamentous carbon Depositing a metal on the filamentous carbon film supported on a support;
  • a method for producing a composite membrane comprising a step of separating the filamentous carbon membrane and the composite membrane of metal from the support.
  • the filamentous carbon film having a network structure may be produced.
  • the step of producing the filamentous carbon film of the method for producing the composite film may include forming the filamentous carbon so that the filamentous carbon is oriented in a thickness direction of the filamentous carbon film. . Further, after the step of separating the filamentous carbon film and the metal composite film from the support, the filamentous carbon film is contracted to reduce the thickness of the filamentous carbon layer comprising the bundle of filamentous carbon. Forming a wall upright in the direction may be included.
  • the method for producing the composite film may include a step of supporting the filamentous carbon film by the support before the step of depositing a metal on the filamentous carbon film.
  • the filament-like carbon membrane is produced on the support on the upstream side in the movement direction while moving the support, and the filament-like carbon on the support on the downstream side in the movement direction.
  • the metal may be deposited on the carbon film.
  • the method for producing the composite film may further include a step of attaching an active material on the surface of the filamentous carbon film opposite to the surface on which the metal is deposited.
  • an electrode having the composite film of the first, second or fifth aspect or the functional composite film of the third aspect.
  • an electricity storage device including the electrode of the sixth aspect is provided.
  • the eighth aspect of the present invention only the metal layer and the filamentous carbon aggregate are included, and a part of the filamentous carbon aggregate is included in the metal layer,
  • An assembly forming portion that is provided on the upstream side in the moving direction and forms an assembly of the filamentous carbon on the support;
  • a composite film manufacturing apparatus provided with a vapor deposition mechanism provided on the downstream side in the moving direction and vapor-depositing metal on the aggregate of filamentous carbon.
  • the composite film manufacturing apparatus may include a roll in which the moving mechanism rotates and moves the support.
  • the composite film manufacturing apparatus by continuously operating the assembly forming unit and the vapor deposition mechanism, a long composite film is formed on the support, and the long composite film is continuously formed from the support.
  • the long composite film may be obtained by peeling off the film.
  • the composite film manufacturing method of the present invention by depositing a metal on the filamentous carbon film, a part of the metal layer enters the filamentous carbon film. Therefore, there is a coexistence layer in which the filamentous carbon and the metal coexist. It is formed. Therefore, the composite film manufactured by the manufacturing method of the present invention has a small electrical resistance between the filamentous carbon film and the metal layer. Furthermore, a functional composite film in which a material that can be used as an active material of a lithium ion battery is attached to the surface of the composite film opposite to the metal-deposited surface of the filamentous carbon film is used as an electrode of a lithium ion battery. Can be used.
  • a composite film to which an active material of an electricity storage device such as various secondary batteries or electric double layer capacitors is attached can be used as an electrode of the electricity storage device.
  • the electrode using the composite film of the present invention has low electrical resistance between the current collector and the active material, and even if the active material occludes and releases lithium ions and changes its volume, it peels off from the current collector. Hateful. Therefore, the composite film and the manufacturing method thereof of the present invention can be suitably used for applications such as electrodes of power storage devices such as lithium ion batteries.
  • FIG. 1A is a schematic cross-sectional view of the composite film of the first embodiment
  • FIGS. 1B and 1C are schematic cross-sectional views of the functional composite film of the second embodiment
  • 2A is a schematic cross-sectional view of the composite film of the third embodiment
  • FIG. 2B is a schematic cross-sectional view of a modified form of the composite film of FIG. 2A
  • FIG. (D) is a schematic sectional drawing of the functional composite film of 4th Embodiment.
  • FIG. 3 is a flowchart showing a method for manufacturing the composite membrane.
  • 4 (a) to 4 (e) are diagrams conceptually showing each process of the manufacturing method of the composite film of the first embodiment and the functional composite film of the second embodiment.
  • FIGS. 7A and 7B show planar SEM photographs of the sample obtained by dividing the CNT-Cu composite film of Example 1 into two
  • FIGS. 7C to 7E show the CNT-Cu of Comparative Example 1.
  • FIG. 8A shows a planar SEM image of the CNT film of Example 2.
  • FIG. 8B shows a planar SEM image of the CNT—Cu composite film of Example 2 as seen from the Cu side.
  • FIG. 8C shows a planar SEM image of the CNT—Cu composite film of Example 3 viewed from the Cu side.
  • FIG. 8D shows a planar SEM image of the CNT—Cu composite film of Example 4 as viewed from the Cu side.
  • FIG. 8E shows a planar SEM image of the CNT—Cu composite film of Example 5 viewed from the Cu side.
  • FIG. 8F shows a planar SEM image of the CNT—Cu composite film of Example 6 viewed from the Cu side.
  • FIG. 8G shows a planar SEM image of the CNT—Cu composite film of Example 7 viewed from the Cu side.
  • FIG. 8H shows a planar SEM image of the CNT—Cu composite film of Example 8 viewed from the Cu side.
  • FIG. 9 shows a cross-sectional SEM image of the Si—CNT—Cu composite film produced in Example 9.
  • FIG. 10 shows the charge / discharge cycle characteristics of the composite films of Example 9 and Comparative Example 2.
  • FIG. 11A is a digital camera photograph showing a state in which the CNT—Cu composite film is peeled from the substrate in Example 10
  • FIGS. 11B to 11D are self-supporting CNT—Cu composites of Example 10. It is a digital camera photograph of the film.
  • FIGS. 12A to 12C are digital camera photographs of the self-supporting CNT—Cu composite film of Example 11.
  • FIG. 13A is a cross-sectional SEM image of the self-supporting CNT—Cu composite film of Example 12.
  • FIG. 13B is a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 12 taken from the Cu film side.
  • FIG. 13C is a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 12 taken from the CNT film side.
  • 13D is a cross-sectional SEM image showing a network structure of a CNT-Cu composite film obtained by shrinking a CNT vertical alignment film in Example 12.
  • FIG. FIG. 13E is a planar SEM image showing the network structure of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 12.
  • FIG. 14A is an SEM image of the surface of the Cu substrate used in Example 13.
  • FIG. 14B is a digital camera photograph of the substrate after the CNT-Cu composite film and the CNT-Cu composite film of Example 13 were peeled off, and the CNT-Cu composite film was taken from the CNT film side.
  • FIG. 14C is a cross-sectional SEM image of the self-supporting CNT—Cu composite film of Example 13.
  • FIG. 14D is a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 13 taken from the CNT film side.
  • FIG. 14E is an oblique SEM image showing the streak structure of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 13.
  • FIG. 14A is an SEM image of the surface of the Cu substrate used in Example 13.
  • FIG. 14B is a digital camera photograph of the substrate after the CNT-Cu composite film and the CNT-Cu composite film of Example 13 were peeled off, and the C
  • FIG. 14F is a planar SEM image showing the streak structure of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 13.
  • FIG. 15A is a digital camera photograph of the self-supporting CNT-Al composite film and the remaining CNT film of Example 14, and the CNT-Al composite film is taken from the Al film side.
  • FIG. 15B is a digital camera photograph of the self-supporting CNT-Al composite film of Example 14 taken from the CNT film side.
  • FIG. 15C is a planar SEM image of the self-supporting CNT—Al composite film of Example 14.
  • FIG. 15D is a cross-sectional SEM image of the self-supported CNT—Al composite film of Example 14.
  • FIG. 16A is a digital camera photograph of the substrate after peeling the self-standing CNT-Al composite film and the CNT-Al composite film of Example 15, and the CNT-Al composite film was taken from the Al film side.
  • FIG. 16B is a digital camera photograph of the self-standing CNT-Al composite film of Example 15 taken from the CNT film side.
  • FIG. 16C is a planar SEM image of the self-supporting CNT—Al composite film of Example 15.
  • FIG. 16D is a cross-sectional SEM image of the self-supporting CNT—Al composite film of Example 15.
  • FIG. 17A is a digital camera photograph of the substrate after peeling the self-supporting CF + CNT-Al composite film and CF + CNT-Al composite film of Example 16, and the CF + CNT-Al composite film is taken from the Al film side.
  • FIG. 17B is a digital camera photograph of the self-supporting CF + CNT-Al composite film of Example 16 taken from the CNT film side.
  • FIG. 17C is a planar SEM image of the self-supported CF + CNT-Al composite film of Example 16.
  • FIG. 17D is a cross-sectional SEM image of the self-supporting CF + CNT-Al composite film of Example 16.
  • 18A is a cross-sectional SEM image of the vertically aligned CNT film of Example 17.
  • FIG. 18B is a digital camera photograph of the substrate after peeling the self-standing CNT-Al composite film and the CNT-Al composite film of Example 17, and the CNT-Al composite film was taken from the CNT film side.
  • FIG. 18C is a digital camera photograph of the self-supported CNT-Al composite film of Example 17 taken from the Al film side.
  • FIG. 18D is a cross-sectional SEM image of the self-supported CNT—Al composite film of Example 17.
  • FIG. 19A is a digital camera photograph of the self-supporting AC + CNT-Al composite film of Example 18 taken from the Al film side.
  • FIG. 19B is a planar SEM image of the self-supporting AC + CNT-Al composite film of Example 18.
  • FIG. 19C is a cross-sectional SEM image of the self-supported AC + CNT—Al composite film of Example 18.
  • FIG. 19D is a graph plotting the sheet resistance of the AC + CNT-Al composite film of Example 18 against the equivalent film thickness of the Al film.
  • FIG. 19E is a graph showing the sweep rate dependence of the specific capacity in cyclic voltammetry using the AC + CNT composite film and the AC + CNT-Al composite film of Example 18.
  • FIG. 20 is a schematic cross-sectional view of an electrode of a prior art lithium ion battery using a binder made of a non-conductive polymer.
  • FIG. 21 is a schematic cross-sectional view of an electrode of a prior art lithium ion battery having a Si columnar structure.
  • the composite film 100 of the first embodiment is composed of only a filamentous carbon layer (film) 20 that is an aggregate of filamentous carbon and a metal layer 10 made of metal.
  • a part of the metal layer 10 overlaps with a part of the filamentous carbon layer 20. Therefore, a coexistence layer (coexistence region) 60 in which filamentous carbon and metal coexist exists in the metal layer 10 or the filamentous carbon layer 20. That is, the filamentous carbon film 20 includes the first layer 40 made of only the filamentous carbon 42 and the coexistence layer 60, and the metal layer 10 includes the second layer 80 made of only the metal and the coexistence layer 60.
  • the composite film 100 does not have another layer (intermediate layer) between the first layer 40 and the coexistence layer 60 and between the coexistence layer 60 and the second layer 80. It forms an interface or boundary between the two layers 80. If attention is paid to the filamentous carbon layer 20, one side of the filamentous carbon film 20 (a part of the aggregate of filamentous carbon) is included in the metal layer 10, and the other side of the filamentous carbon film 20. (The other part of the aggregate 20 of filamentous carbon) is exposed on the metal layer 10.
  • the filamentous carbon film 20 may contain granular carbon such as activated carbon in addition to the filamentous carbon 42. That is, in the present application, the “filamentous carbon layer”, “aggregate of filamentous carbon”, and “first layer made of only filamentous carbon” may contain granular carbon in addition to the filamentous carbon.
  • the composite film according to the present invention only needs to have the first layer 40 made of only filamentous carbon and the coexistence layer 60 in which the filamentous carbon and metal coexist, and is made of only the metal shown in FIG.
  • the second layer 80 is not essential. That is, all of the metal layer 10 may overlap with a part of the filamentous carbon layer 20.
  • the composite film 100 of the first embodiment includes the filamentous carbon film 20 including the first layer 40 and the coexistence layer 60 made of only the filamentous carbon 42, the second layer 80 and the coexistence layer made of only the metal. First, the first layer 40, the second layer 80, and the coexistence layer 60 will be described.
  • the first layer 40 is composed of conductive filamentous carbon 42, in particular, an aggregate of filamentous carbon 42.
  • “Aggregate of filamentous carbon” is an aggregate formed by overlapping or intersecting a large number of filamentous carbons while maintaining voids.
  • the filamentous carbon is arranged in a predetermined direction such as a mesh or vertical arrangement type. Including the structure.
  • the filamentous carbon 42 include carbon nanotubes (hereinafter abbreviated as “CNT” as appropriate), carbon nanofibers represented by vapor-grown carbon fibers (hereinafter abbreviated as “CNF” as appropriate), carbon fibers (hereinafter, as appropriate).
  • the filamentous carbon 42 preferably contains CNT, CNF, or a mixture thereof, and more preferably contains CNT.
  • CNT it is more preferable to use CNT composed of graphene cylinders having an average of 1 to 30 layers.
  • CNTs for example, those synthesized by the method described in Carbon 49 (6), 1972-1979 (2011), Carbon 80, 339-350 (2014), etc. can be used.
  • Commercially available CNT, CNF and / or CF may be used.
  • the filamentous carbon 42 forms a network structure 44.
  • the network structure 44 preferably includes a network (steric void) having a size within a range of 3 nm to 1000 nm.
  • the second layer 80 is made of a metal, and is particularly preferably made of a low resistance metal.
  • the composite film 100 is used for a positive electrode of a lithium ion battery, aluminum or the like may be used as a metal.
  • the composite film 100 is used for the negative electrode of a lithium ion battery, copper, nickel, or the like may be used as the metal.
  • the thickness of the second layer 80 can be set to any thickness depending on the application. For example, when the composite film 100 of the present embodiment is used for the negative electrode of a lithium ion battery, the thickness is in the range of 0.03 ⁇ m to 30 ⁇ m. Is preferably within the range of 1 to 10 ⁇ m. When the thickness of the second layer 80 is 10 ⁇ m or less, the composite film 100 is further reduced in weight. When the thickness of the second layer 80 is 1 ⁇ m or more, the resistance of the composite film 100 can be further reduced.
  • the coexistence layer 60 is a layer or region in which the filamentous carbon 42 and metal coexist.
  • the metal of the coexistence layer 60 is the same metal as the metal constituting the second layer 80. That is, the coexistence layer 60 has a structure in which the filamentous carbon 42 of the first layer 40 and the metal of the second layer 80 are partially mixed. For this reason, as shown in FIG. 1A, the coexistence layer 60 has a network structure 44 of filamentous carbon 42 as in the first layer 40, and the network (three-dimensional voids) of the network structure 44. There is metal inside.
  • the mesh structure 44 may include a mesh having a size in the range of 3 nm to 1000 nm. Since the metal has entered the mesh with the filamentous carbon 42, the filamentous carbon 42 and the metal are mechanically and electrically connected.
  • the thickness of the coexistence layer 60 can be set within the range of 0.01 ⁇ m to 10 ⁇ m by manufacturing the composite film 100 by the manufacturing method described later. When the thickness of the coexistence layer 60 is within the above range, the first layer 40 and the second layer 80 are sufficiently mechanically and electrically connected.
  • the metal enters the mesh of the filamentous carbon 42 as described above, so that the filamentous carbon and the metal are mechanically connected without using a binder made of a nonconductive material. Is done. Further, since the metal enters the mesh of the filamentous carbon 42, the filamentous carbon and the metal are also electrically connected, and the composite film 100 includes a binder made of a non-conductive material as described above. Therefore, the composite film 100 of this embodiment has a low resistance. Furthermore, since the filamentous carbon 42 is exposed from the metal, the composite film 100 of this embodiment has a large surface area. Therefore, the composite film 100 of the present embodiment can be suitably used as a current collector foil for an electrode of a lithium ion battery.
  • [Second Embodiment] 1B and 1C show a functional composite film in which an active material is attached to the self-supporting composite film of the first embodiment.
  • the functional composite films 300 and 400 of the second embodiment are the same as the composite film 100 of the first embodiment shown in FIG. 1A, and the first layer 40 made of filamentous carbon 42 and the second made of metal.
  • the composite film has a layer 80, a filamentary carbon 42 formed between the first layer 40 and the second layer 80, and a coexistence layer 60 in which a metal coexists.
  • the functional composite films 300 and 400 adhere to the filamentous carbon 42 on the surface opposite to the surface on which the coexisting layer 60 of the first layer 40 is formed and the self-supporting composite film of the first embodiment.
  • Electrode active material 34 Electrode active material 34. That is, the functional composite films 300 and 400 have a configuration in which the active material 34 is attached to the filamentous carbon 42 that forms the first layer 40 of the composite film 100 of the first embodiment.
  • the first layer 40, the second layer 80, and the coexistence layer 60 of the functional composite films 300, 400 are configured in the same manner as the first layer 40, the second layer 80, and the coexistence layer 60 of the composite film 100 of the first embodiment. Therefore, the description is omitted.
  • active material 34 materials having various functions can be used.
  • a material capable of inserting and extracting lithium ions as the active material 34 for example, Si, Si oxide, other metal elements other than Si and Si Si composite oxides containing, carbon materials such as graphite, hard carbon, graphite, and amorphous carbon, materials that form alloys with Li, such as Li, Sn, Al, Sn oxides such as SnO, other than Sn and Sn Sn composite oxides containing other metal elements, lithium titanate, Li, or the like can be used.
  • LiCoO 2 , LiMn 2 O 4 , LiFePO 4 , Li (Ni—Mn—Co) O 2 , S, or the like can be used as the active material 34. These may be used alone or in combination of two or more.
  • the active material 34 is attached to the filamentous carbon means that the active material 34 is inside the network structure 44 of the first layer 40 from the surface opposite to the surface on which the coexisting layer 60 of the first layer 40 is formed. It includes a form in which the active material 34 has entered (see FIG. 1B) and a form in which the active material 34 is attached so as to cover the surface of the filamentous carbon 42 (see FIG. 1C). Further, a part of the active material 34 included in the functional composite films 300 and 400 may enter the network structure 44 of the filamentous carbon 42, or all of the active material 34 included in the functional composite films 300 and 400 may be filaments. It may enter the network structure 44 of the carbon-like carbon 42.
  • the active material 34 included in the functional composite films 300 and 400 may enter the entire network structure 44 of the filamentous carbon 42 and may be in direct contact with the coexisting layer 60, or the functional composite films 300 and 400 may include the active material 34.
  • the active material 34 does not need to be in direct contact with the coexistence layer 60 by entering a part of the network structure 44 of the filamentous carbon 42.
  • the active material 34 greatly changes in volume with the insertion and extraction of lithium ions during charge and discharge. 34 has entered the network structure 44 of the filamentous carbon 42, or the active material 34 is attached so as to cover the surface of the filamentous carbon 42, so that the volume of the active material 34 is deformed by the deflection of the filamentous carbon 42. The change can be absorbed (relaxed), and the active material 34 is prevented from peeling from the first layer 40.
  • the composite film 100 of the first embodiment has a large surface area because the filamentous carbon 42 is exposed from the metal. Therefore, the functional composite films 300 and 400 of this embodiment having a configuration in which the active material 34 is attached to the filamentous carbon 42 constituting the first layer 40 of the composite film 100 of the first embodiment include the active material 34 and the first active material 34.
  • the contact area of one layer 40 is large (many contact points). Therefore, in the functional composite films 300 and 400, the first layer 40 composed of the active material 34 and the filamentous carbon 42 is mechanically well connected.
  • the active material 34 is unlikely to peel from the first layer 40 even if the volume of the active material 34 changes greatly during charging and discharging. Therefore, a long-life secondary battery can be manufactured by using the functional composite films 300 and 400 as electrodes of a secondary battery represented by a lithium ion battery.
  • the contact area between the active material 34 and the first layer 40 is large, the first layer 40 composed of the active material 34 and the filamentous carbon 42 is electrically connected well (the contact resistance is small).
  • the functional composite films 300 and 400 of the present embodiment as in the composite film 100 of the first embodiment, since the metal enters the mesh of the filamentous carbon 42, the filamentous carbon 42 and the metal are separated from each other. The connection is made without using a binder made of a non-conductive material. Therefore, the first layer 40 made of filamentary carbon 42 and the metal are connected with low resistance. Therefore, in the functional composite films 300 and 400 of the present embodiment, the active material 34 and the metal are connected with low resistance. Therefore, by using the functional composite films 300 and 400 as electrodes of a secondary battery such as a lithium ion battery, a secondary battery such as a high capacity lithium ion battery can be manufactured.
  • a secondary battery such as a high capacity lithium ion battery can be manufactured.
  • the active material 34 can be fixed on the first layer 40 without using a binder.
  • a binder (not shown) made of a non-conductive polymer for fixing the active material 34 to the first layer 40 may be included.
  • the functional composite film 300 may further include a conductive material (not shown) made of carbon nanofiber (CNF), carbon black, or the like.
  • the first layer 40 is composed of the conductive filamentous carbon 42 and has a high surface area. Therefore, the contact area between the active material 34 and the filamentous carbon 42 is large, and sufficient conductivity is obtained even when a binder is added.
  • the conductivity in the vertical direction of the layer made of the active material 34 can be sufficiently secured even when the layer made of the active material 34 is thicker than the first layer 40.
  • the conductive material enters the network of the first layer 40, sufficient conductivity between the active material 34 and the first layer 40 can be ensured.
  • the composite film 100a of the third embodiment is a filamentous carbon (film) 20a that is an aggregate of filamentous carbon, It is a self-supporting film comprised only from the metal layer 10a comprised from the metal, and a part of metal layer 10 has overlapped with a part of filamentous carbon layer 20a.
  • region) 60a in which filamentous carbon and a metal coexist exists in the metal layer 10a or the filamentous carbon layer 20a.
  • the filamentous carbon film 20a has a first layer 40a made only of the filamentous carbon 42 and a coexistence layer 60a
  • the metal layer 10 has a second layer 80a made only of a metal and a coexistence layer 60a.
  • the composite film 100a does not have another layer (intermediate layer) between the first layer 40a and the coexistence layer 60a, and between the coexistence layer 60a and the second layer 80a. It forms an interface or boundary between the two layers 80a.
  • one surface of the filamentous carbon film 20 (part of the aggregate of filamentous carbon) is included in the metal layer 10a, and the other surface of the filamentous carbon film 20a. (The other part of the filament-like carbon aggregate 20) is exposed on the metal layer 10a.
  • the filamentous carbon 42a is oriented (perpendicular in the thickness direction of the first layer 40a and the coexistence layer 60a.
  • the vertical alignment structure 46 of the filamentous carbon 42a is formed.
  • a plurality of filamentous carbons 42a extending in a direction perpendicular to the surface of the second layer 80a are adjacent to each other with a gap, and in the coexistence layer 60a, metal enters the gap. It is out.
  • the vertical alignment structure 46 of the filamentous carbon 42a may include voids having a size in the range of 3 nm to 1000 nm.
  • the first layer 40a, the second layer 80a, and the coexistence layer 60a of the composite film 100a are made of the same material as the first layer 40, the second layer 80, and the coexistence layer 60 of the composite film 100 of the first embodiment. ing.
  • the filament-like carbon and the metal can be used without using a binder made of a non-conductive material. Are mechanically connected. Further, since the metal enters the mesh of the filamentous carbon 42a, the filamentous carbon and the metal are also electrically connected, and the composite film 100a includes a binder made of a nonconductive material as described above. Therefore, the composite film 100a of this embodiment has a low resistance. Furthermore, since the filamentous carbon 42a is exposed from the metal, the composite film 100a of this embodiment has a large surface area. Therefore, like the composite film 100 of the first embodiment, the composite film 100a of the third embodiment can be suitably used as a current collector foil or the like used for an electrode of an electricity storage device such as a lithium ion battery.
  • FIG. 2B shows a modification of the composite film 100a of the third embodiment.
  • the vertically oriented filamentous carbon 42b is bundled to form a wall 41b that stands upright in the thickness direction of the first layer 40b and the coexistence layer 60b.
  • the wall 41b forms a random network structure 46b when viewed from the thickness direction of the first layer 40b and the coexistence layer 60b (see FIG. 13E).
  • the network structure 46b may include a network (void) of 1 to 200 ⁇ m. With such a structure, various active materials can be introduced into the mesh, the filamentous carbon is less likely to collapse, and an upright structure can be easily maintained, and an electrode of an electricity storage device with excellent performance can be manufactured. Further, the upright wall made of a bundle of filamentous carbon may form an arbitrary structure different from a network structure such as a streak structure regularly arranged in one direction.
  • the functional composite films 300a and 400a shown in FIGS. 2C and 2D are functional composite films in which an active material is attached to the self-supporting composite film 100a of the third embodiment. Similar to the composite film 100a shown in FIG. 2A, a first layer 40a made of filamentary carbon 42a, a second layer 80a made of metal, and a filament formed between the first layer 40a and the second layer 80a. A coexistence layer 60a in which the carbon-like carbon 42a and the metal coexist.
  • the functional composite films 300a and 400a further have an active material 34a attached to the filamentous carbon 42a on the surface of the first layer 40a opposite to the surface on which the coexistence layer 60a is formed.
  • the functional composite films 300a and 400a of the fourth embodiment have a configuration in which the active material 34a is attached to the filamentous carbon 42a that constitutes the first layer 40a of the composite film 100a of the third embodiment.
  • the first layer 40a, the second layer 80a and the coexistence layer 60a of the functional composite films 300a and 400a are the same as the first layer 40a, the second layer 80a and the coexistence layer 60a of the functional composite film 300 of the third embodiment. Since the active material 34a of the functional composite films 300a and 400a is configured similarly to the active material 34 of the functional composite films 300 and 400 of the second embodiment, detailed description thereof will be omitted.
  • the active material 34a is attached to the filamentous carbon means that the active material 34a is inside the vertical alignment structure 46 of the first layer 40a from the surface opposite to the surface on which the coexisting layer 60a of the first layer 40a is formed. In which the active material 34a enters (see FIG. 2 (c)), or the surface of the filamentous carbon 42a is attached so as to cover the active material 34a (see FIG. 2 (d)). Further, a part of the active material 34a included in the functional composite films 300a and 400a may enter the vertical alignment structure 46 of the filamentous carbon 42a, or the entire active material 34a included in the functional composite films 300a and 400a may be included. It may enter the vertical alignment structure 46 by the filamentous carbon 42a.
  • the active material 34a included in the functional composite films 300a and 400a may enter the entire network structure 44a of the filamentous carbon 42a and may be in direct contact with the coexistence layer 60a, or the functional composite films 300a and 400a may include the active material 34a.
  • the active material 34a may enter a part of the network structure 44a of the filamentous carbon 42a and may not be in direct contact with the coexistence layer 60a.
  • the active material 34a changes greatly in volume with the insertion and extraction of lithium ions during charging and discharging, but the active material 34a is made of filamentous carbon 42a. Since the vertical alignment structure 46 enters or the active material 34a adheres so as to cover the surface of the filamentous carbon 42a, the filamentous carbon 42a bends to absorb (relax) the volume change of the active material 34a. It is possible to prevent the active material 34a from peeling from the first layer 40a.
  • the composite film 100a of the third embodiment has a large surface area because the filamentous carbon 42a is exposed from the metal. Therefore, the functional composite films 300a and 400a of the present embodiment having a configuration in which the active material 34a is attached to the filamentous carbon 42a constituting the first layer 40a of the composite film 100a of the third embodiment includes the active material 34a and the first active material 34a.
  • the contact area of one layer 40a is large (many contact points). Therefore, in the functional composite films 300a and 400a, the first layer 40a composed of the active material 34a and the filamentous carbon 42a is mechanically well connected.
  • the functional composite films 300a and 400a are used as electrodes typified by a lithium ion battery, even if the volume of the active material 34a changes greatly during charging and discharging, the active material 34a is difficult to peel from the first layer 40a. . Therefore, by using the functional composite films 300a and 400a as electrodes of an electricity storage device such as a lithium ion battery, a long-life electricity storage device can be manufactured.
  • the contact area between the active material 34a and the first layer 40a is large, the first layer 40a composed of the active material 34a and the filamentous carbon 42a is electrically connected well (the contact resistance is small).
  • the metal enters the vertical alignment structure 46 of the filamentous carbon 42a, whereby the filamentous carbon 42a. And the metal are connected without a binder made of a non-conductive material. Therefore, the first layer 40a made of filamentary carbon 42a and the metal are connected to a low resistance. Therefore, in the functional composite films 300a and 400a of the present embodiment, the active material 34a and the metal are connected with low resistance.
  • the filamentous carbon 42a is oriented perpendicular to the second layer 80a made of metal, the filamentous carbon 42a has the shortest distance and the active material 34a is made of metal. It can be connected to the two layers 80a. Therefore, even when the layer of the active material 34a is thick, the active material 34a and the second layer 80a can be connected with low resistance. Therefore, a secondary battery such as a high-capacity lithium ion battery can be manufactured by using the functional composite films 300a and 400a as electrodes of a secondary battery represented by a lithium ion battery.
  • the active material 34a can be fixed on the first layer 40a without using a binder.
  • a binder made of a nonconductive polymer for fixing the active material 34a to the first layer 40a may be included.
  • the functional composite film 300a may further include a conductive material made of carbon nanofiber (CNF), carbon black, or the like.
  • the first layer 40a is made of the conductive filament carbon 42a and has a high surface area.
  • the contact area between the active material 34a and the filament carbon 42a is large, and sufficient conductivity can be obtained even if a binder is added. Can be secured. Further, by adding a conductive material, it is possible to sufficiently ensure the conductivity in the vertical direction of the layer made of the active material 34a even when the layer made of the active material 34a is thicker than the first layer 40a. In addition, since the conductive material enters the gap between the first layers 40a, the conductivity between the active material 34a and the first layer 40a can be sufficiently ensured.
  • the functional composite film can be obtained by attaching the active material to the composite film 100b in a modified form.
  • the manufacturing method of the present embodiment includes a step S1 for mainly producing a film made of filamentous carbon (hereinafter referred to as “filamentous carbon film” as appropriate), and the produced filamentous carbon film.
  • filamentous carbon film a film made of filamentous carbon
  • the manufacturing method of the composite film according to this invention does not need to have filamentous carbon film support process S2 and active material adhesion process S5. That is, in the method for manufacturing a composite film according to the present embodiment, the filamentous carbon film supporting step S2 and the active material attaching step S5 are optional steps.
  • Filamentous carbon films are, for example, a method of applying and drying a dispersion of filamentous carbon on a substrate by spray coating or blade coating, a dispersion of filamentous carbon using a membrane filter It can form by the method of filtering.
  • the dispersion of filamentous carbon can be adjusted by adding filamentous carbon such as CNT or CNF to an aqueous solution of a surfactant and ultrasonically dispersing it.
  • a surfactant for example, sodium dodecylbenzenesulfonate (SDBS) can be used.
  • SDBS sodium dodecylbenzenesulfonate
  • a commercially available CNT dispersion or CNF dispersion may be used.
  • the filamentous carbon dispersion 120 is suction filtered using a membrane filter 140 as shown in FIG.
  • the filamentous carbon film 20 can be obtained on the membrane filter 140 by separating the filamentous carbon from the dispersion medium.
  • a VCWP filter, a PTFE filter, a silica fiber filter, or the like can be used as the membrane filter 140.
  • the filamentous carbon film 20 having the network structure 44 in which filamentous carbon is intertwined can be formed by the above method.
  • the network structure of the filamentous carbon film 20 formed by the above method can include a network (steric void) having a size in the range of 3 nm to 1000 nm.
  • the size of the mesh is generally determined in correlation with the diameter of the filamentous carbon, but further depends on the viscosity of the dispersion, the size of the mesh of the filter, the degree of unevenness of the surface, the presence or absence of compression after drying the filamentous carbon film, etc. Can be adjusted.
  • the size of the mesh can also be adjusted by removing the polymer particles with a solvent after filtration with polymer particles soluble in an organic solvent to form a filamentous carbon film. Since the filamentous carbon film 20 includes a mesh having such a size, metal can enter the filamentous carbon film 20 in a metal vapor deposition step S3 described later.
  • the filamentous carbon film 20 formed on the membrane filter 140 is supported (transferred) on the substrate (support) 160.
  • the substrate 160 a stainless steel substrate, a glass substrate, a ceramic substrate, a silicon substrate, or the like can be used.
  • the filamentous carbon film 20 can be supported on the substrate 160 as follows, for example. A binder is applied onto the substrate 160, the filament carbon film 20 and the binder on the substrate 160 are made to face each other, and the membrane filter 140 on which the filament carbon film 20 is formed is pressed against the substrate 160. After the filamentous carbon film 40 adheres to the substrate 160 via the binder, the membrane filter 140 is peeled off from the filamentous carbon film 20. By these operations, the filamentous carbon film 20 is supported on the substrate 160.
  • the filamentous carbon film 20 can be supported on the substrate 160 by the following method.
  • the membrane filter 140 on which the filamentous carbon film 20 is formed is pressed against the substrate 160 with the filamentous carbon film 20 and the substrate 160 facing each other.
  • the membrane filter 140 is wetted with a mixed solution of ethanol and water and then dried, and the membrane filter 140 is peeled off from the filamentous carbon film 20.
  • the filamentous carbon film 20 can be supported on the substrate 160.
  • the filamentous carbon film 20 can be supported on the substrate 160 by the following method.
  • the membrane filter 140 on which the filamentous carbon film 20 is formed is impregnated with pure water. Then, since only the filamentous carbon film 20 floats on the water surface, it is scooped by the substrate 160. Thereby, the filamentous carbon film 20 can be supported on the substrate 160. Before scrubbing with the substrate 160, the filamentous carbon film 20 may be washed with heated pure water to remove the surfactant attached to the filamentous carbon film 20.
  • the filamentous carbon film 20 supported on the substrate 160 by these methods may be annealed in a reducing atmosphere. Thereby, the surfactant remaining on the filamentous carbon film 20 can be decomposed.
  • the membrane filter is a substrate. It can also serve as a (supporting substrate). That is, after filtering the filamentous carbon in step S1 to form a film on the membrane filter, step S3 can be entered immediately.
  • the filamentous carbon film support step is also used when the filamentous carbon film is produced on the substrate by applying and drying the filamentous carbon dispersion by spray coating or blade coating. A filamentous carbon film supported on the substrate can be obtained without performing S2.
  • a metal is deposited on the filamentous carbon film 20 supported by the substrate 160.
  • the metal layer 10 can be formed on the filamentous carbon film 20.
  • Metal vapor deposition can be performed by any vapor deposition method such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, and CVD.
  • the vapor deposition thickness of the metal can be set to any thickness depending on the application.
  • the composite film produced by the production method of the present embodiment is used as the negative electrode of the lithium ion battery. When it is used in the above, it is preferably in the range of 0.03 to 30 ⁇ m, more preferably in the range of 1 to 10 ⁇ m.
  • the composite film 100 composed of the filamentous carbon film 20 and the metal layer 10 is peeled from the substrate 160 (see FIG. 4D).
  • the filamentous carbon film 20 and the metal layer 10 can be mechanically separated from the substrate 160 by, for example, a method of picking the outer periphery of the filamentous carbon film 20 with tweezers and pulling it up from the substrate 160. That is, a self-supporting filamentous carbon and metal composite film 100 is obtained.
  • the composite film 100 obtained in this way has a structure in which a part of the metal layer 10 has entered (sunk into) the mesh of the filamentous carbon film 20 as shown in FIG.
  • the obtained composite film 100 includes a filamentous carbon formed between the first layer 40 made of filamentous carbon, the second layer 80 made of metal, and the first layer 40 and the second layer 80. And a coexistence layer 60 in which a metal coexists.
  • the metal By depositing a metal on the filamentous carbon film by the method as described above, the metal can be penetrated from the surface layer of the filamentous carbon film 20 to a depth in the range of 0.01 ⁇ m to 10 ⁇ m. That is, the coexistence layer 60 having a thickness in the range of 0.01 ⁇ m to 10 ⁇ m can be formed.
  • Step S5 for attaching an active material The process of making the self-supporting composite film obtained from the above process into a functional composite film having a predetermined function will be described.
  • An active material (a material capable of inserting and extracting lithium ions) 34 is attached to the self-supporting composite film 100 obtained as described above. As shown in FIG. 4E, the active material 34 is attached so that the active material 34 enters the inside of the network structure 44 of the filamentous carbon film 20 from the surface opposite to the surface on which the metal of the filamentous carbon film 20 is deposited.
  • the active material 34 may be attached so that the active material 34 covers the surface of the filamentous carbon film 20.
  • a paste in which a binder, a conductive material, and the like are mixed with a particulate active material is prepared, applied to the filamentous carbon film 20, and then dried, as shown in FIG.
  • the active material 34 can be attached so that the gas enters the inside of the network structure 44 of the filamentous carbon film 20.
  • the active material 34 can be deposited by depositing the active material 34 on the filamentous carbon film 20 so that the active material 34 covers the surface of the filamentous carbon film 20 (see FIG. 1C). ).
  • a deposition source Si, Sn, SnO, a mixture of Si or Sn and other metals, S, or the like can be used.
  • the evaporation source may be doped with impurities. Examples of such impurities include elements such as nitrogen, phosphorus, aluminum, arsenic, boron, gallium, indium, oxygen, and carbon.
  • the active material 34 adheres to the filamentous carbon film 20, and the function composed of filamentous carbon, metal, and active material.
  • Conductive composite films 300 and 400 are obtained.
  • the obtained functional composite films 300 and 400 are filaments formed between the first layer 40 made of filamentary carbon, the second layer 80 made of metal, and the first layer 40 and the second layer 80.
  • the active material 34 is attached to the filamentous carbon 42 constituting the first layer 40.
  • the functional composite films 300 and 400 manufactured by the above method have a structure in which part or all of the active material 34 enters the network structure 44 of the filamentous carbon film 20, or the active material 34 has a surface of the filamentous carbon 42. It can have a structure attached so that it may cover.
  • the apparatus 150 shown in FIG. 6A mainly includes a roller pair 52 including a driving roller 52a and a driven roller 52b, an endless conveying belt 54 that moves across the roller pair 52, and an upper portion of the conveying belt 54.
  • a suction filter 63 installed below the feeder 56 via the conveyor belt 54, and downstream of the feeder 56 in the conveyance direction and below the conveyor belt 54.
  • the vapor deposition device 58 is provided.
  • the conveyor belt 54 is a mesh belt having heat resistance and a membrane filter function.
  • the supply unit 56 supplies the filamentous carbon dispersion 51 prepared in the above-described step S ⁇ b> 1 to the conveyor belt 54, sucks the dispersion on the conveyor belt 54 by the suction filter 63, and collects the aggregate of filamentous carbon. It remains on the conveyor belt 54.
  • the vapor deposition device 58 includes a boat that accommodates metal pieces therein as a vapor deposition source, and deposits metal on an aggregate of filamentous carbon.
  • the driving roller 52a rotates in the direction indicated by the arrow and the conveyor belt 54 starts to move
  • the filament-like carbon dispersion 51 is continuously supplied from the supply device 56 onto the conveyor belt 54 in a predetermined amount.
  • the liquid component of the dispersion liquid is filtered by 63 and the conveyor belt 54 to form a filamentous carbon aggregate 53 as a solid component on the conveyor belt 54.
  • the filamentous carbon aggregate 53 is conveyed to a position facing the downstream vapor deposition unit 58 by the conveyance belt 54, the metal from the vapor deposition source heated and melted by the vapor deposition unit 58 becomes the filamentous carbon aggregate 53. Adhere to the surface.
  • a composite film 59 in which the metal 55 is attached to one surface of the filamentous carbon aggregate 53 is obtained. Since the composite film 59 is a continuous film, when the front end in the conveyance direction of the composite film 59 is wound up by the driven roller 52b, the tensile force in the tangential direction (horizontal direction) of the driven roller at the front end is sequentially applied. Thus, a long and self-supporting composite film 59 (composite continuous film) is obtained by removing from the conveyor belt 54. The long self-supporting composite film 59 can be appropriately wound around a roller and collected and managed.
  • the feeder 56, the suction filter 63, and the conveyor belt 54 functioned as the filament-like carbon aggregate forming unit, but a coater such as a spray coater or a blade coater and a dryer may be used.
  • the dispersion liquid can be applied onto the conveyor belt with a coater, and the applied dispersion liquid can be dried with a dryer, and the conveyor belt need not have a filter function.
  • a mechanism such as a peeling roller for separating (separating) from the conveying belt 54 by applying a tensile force in the tangential direction (horizontal direction) of the driven roller 52b of the front end of the composite film 59 may be provided.
  • the conveyance belt 54 can also serve as the driving roller 52.
  • a cylinder is used instead of the conveyor belt, and while rotating the cylinder, filamentary carbon is continuously deposited on the upper part, and metal is deposited on the filamentous carbon deposited on the lower part. can do.
  • an aggregate of filamentous carbon can be formed from a dispersion of filamentous carbon by suction filtration.
  • an aggregate of filamentous carbon can be formed from a dispersion of filamentous carbon using a spray coater or a blade coater.
  • One cylinder serves as both the conveyor belt 54 and the driving rollers 52a and 52b.
  • the manufacturing method of the composite film 100a and the functional composite films 300a and 400a mainly includes a step S1 for producing a film made of filamentous carbon (filamentous carbon film), and a filament shape supported by a support (substrate). Step S3 for depositing metal on the carbon film, Step S4 for separating the filamentary carbon film and the metal composite film from the support, and an active material on the surface of the filamentous carbon film opposite to the surface on which the metal is deposited. And attaching step S5.
  • the manufacturing method of the composite film according to this embodiment does not need to have active material adhesion process S5.
  • Step S1 for producing filamentary carbon film> In the embodiment of the manufacturing method of the composite film 100 of the first embodiment and the functional composite films 300 and 400 of the second embodiment, the filamentous carbon film having a network structure is formed in the filamentous carbon film manufacturing step S1. However, in the method of manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment, the filamentous carbon film in which filamentous carbon is oriented (vertically oriented) in the thickness direction of the filamentous carbon film. Form.
  • a substrate (support) 160a on which particles 48 as a catalyst for synthesizing filamentary carbon are formed is disposed in a reactor. Then, the substrate 160a can be produced by circulating the source gas in the reactor while heating. Fe, Co, Ni, etc. can be used as the catalyst, and Si, Al, Mg oxides, etc. can be used as the catalyst carrier. As the source gas, acetylene, ethylene, ethanol, methane or the like can be used. In this manner, as shown in FIG. 5B, the filamentous carbon film 20a having the structure 46 in which the filamentous carbon 42a is vertically oriented can be formed on the substrate 160a. Since the filamentous carbon film 20a produced by the step S1 for producing the filamentous carbon film is supported by the substrate 160a, the manufacturing method includes the step S2 for supporting the produced filamentary carbon film on the substrate. You don't have to.
  • Step S3 for depositing metal in the method of manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment is a process of the method of manufacturing the composite film 100 and the functional composite films 300 and 400. Since it can be performed in the same manner as S3, detailed description is omitted.
  • the metal layer 10a can be formed on the filamentous carbon film 20a.
  • a part of the metal layer 10a has entered (submitted) into the gaps between the filamentous carbons 42a of the filamentous carbon film 20a.
  • Step S4 of separating the composite film from the substrate in the method of manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment includes the composite film 100 and the functional composite films 300 and 400. Since it can carry out similarly to process S4 of this manufacturing method, detailed description is abbreviate
  • the composite film 100a composed of the filamentous carbon film 20a and the metal layer 10a is peeled from the substrate 160a, as shown in FIG. 5D, the metal layer 10a is formed in the gap between the filamentous carbons 42a of the filamentous carbon film 20a.
  • a composite film 100a having a structure in which a part of the film has entered (submerged) is obtained. That is, the obtained composite film 100a has a filament-like shape formed between the first layer 40a made of filamentous carbon 42a, the second layer 80a made of metal, and the first layer 40a and the second layer 80a. It has a coexistence layer 60a in which carbon 42a and metal coexist.
  • Step S5 for attaching an active material The step S5 of attaching the active material in the manufacturing method of the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment is the method of manufacturing the composite film 100 and the functional composite films 300 and 400. Since it can carry out similarly to process S5, detailed description is abbreviate
  • a paste is prepared by mixing a particulate active material with a binder, a conductive material, etc., and this is applied onto the filamentous carbon film 20a and then dried, as shown in FIG. 5 (e).
  • the active material 34a can be attached so that the active material 34a enters the inside of the vertical alignment structure 46 of the filamentous carbon film 20a.
  • the active material 34a can be attached so that the active material 34a covers the surface of the filamentous carbon film 20a (see FIG. 2D).
  • the active material 34a is attached to the filamentous carbon film 20a, and the function is composed of filamentous carbon, metal, and active material.
  • Composite films 300a and 400a are obtained.
  • the obtained functional composite films 300a and 400a are filaments formed between the first layer 40a made of filamentary carbon, the second layer 80a made of metal, and the first layer 40a and the second layer 80a.
  • the active carbon 34a is attached to the filamentous carbon 42a constituting the first layer 40a.
  • the functional composite films 300a and 400a manufactured by the above method have a structure in which part or all of the active material 34a enters the vertical alignment structure 46 of the filamentous carbon film 20a, or the active material 34a is made of the filamentous carbon 42a. It can have a structure attached to cover the surface.
  • the filamentary carbon vertical alignment film is contracted to form a filamentous carbon film 20b having a random network structure 46b composed of the walls 41b of the filamentous carbon 42b.
  • the network structure 46b composed of the walls 41b of the filamentous carbon 42b can be formed as follows. For example, by exposing the filamentary carbon vertical alignment film to a solvent vapor such as ethanol to condense the solvent on the filament carbon film, and then drying the condensed solvent, the filamentous carbon film 20a is formed by the surface tension of the solvent.
  • the network structure 46b which consists of the wall 41b of the filament-like carbon 42b is shrunk and formed.
  • the mesh size of the mesh structure 46b can be controlled, for example, by changing the height of the vertical alignment film of the filamentous carbon 42b.
  • the height of the filamentary carbon vertical alignment film can be controlled, for example, by changing the time for synthesizing the filamentous carbon in the filamentous carbon film manufacturing step S1.
  • the structure formed by the filamentous carbon walls can be controlled by the texture (unevenness) of the surface of the substrate 160a used for synthesizing the filamentous carbon in step S1. Therefore, it is possible to form an arbitrary structure different from the network structure.
  • a vertical alignment film of filamentous carbon is formed using a substrate having a streaky (line-like) texture extending in one direction on the surface as the substrate 160a in step S1, and the composite film 100a is formed in step S4.
  • the filamentary carbon vertical alignment film is contracted to form a streak structure in which filamentary carbon walls are regularly arranged in one direction.
  • the apparatus 170 shown in FIG. 6 (b) mainly includes a roller pair 52 composed of a driving roller 52a and a driven roller 52b, an endless conveying belt 54a that moves across the roller pair 52, and an upper portion of the conveying belt 54a. , A CVD device 73 installed on the downstream side in the transport direction, and a vapor deposition device 58 installed on the downstream side in the transport direction of the CVD device 73 and below the transport belt 54a. .
  • the sputtering apparatus 71 attaches a catalyst 74 such as Fe for synthesizing filamentary carbon to a conveyor belt 54 as a support. It is more preferable that a catalyst carrier such as Al 2 O 3 is attached to the transport belt and then a catalyst 74 such as Fe is attached.
  • the CVD apparatus 73 supplies a synthesis gas such as acetylene to the catalyst in order to synthesize and grow filamentous carbon on the catalyst 74.
  • a CVD apparatus provided with a nozzle having a shower head structure is suitable. Note that the transport belt 54a in this example does not need to have a filter function, unlike the transport belt 54 used in the apparatus shown in FIG.
  • a composite film 79 in which the metal 55 is adhered to one surface of the filamentous carbon aggregate is obtained. Since the composite film 79 is a continuous film, when the front end in the transport direction of the composite film 59 is wound up by the driven roller 52b, a tensile force in the tangential direction (horizontal direction) of the driven roller at the front end is sequentially applied. Then, a long and self-supporting composite film 79 (composite continuous film) is obtained by separating from the transport belt 54a.
  • the conveyance belt 54 a can also serve as the driving roller 52. That is, a cylinder is used instead of the conveyor belt, and while rotating the cylinder, the catalyst is attached to the surface of the cylinder, the filamentous carbon is synthesized, the metal is vapor-deposited, and continuously peeled and recovered.
  • the single cylinder serves as both the conveying belt 54a and the driving rollers 52a and 52b.
  • a mechanism such as a peeling roller for separating (separating) from the conveying belt 54a by applying a tensile force in the tangential direction (horizontal direction) of the driven roller 52b at the front end of the composite film 79 may be provided.
  • the composite membranes 100, 100a, 100b and the functional composite membranes 300, 400, 300a, 400a of the above-described embodiments and modifications are suitable as electrodes in an electrochemical storage device such as a secondary battery typified by a lithium ion battery. Can be used.
  • a lithium ion battery having the functional composite film 300 of the above embodiment as an electrode will be described as an example.
  • an electrode group obtained by laminating or laminating and winding a separator, a negative electrode, a separator, and a positive electrode is housed in a battery case such as a battery can, and then an electrolyte is injected into the battery case.
  • a battery case such as a battery can, and then an electrolyte is injected into the battery case.
  • Can be manufactured.
  • the composite film 300 having the second layer 80 made of aluminum can be used as the positive electrode.
  • the first layer 40 made of filamentous carbon 42, the second layer 80 made of aluminum, and the coexisting layer 60 of filamentous carbon 42 and aluminum are current collectors. Work as.
  • the composite film 300 having the second layer 80 made of copper or nickel can be used as the negative electrode.
  • the first layer 40 made of filamentous carbon 42, the second layer 80 made of copper or nickel, and the coexisting layer 60 of the filamentous carbon 42 and copper or nickel (that is, the filamentous carbon film 20 and the metal layer 10). Works as a current collector.
  • the metal layers 10 it is more preferable to use two electrodes formed as described above and overlap the metal layers 10 so as to face each other because the capacity of the lithium ion battery can be increased. Furthermore, when two electrodes are overlapped, it is more preferable to apply a binder on the surface of at least one metal layer 10 and then bond them together to improve the strength of the electrodes. In addition, since the binder is sandwiched on both sides by the metal layer, the binder is not easily deteriorated and does not inhibit the in-plane conductivity of the metal layer.
  • Examples of the shape of the electrode group include 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, or the like. Can do.
  • examples of the shape of the battery case include a paper shape, a coin shape, a cylindrical shape, and a square shape.
  • the separator may be of any type, and may be, for example, a film having a form of a porous film made of a material such as a polyolefin resin such as polyethylene or polypropylene, or a fluororesin, a nonwoven fabric, or a woven fabric.
  • the electrolyte usually contains an electrolyte and an organic solvent.
  • an electrolyte made of a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) is converted into propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), It is obtained by dissolving in an organic solvent such as ethyl methyl carbonate (EMC).
  • LiPF 6 lithium hexafluorophosphate
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • the composite film 300 used as the electrode of the lithium ion battery of the present embodiment is that the active material 34 is difficult to peel from the first layer 40 even if the volume of the active material 34 changes greatly during charging and discharging. There is an advantage that the electric resistance between the active material 34 and the metal is small. Therefore, the lithium ion battery of this embodiment using the composite film 300 as an electrode has a long life and a high capacity.
  • the composite film 300 of the second embodiment is used as an electrode.
  • the electrode of the lithium ion battery uses the composite film 100, 100a, 100b or the functional composite film 300a of the above-described embodiment and the modified embodiment. It can also be manufactured.
  • the lithium ion battery produced thereby also has a high capacity and a long life.
  • the composite film and the functional composite film according to the present invention are not limited to the electrode of an electricity storage device such as a lithium ion battery, but can also be applied as an electrode of an electricity storage device in various forms, depending on the combination of materials. It is applicable as both a positive electrode and a negative electrode.
  • an electrode active material such as activated carbon is attached on the layer made of filamentous carbon of the composite film, and can be applied as an electrode of an electric double layer capacitor (whether positive electrode or negative electrode).
  • an electrode active material such as graphite is attached on the layer made of filamentous carbon, and can be applied as an electrode (a positive electrode or a negative electrode) of a lithium ion capacitor.
  • the “storage device” means a device that can be repeatedly charged and discharged, and includes a secondary battery such as a lithium ion battery, a capacitor such as an electric double layer capacitor and a lithium ion capacitor.
  • Example 1 4 mg of CNT (eDIPS made by Meijo Nanocarbon) is added to 40 mL of 0.5 wt% SDBS aqueous solution as filamentous carbon, and dispersed for 2 hours at an output of 30 W and a frequency of 45 kHz using an ultrasonic dispersion device (CLEAR VS-50R made by VELVO). To obtain a CNT dispersion. 10 mL of the CNT dispersion was filtered under reduced pressure using a membrane filter having a pore size of 0.1 ⁇ m (VCWP manufactured by Millipore) to produce a CNT film having a thickness of about 20 ⁇ m on the membrane filter.
  • VMWP membrane filter having a pore size of 0.1 ⁇ m
  • the membrane filter with the CNT film formed was impregnated with pure water in a beaker to separate the CNT film and the membrane filter.
  • pure water in the beaker was heated to 100 ° C. with a heater.
  • the CNT film floating on the water surface was scraped off with a Si substrate with a thermal oxide film (hereinafter simply referred to as “substrate”). By these operations, the CNT film was supported on the substrate.
  • Cu was deposited on the CNT film on the substrate as follows.
  • An 80 mm ⁇ 6 mm tungsten boat was installed in the vapor deposition chamber, and a Cu piece (Nilaco Corp. Cu111487, purity 99.9%) was placed thereon, which was used as a vapor deposition source. Since the Cu piece is melted by heating and spreads on the boat, the size of the vapor deposition source is about 30 mm ⁇ 6 mm.
  • the substrate was placed so that the CNT film faced the tungsten boat in parallel. At this time, the distance between the evaporation source and the CNT film was set to 35 mm.
  • the substrate was placed on a quartz glass plate stage having an 18 mm square opening at the center with the CNT film surface facing down, and heated to about 400 ° C. with a PG / PBN heater from the top.
  • the inside of the chamber was depressurized to a level of 10 ⁇ 4 Pa with a turbo pump.
  • a turbo pump By energizing the tungsten boat at 588 W and heating the tungsten boat to about 1790 ° C., the Cu piece was melted and Cu was deposited for 80 seconds.
  • the substrate temperature during vapor deposition was 400 ° C. By the above operation, a Cu film was formed on the CNT film on the substrate.
  • substrate area and the density of copper be a conversion film thickness.
  • CNT-Cu composite film a composite film in which Cu was deposited on the CNT film on the substrate was obtained. Thereafter, the CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film.
  • the obtained CNT-Cu composite film was torn into two and observed with a scanning electron microscope (SEM, Hitachi S-4800). At low magnification, the CNT film appeared to peel off from the Cu film near the tear. However, when observed at a higher magnification, countless fluffy CNTs adhered to the Cu film (see FIG. 7B). From this, it was found that CNT and Cu were mechanically well connected.
  • Comparative Example 1 CNT was added to 4 mg and 10 mL of N-methylpyrrolidone, and after dispersion treatment for 1 hour at an output of 40 W and a frequency of 45 kHz using an ultrasonic dispersion device (CLEAR VS-50R manufactured by VELVO), 0.4 mg of PVDF was added.
  • a paste was prepared by stirring. 1 mL of this paste was applied onto a 10 ⁇ m thick electrodeposited copper foil (Niraco Cu113173, purity 99.9%) and dried at 200 ° C. and 0.01 Torr for 1 hour. The resulting composite film was mechanically peeled from the substrate and torn into two.
  • Example 2 A CNT film supported on a substrate was produced in the same manner as in Example 1 except that the filtration amount of the CNT dispersion was 0.3 mL. When the planar structure of the obtained CNT film was observed with an SEM, a network structure in which CNTs were intertwined was formed (see FIG. 8A).
  • a Cu film was formed on the CNT film on the substrate in the same manner as in Example 1 except that the tungsten boat was heated to about 1640 ° C. at 462 W during Cu deposition and the deposition time was 1 second.
  • the Cu film thickness (converted film thickness) obtained in the same manner as in Example 1 was 0.033 ⁇ m.
  • FIG. 8B shows a planar SEM image of the CNT-Cu composite film obtained as described above. Note that the planar SEM image in FIG. 8B has a higher magnification than the planar SEM image in FIG. 8A. From the planar SEM image of FIG. 8B, it was observed that particulate Cu was embedded in the CNT network structure. From this, it was found that a coexistence layer in which CNT and Cu coexist was formed.
  • Example 3 A CNT—Cu composite film was produced in the same manner as in Example 2 except that the tungsten boat was heated to about 1780 ° C. at 576 W during Cu deposition and the deposition time was 3 seconds. The converted film thickness of the Cu film formed by vapor deposition was 0.14 ⁇ m.
  • a planar SEM image of the CNT—Cu composite film produced in this example is shown in FIG. 8C. Note that the planar SEM image in FIG. 8C has a higher magnification than the planar SEM image in FIG. 8A. From the planar SEM image of FIG. 8C, it was observed that the particulate Cu was embedded in the CNT network structure. From this, it was found that a coexistence layer in which CNT and Cu coexist was formed.
  • Example 4 A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1750 ° C. at 550 W during Cu deposition and the deposition time was 4 seconds. The converted film thickness of the Cu film formed by vapor deposition was 0.38 ⁇ m.
  • FIG. 8D shows a planar SEM image of the CNT—Cu composite film produced in this example. From the planar SEM image, Cu was close to a continuous film, and a small amount of CNT was seen on Cu, indicating that Cu was deposited to the vicinity of the outermost surface of the network structure.
  • Example 5 A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1720 ° C. at 528 W during Cu deposition and the deposition time was 8 seconds. The converted film thickness of the Cu film formed by vapor deposition was 1.36 ⁇ m.
  • FIG. 8E shows a planar SEM image of the CNT—Cu composite film produced in this example. It was found that a continuous film of Cu was formed on the CNT film.
  • Example 6 A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1720 ° C. at 525 W during Cu deposition and the deposition time was 24 seconds. The converted film thickness of the Cu film formed by vapor deposition was 4.97 ⁇ m. A planar SEM image of the CNT-Cu composite film produced in this example is shown in FIG. 8F. It was found that a continuous film of Cu was formed on the CNT film.
  • Example 7 A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1810 ° C. at 600 W during Cu deposition and the deposition time was 60 seconds. The converted film thickness of the Cu film formed by vapor deposition was 6.08 ⁇ m. A planar SEM image of the CNT-Cu composite film produced in this example is shown in FIG. 8G. It was found that a continuous film of Cu was formed on the CNT film.
  • Example 8 A CNT—Cu composite film was produced in the same manner as in Example 2 except that the tungsten boat was heated to about 1740 ° C. at 538 W during the deposition of Cu and the deposition time was set to 80 seconds. The converted film thickness of the Cu film formed by vapor deposition was 17.97 ⁇ m. A planar SEM image of the CNT-Cu composite film produced in this example is shown in FIG. 8H. It was found that a continuous film of Cu was formed on the CNT film.
  • Example 9 A CNT-Cu composite film was obtained in the same manner as in Example 1 except that the filtration amount of the CNT dispersion was 3 mL, and the tungsten boat was heated to about 1720 ° C. at 528 W during Cu deposition, and the deposition time was 80 seconds. . Next, the CNT-Cu composite film was mechanically peeled from the substrate, and Si was deposited on the CNT film of the CNT-Cu composite film as follows. A carbon boat having eight evaporation sections of 2 mm ⁇ 4 mm is installed in the vapor deposition chamber, and an organic substance and oxide adhering to the surface are removed on this using a 5 to 10% HF solution (purity) 99.9999% or more) was placed and used as a deposition source.
  • a 5 to 10% HF solution purity
  • the size of the deposition source is about 50 mm 2 .
  • the CNT-Cu composite film was disposed so that the CNT film faced the tungsten boat in parallel. At this time, the distance between the deposition source and the CNT film was 45 mm.
  • the CNT-Cu composite film was fixed in close contact with the surface of a copper block whose temperature can be controlled with a ceramic heater and an air-cooled tube.
  • the pressure in the chamber was reduced to 1 Pa with a rotary pump, and then argon gas was introduced at 10 sccm, and the pressure in the chamber was set to 13.3 Pa (0.1 Torr). After the pressure became constant, the CNT-Cu composite film was heated to 300 ° C.
  • Comparative Example 2 On the electrodeposited copper foil having a thickness of 10 ⁇ m (Niraco Cu113173, purity 99.9%), Si was deposited under the same conditions as in Example 9 to prepare a Cu—Si composite film.
  • a coin cell was prepared using the composite film of Comparative Example 2 as a negative electrode, a charge / discharge cycle test was performed, and changes in the discharge capacity were examined.
  • Example 10 CNT dispersion was adjusted by adding 2.5 mg of CNT to 20 mL of isopropanol and dispersing with ultrasonic waves, except that 20 mL of the dispersion was filtered using PTFE manufactured by Millipore with a pore size of 0.5 ⁇ m as a membrane filter.
  • PTFE manufactured by Millipore with a pore size of 0.5 ⁇ m as a membrane filter.
  • a CNT film supported on a substrate was produced.
  • a Cu film was formed on the CNT film on the substrate in the same manner as in Example 1 except that the tungsten boat was heated to about 1610 ° C. at 440 W during the deposition of Cu and the deposition time was set to 3 seconds.
  • the obtained CNT—Cu composite film had a CNT film thickness of 37 ⁇ m and a Cu film thickness of 0.031 ⁇ m.
  • FIGS. 11B to 11D show digital camera photographs of the CNT-Cu composite film after peeling from the substrate.
  • Cu itself is 0.031 ⁇ m, which is only one hundredth of the thickness of a general copper foil, and is not self-supporting, but the CNT film is self-supporting.
  • Cu foil is generally used for the negative electrode of a lithium ion battery, it is problematic that the Cu foil is heavy.
  • the weight per unit area was reduced to about 1/10 for the CNT film of this example and about 1/500 for the Cu vapor deposition film, compared to the commercially available Cu foil.
  • Example 11 A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1720 ° C. at 525 W during Cu deposition and the deposition time was 24 seconds. The thickness of the CNT film was about 1.5 ⁇ m. The converted film thickness of the Cu film formed by vapor deposition was 4.97 ⁇ m.
  • the obtained CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film.
  • Digital camera photographs of the obtained CNT-Cu composite film are shown in FIGS. 12 (a) to 12 (c).
  • a CNT-Cu composite film could be obtained as a self-supporting film.
  • Cu foil is generally used for the negative electrode of a lithium ion battery, it is problematic that the Cu foil is heavy. The weight per unit area was reduced to about 1/50 for the CNT film of this example and about 1/3 for the Cu vapor deposition film, compared to the commercially available Cu foil.
  • Example 12 Al was deposited with an average film thickness of 15 nm by RF magnetron sputtering on a Si substrate with a thermal oxide film (hereinafter simply referred to as “substrate”), and Al was oxidized by exposure to the atmosphere to form an Al 2 O 3 film. Furthermore, Fe was laminated with an average film thickness of 1 nm by RF magnetron sputtering to prepare a substrate with a catalyst. After the substrate was placed in a quartz glass circular tubular reactor and reduced for 10 minutes at 800 ° C.
  • a CNT-Cu composite film was obtained. Thereafter, the CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film.
  • a cross-sectional SEM image of the obtained CNT-Cu composite film is shown in FIG. 13A. It was found that a continuous film of Cu was formed on the vertically aligned CNT film.
  • FIGS. 13B and 13C A digital camera photograph of the CNT-Cu composite film in which the CNT vertical alignment film is contracted is shown in FIGS. 13B and 13C, a cross-sectional SEM image is shown in FIG. 13D, and a planar SEM image is shown in FIG. 13E.
  • FIG. 13B shows a CNT-Cu composite film viewed from the Cu film side
  • FIG. 13C shows a CNT-Cu composite film viewed from the CNT film side.
  • a network structure was obtained in which the CNT walls were standing upright at intervals of 10 to 20 ⁇ m on the Cu thin film. The interval between CNT walls can be changed over a wide range from 6 to 42 ⁇ m by performing the same operation except that the height of the CNT vertical alignment film is changed to 10 to 120 ⁇ m by changing the CNT synthesis time. It was.
  • Example 13 A Cu plate (Niraco Cu113321, purity 99.96%) (hereinafter simply referred to as “Cu substrate”) was prepared. An SEM image of the surface of the Cu substrate is shown in FIG. 14A. The Cu substrate had a streak texture (unevenness) extending in one direction on the surface. The average pitch of the irregularities was about 9 ⁇ m.
  • a Cu substrate with a catalyst was prepared by depositing Ta with an average film thickness of 30 nm, Al 2 O 3 with an average film thickness of 50 nm, and Fe with an average film thickness of 1 nm on a Cu substrate by RF magnetron sputtering. After the substrate was placed in a quartz glass circular tubular reactor and reduced for 10 minutes at 800 ° C.
  • Cu was deposited on the CNT film in the same manner as the Cu deposition in Example 12. Thereby, a Cu film was formed on the single-walled CNT vertical alignment film on the Cu substrate.
  • the converted film thickness of the Cu film formed by vapor deposition was 11 ⁇ m.
  • FIG. 14B A digital camera photograph of the obtained CNT-Cu composite film is shown in FIG. 14B, and a cross-sectional SEM image is shown in FIG. 14C.
  • the left side of FIG. 14B shows the Cu substrate after the CNT-Cu composite film is peeled off, and the right side shows the CNT-Cu composite film as viewed from the CNT film side. From these figures, it was found that a continuous film of Cu was formed on the vertically aligned CNT film.
  • the CNT vertical alignment film was shrunk by surface tension by exposing it to ethanol vapor with the CNT side facing down, condensing ethanol on the CNT, and then drying.
  • a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film is shown in FIG. 14D
  • an oblique SEM image is shown in FIG. 14E
  • a planar SEM image is shown in FIG. 14F.
  • a streak structure in which the CNT walls were regularly arranged in one direction on the Cu thin film was obtained.
  • the wall height was 5-7 ⁇ m.
  • the interval between CNT walls can be changed over a wide range from 10 to 64 ⁇ m by performing the same operation except that the height of the CNT vertical alignment film is changed to 9 to 64 ⁇ m by changing the CNT synthesis time. It was.
  • Example 14 Add 2 mg of several CNTs produced by the fluidized bed method described in Carbon 80, 339-350 (2014) as filamentous carbon to 30 mL of ethanol, and disperse for 40 minutes at an output of 90 W and a frequency of 45 kHz using an ultrasonic dispersing device. To obtain a CNT dispersion. 30 mL of the CNT dispersion liquid was filtered under reduced pressure using a membrane filter having a pore size of 0.1 ⁇ m to produce a CNT film having a thickness of about 30 ⁇ m on the membrane filter.
  • the CNT film and the membrane filter were separated from the membrane filter on which the CNT film was formed using tweezers to obtain a CNT self-supporting film.
  • the CNT film was supported on the substrate by placing the CNT film on the substrate while being wetted with ethanol and drying.
  • the sheet resistance of the CNT film was 5 ⁇ / sq.
  • an Al piece (Nilaco Al011487, purity 99.99%) was used as the deposition source, the substrate heating temperature was about 150 ° C., the tungsten boat was heated to about 1700 ° C. at 550 W, and the deposition time was 10 seconds. Except for the above, an Al film was deposited on the CNT film on the substrate in the same manner as Cu deposition in Example 12. The converted film thickness of the Al film formed by vapor deposition was 6.3 ⁇ m.
  • FIGS. 15A and 15B A digital camera photograph of the obtained CNT-Al composite film is shown in FIGS. 15A and 15B, a planar SEM image is shown in FIG. 15C, and a cross-sectional SEM image is shown in FIG. 15D. The left side of FIG.
  • FIG. 15A shows the CNT-Al composite film seen from the Al film side, and the right side shows the remaining CNT film removed from the substrate after the CNT-Al composite film is peeled off.
  • FIG. 15B shows the CNT-Al composite film viewed from the CNT film side.
  • a composite film was obtained in which both were composed of CNT and Al but were well connected.
  • the sheet resistance of the CNT-Al composite film was 0.011 ⁇ / sq, which was lower than that of the CNT film alone.
  • the remaining CNTs after peeling the CNT-Al composite film maintained the film structure.
  • Another CNT-Al composite film can be newly obtained by holding the CNT film on the substrate again and forming a metal such as Al and peeling it off. That is, a CNT-Al composite film can be repeatedly obtained from the CNT film supported on the substrate.
  • Example 15 A CNT dispersion was obtained in the same manner as in Example 14 except that 0.5 wt% SDBS aqueous solution was used instead of ethanol. The CNT dispersion was centrifuged at 3000 rpm for 60 minutes, and the supernatant was collected. 20 mL of pure water was added to 0.5 mL of the supernatant and filtered under reduced pressure using a membrane filter having a pore size of 0.1 ⁇ m to produce a CNT film having a thickness of about 0.1 to 0.15 ⁇ m on the membrane filter.
  • the membrane filter on which the CNT film was formed was impregnated with pure water in a beaker to separate the CNT film and the membrane filter.
  • the CNT film floating on the water surface was scraped off with a substrate.
  • the CNT film was supported on the substrate.
  • a substrate with a CNT film was placed in a quartz glass tube, and kept at 800 ° C. for 20 minutes under a flow of 4 vol% H 2 diluted with Ar to decompose and remove SDBS adhering to the CNT film.
  • the substrate was heated to about 350 ° C. with a PG / PBN heater, the tungsten boat was heated to about 1700 ° C. with 500 W, and the deposition time was 30 seconds.
  • An Al film was deposited on the CNT film.
  • the converted film thickness of the Al film formed by vapor deposition was 5.2 ⁇ m.
  • FIGS. 16A and 16B A digital camera photograph of the obtained CNT-Al composite film is shown in FIGS. 16A and 16B, a planar SEM image is shown in FIG. 16C, and a cross-sectional SEM image is shown in FIG. 16D.
  • the left side of FIG. 16A shows the substrate after the CNT-Al composite film is peeled off, and the right side shows the CNT-Al composite film as viewed from the Al film side.
  • FIG. 16B shows a CNT-Al composite film viewed from the CNT film side.
  • a composite film was obtained in which both were composed of CNT and Al but were well connected.
  • a single CNT film having a thickness of 0.1 to 0.15 ⁇ m is too thin to be self-supporting, but it can be made self-supporting by being combined with Al, and a low resistance of 0.011 ⁇ / sq has been realized.
  • Example 16 Filamentous carbon dispersion was filtered under reduced pressure in the same manner as in Example 14 except that 0.1 mg of several layers of CNT and 0.9 mg of vapor grown carbon fiber (CF) (VGCF manufactured by Showa Denko KK) were used as the filamentous carbon. On the membrane filter, a composite film (CF + CNT composite film) made of a mixture of CF and CNT having a thickness of about 13 ⁇ m was produced.
  • CF vapor grown carbon fiber
  • the CF + CNT composite membrane was separated from the membrane filter using tweezers and supported on the substrate.
  • FIGS. 17A and 17B A digital camera photograph of the obtained CF + CNT-Al composite film is shown in FIGS. 17A and 17B, a planar SEM image is shown in FIG. 17C, and a cross-sectional SEM image is shown in FIG. 17D.
  • FIGS. 17A and 17B A digital camera photograph of the obtained CF + CNT-Al composite film is shown in FIGS. 17A and 17B, a planar SEM image is shown in FIG. 17C, and a cross-sectional SEM image is shown in FIG. 17D. The left side of FIG.
  • FIG. 17A shows the substrate after the CF + CNT-Al composite film is peeled off, and the right side shows the CF + CNT-Al composite film as viewed from the Al film side.
  • FIG. 17B shows a CF + CNT-Al composite film viewed from the CF + CNT composite film side.
  • Example 17 CNT was synthesized in the same manner as in Example 12, and a single-walled CNT vertical alignment film having a thickness of 6 ⁇ m was formed on the substrate.
  • a cross-sectional SEM image of the single-walled CNT vertical alignment film is shown in FIG. 18A.
  • an Al film was deposited on the CNT film on the substrate in the same manner as in Example 15 except that the tungsten boat was heated to about 1700 ° C. at 520 W.
  • the converted film thickness of the Al film formed by vapor deposition was 5.0 ⁇ m.
  • FIGS. 18B and 18C A digital camera photograph of the obtained CNT-Al composite film is shown in FIGS. 18B and 18C, and a cross-sectional SEM image is shown in FIG. 18D.
  • the substrate after the CNT-Al composite film is peeled off is shown on the left side of FIG. 18B, and the CNT-Al composite film viewed from the CNT film side is shown on the right side.
  • FIG. 18C shows a CNT-Al composite film viewed from the Al film side.
  • a composite film was obtained in which both were composed of CNT and Al but were well connected.
  • a single CNT vertical alignment film having a thickness of 6 ⁇ m is not self-supporting because of its vertical alignment and thinness, but it can be made self-supporting by compounding with Al, and a low resistance of 0.013 ⁇ / sq has been realized.
  • Example 18 A CNT dispersion was obtained in the same manner as in Example 14 except that 0.5 mg of several-layer CNT was used as the filamentous carbon. Moreover, activated carbon particles (AC) (YP-80F manufactured by Kuraray Chemical Co., Ltd.) (4.5 mg) was added to ethanol (30 mL), and the dispersion liquid was subjected to dispersion treatment at an output of 90 W and a frequency of 45 kHz for 40 minutes using an ultrasonic dispersion device. Obtained. By mixing these two dispersions, 60 mL of a dispersion (AC + CNT mixed dispersion) containing AC and CNT at a mass ratio of 9: 1 was obtained.
  • AC activated carbon particles
  • the AC + CNT mixed dispersion was filtered under reduced pressure using a membrane filter (JMWP manufactured by Millipore) having a pore size of 5 ⁇ m, and a composite film (AC + CNT composite film) made of a mixture of AC and CNT having a thickness of about 70 ⁇ m was formed on the membrane filter.
  • a membrane filter JMWP manufactured by Millipore
  • AC + CNT composite film made of a mixture of AC and CNT having a thickness of about 70 ⁇ m was formed on the membrane filter.
  • the AC + CNT composite membrane was separated from the membrane filter using tweezers, dried at 150 ° C. for 2 hours, and then supported on the substrate.
  • Al piece (Niraco Al011487, purity 99.99%) was used as a deposition source, the substrate heating temperature was about 150 ° C., the pressure in the chamber was 1 ⁇ 10 ⁇ 3 Pa, and the tungsten boat was about 110 W.
  • Al was vapor-deposited on the AC + CNT composite film in the same manner as the Cu vapor deposition in Example 1 except that the temperature was raised to 1700 ° C. and the vapor deposition time was 10 seconds.
  • the amount of Al source material during vapor deposition was changed to four types of 10, 20, 30, 40 mg, so that the equivalent film thickness was 0.3, 0.5, 0.8, 1.7 ⁇ m and 4 A street Al film was obtained.
  • FIG. 19A shows an AC + CNT-Al composite film viewed from the Al film side. As shown in these figures, a composite film composed of only AC, CNT, and Al and well connected to each other was obtained.
  • AC alone does not stand by itself because the adhesion between ACs is too low, but it can be made independent by combining CNT and Al.
  • the sheet resistance of the AC + CNT-Al composite film is 0.24, 0.14, 0.073, 0.003 when the equivalent film thickness of the Al film is 0.3, 0.5, 0.8, and 1.7 ⁇ m, respectively. It was 036 ⁇ / sq (see FIG. 19D).
  • the AC + CNT-Al composite film and the AC + CNT-Al composite film having an equivalent film thickness of 0.3, 0.5, 0.8, 1.7 ⁇ m are used as the working electrode, the AC-CNT film as the counter electrode, and Ag / AgCl.
  • the electrode as a reference electrode, cyclic voltammetry was performed in a 1M Na 2 SO 4 aqueous solution. The sweep potential range was ⁇ 1.0 to 0.6 V, and the sweep rate was 5 to 1000 mV / s.
  • FIG. 19E shows the sweep rate dependence of the specific capacity.
  • the AC + CNT film showed a high capacity of 108 F / g (based on the total electrode mass AC + CNT) at a low scanning speed of 5 mV / s, but the capacity greatly decreased to 15 F / g at a high scanning speed of 200 mV / s.
  • the AC + CNT-Al composite film on which Al with a converted film thickness of 0.8 ⁇ m is deposited exhibits a high capacity of 116 F / g (total electrode mass AC + CNT + Al standard) at a low scanning speed of 5 mV / s, and a high scanning speed of 200 mV / s. Even in s, the high capacity of 86 F / g was maintained.
  • the rate characteristics of the AC + CNT composite film were dramatically improved.
  • the composite film of this invention and its manufacturing method are not limited to the said embodiment, It can change suitably within the range of the technical idea described in the claim. it can.
  • the apparatuses for continuously producing the composite membranes of the first embodiment and the third embodiment have been described by taking the apparatus shown in FIGS. 6A and 6B as an example. It is only a specific example, and various changes and improvements can be made.
  • the conveyance belt is circulated using a pair of rolls around which the conveyance belt is stretched as the conveyance apparatus.
  • the conveyance belt is linear or curved or You may arrange
  • a drum (single roll) can be used instead of using a conveyor belt or a roll pair as the conveyor.
  • the surface of the drum can be a support on which an aggregate of filamentous carbon is formed, and a mechanism for forming an aggregate of filamentous carbon or a mechanism for depositing metal can be installed around the drum. it can.
  • a vapor deposition apparatus and a supply device for applying an active material on the downstream side in the transport direction of the apparatus shown in FIGS. 6A and 6B, the composite of the second embodiment and the fourth embodiment is provided. It can be retrofitted into a device that continuously produces membranes.
  • the composite film of the present invention has an advantage that it has low resistance and is difficult to peel from the current collector even if the volume of the active material changes. Therefore, by applying the composite film of the present invention to an electrode of a lithium ion battery, it is possible to increase the capacity and life of the lithium ion battery.

Abstract

A composite film 100 consisting exclusively of a filamentous carbon layer 20 formed of filamentous carbon 42 and a metal layer 10 formed of a metal, wherein a part or the whole of the metal layer 10 overlaps a part of the filamentous carbon layer 20 so as to give a coexisting area 60 where the filamentous carbon 42 and the metal coexist. Provided are the composite film 100 that has a novel structure and is self-supporting and a method for manufacturing the same.

Description

複合膜及びその製造方法Composite membrane and manufacturing method thereof
　本発明は、複合膜及びその製造方法、並びに、その複合膜を用いた電極及び蓄電デバイスに関する。 The present invention relates to a composite film, a manufacturing method thereof, and an electrode and an electricity storage device using the composite film.
　リチウムイオン電池のような二次電池や電気二重層キャパシタなどの蓄電デバイスは、パソコン、携帯電話などのモバイル機器の電源として使用されており、近年はこれらのモバイル機器用途のみならず、電気自動車やハイブリッド車などＣＯ２の環境負荷を小さくすることができる自動車の電源としても使用されている。しかし、電気自動車の普及のためには、リチウムイオン電池の重さ及び体積あたりの容量を増加させ、電気自動車による長距離の移動を可能にすることが必要である。 Energy storage devices such as secondary batteries such as lithium-ion batteries and electric double layer capacitors are used as power sources for mobile devices such as personal computers and mobile phones. In recent years, not only mobile devices but also electric vehicles and It is also used as a power source for automobiles that can reduce the environmental load of CO 2 such as hybrid cars. However, for the popularization of electric vehicles, it is necessary to increase the weight and capacity per volume of a lithium ion battery and to enable long-distance movement by electric vehicles.
　リチウムイオン電池の電極は、充放電時にリチウムイオンの吸蔵及び放出を行う活物質を備えている。活物質としては、一般的に、正極ではリチウム金属酸化物が使用され、負極では黒鉛が使用される。このような活物質を用いた電極は一般的に、活物質の粉末を、ポリフッ化ビニリデン等の非導電性ポリマーからなるバインダー、及び炭素繊維（ＣＦ）、カーボンブラック等からなる導電体と混合してペースト状にし、これを集電体であるアルミニウム（Ａｌ）箔や銅（Ｃｕ）箔に塗布して焼成することによって製造される。なお、バインダーは活物質を集電体上に固定する目的で使用され、導電体は集電体と活物質を電気的に接続する目的で使用されている。図２０に示すように、このようにして製造された電極５００では、集電体１８０上に、活物質１３０、導電体１４０及び非導電性のバインダー１５０が混在する層が形成されている。 The electrode of the lithium ion battery includes an active material that occludes and releases lithium ions during charging and discharging. As the active material, lithium metal oxide is generally used for the positive electrode, and graphite is used for the negative electrode. In an electrode using such an active material, an active material powder is generally mixed with a binder made of a non-conductive polymer such as polyvinylidene fluoride and a conductor made of carbon fiber (CF), carbon black, or the like. It is manufactured by applying a paste to an aluminum (Al) foil or a copper (Cu) foil as a current collector and baking it. The binder is used for the purpose of fixing the active material on the current collector, and the conductor is used for the purpose of electrically connecting the current collector and the active material. As shown in FIG. 20, in the electrode 500 manufactured in this way, a layer in which the active material 130, the conductor 140, and the nonconductive binder 150 are mixed is formed on the current collector 180.
　現在、リチウムイオン電池を高容量化するために、負極の活物質として黒鉛に代えてシリコン（Ｓｉ）を使用することが検討されている。Ｓｉを負極の活物質として用いた負極の理論放電容量は約４２００ｍＡｈ／ｇと大きく、黒鉛を用いた負極の理論放電容量の１０倍以上になり得るとされている。特許文献１において、図２１に示すように集電体１８０上に直接Ｓｉからなる柱状構造体１３２を形成した電極が記載されている。 Currently, in order to increase the capacity of lithium ion batteries, the use of silicon (Si) instead of graphite as an active material for the negative electrode is being studied. The theoretical discharge capacity of the negative electrode using Si as the active material of the negative electrode is as large as about 4200 mAh / g, and is said to be 10 times or more the theoretical discharge capacity of the negative electrode using graphite. Patent Document 1 describes an electrode in which a columnar structure 132 made of Si is directly formed on a current collector 180 as shown in FIG.
ＷＯ２０１１／０７１１５４WO2011 / 071154
　図２０に示されるような従来の電極５００では、活物質１３０と集電体１８０の間の界面が二次元的であり接触面積が小さいことに加え、更にその二次元的な界面に非導電性のバインダー１５０が存在するため、活物質１３０と集電体１８０の間の抵抗が大きい。それゆえ、リチウムイオン電池の高容量化が妨げられる。また、リチウムイオン電池の使用中にバインダー１５０が劣化して活物質１３０が集電体１８０から剥離するという問題もある。 In the conventional electrode 500 as shown in FIG. 20, the interface between the active material 130 and the current collector 180 is two-dimensional and the contact area is small, and further, the two-dimensional interface is non-conductive. Therefore, the resistance between the active material 130 and the current collector 180 is large. Therefore, it is impeded to increase the capacity of the lithium ion battery. Further, there is a problem that the active material 130 is peeled off from the current collector 180 due to deterioration of the binder 150 during use of the lithium ion battery.
　また、図２１に示されるような、集電体１８０上に直接Ｓｉの柱状構造体を形成して構成される電極をリチウムイオン電池の負極に用いた場合、充放電時のリチウムイオンの吸蔵及び放出に伴うＳｉ活物質の体積変化が大きいために、充放電サイクル中にＳｉが集電体から剥離することがある。それゆえ、このような負極を用いたリチウムイオン電池は、サイクル特性などの蓄電特性が低いという問題がある。このため、サイクル特性に優れた蓄電デバイスが要望されている。 In addition, when an electrode configured by directly forming a Si columnar structure on a current collector 180 as shown in FIG. 21 is used for a negative electrode of a lithium ion battery, occlusion of lithium ions during charge / discharge and Since the volume change of the Si active material accompanying the release is large, Si may peel from the current collector during the charge / discharge cycle. Therefore, a lithium ion battery using such a negative electrode has a problem of low storage characteristics such as cycle characteristics. For this reason, the electrical storage device excellent in cycling characteristics is desired.
　そこで本発明の目的は、高容量で且つサイクル特性の優れた蓄電デバイスの電極として用いることができる複合膜、並びにその製造方法及び製造装置を提供することにある。また、本発明の別の目的は、新規な構造を有するフィラメント状炭素の集合体を有する自立膜、並びにその製造方法及び製造装置を提供することにある。本発明のさらなる目的は、種々の用途に使用可能で且つ自立性のある機能性複合膜、並びにその製造方法及び製造装置を提供することにある。 Accordingly, an object of the present invention is to provide a composite film that can be used as an electrode of an electricity storage device having a high capacity and excellent cycle characteristics, and a method and an apparatus for manufacturing the composite film. Another object of the present invention is to provide a self-supporting film having an aggregate of filamentous carbon having a novel structure, and a manufacturing method and manufacturing apparatus therefor. It is a further object of the present invention to provide a functional composite film that can be used for various applications and is self-supporting, as well as a manufacturing method and a manufacturing apparatus thereof.
　本発明の第１の態様に従えば、フィラメント状炭素から構成されたフィラメント状炭素層と、
　金属から構成された金属層とだけからなり、
　前記金属層の一部または全部が前記フィラメント状炭素層の一部と重複して、前記フィラメント状炭素と前記金属が共存する共存領域を有することを特徴とする自立した複合膜が提供される。 According to the first aspect of the present invention, a filamentous carbon layer composed of filamentous carbon;
It consists only of a metal layer composed of metal,
A self-supporting composite film is provided in which a part or all of the metal layer overlaps with a part of the filamentous carbon layer to have a coexistence region where the filamentous carbon and the metal coexist.
　前記複合膜において、前記金属層の一部が前記フィラメント状炭素層の一部と重複していてよい。 In the composite film, a part of the metal layer may overlap with a part of the filamentous carbon layer.
　前記複合膜において、前記フィラメント状炭素層が網目構造を有し、
　前記共存領域において、前記網目構造の網目内に前記金属が入り込んでいてよい。 In the composite film, the filamentous carbon layer has a network structure,
In the coexistence region, the metal may enter the mesh of the mesh structure.
　前記複合膜において、前記フィラメント状炭素層が前記フィラメント状炭素層の厚み方向に前記フィラメント状炭素が配向した垂直配向構造を有し、前記共存領域において、前記垂直配向構造の前記フィラメント状炭素間の空隙に前記金属が入り込んでいてよい。前記フィラメント状炭素が束となって、前記フィラメント状炭素層の厚み方向に直立した壁を形成してもよい。 In the composite film, the filamentous carbon layer has a vertical alignment structure in which the filamentous carbon is aligned in a thickness direction of the filamentous carbon layer, and in the coexistence region, the filamentous carbon layer has a vertical alignment structure. The metal may enter the gap. The filamentous carbon may be bundled to form an upright wall in the thickness direction of the filamentous carbon layer.
　本発明の第２の態様に従えば、金属から構成される金属層と
　フィラメント状炭素の集合体とだけからなり、
　前記フィラメント状炭素の集合体の一部が前記金属層中に含まれており、
　前記フィラメント状炭素の集合体の他部が前記金属層上で露出していることを特徴とする自立した複合膜が提供される。 According to the second aspect of the present invention, it consists only of a metal layer composed of metal and an aggregate of filamentous carbon,
A part of the aggregate of filamentous carbon is included in the metal layer,
A self-supporting composite film is provided in which the other part of the aggregate of filamentous carbon is exposed on the metal layer.
　第１の態様及び第２の態様の複合膜において、前記フィラメント状炭素がカーボンナノチューブを含んでよい。 In the composite film of the first aspect and the second aspect, the filamentous carbon may include carbon nanotubes.
　前記複合膜において、前記金属がＣｕ、Ａｌ又はＮｉであってよい。 In the composite film, the metal may be Cu, Al, or Ni.
　本発明の第３の態様に従えば、第１の態様又は第２の態様の自立した複合膜と、
　前記フィラメント状炭素に付着した活物質とを有する機能性複合膜が提供される。 According to a third aspect of the present invention, the self-supporting composite membrane of the first aspect or the second aspect;
A functional composite film having an active material attached to the filamentous carbon is provided.
　本発明の第４の態様に従えば、フィラメント状炭素から構成されたフィラメント状炭素膜を作製する工程と、
　支持体上に支持された前記フィラメント状炭素膜上に金属を蒸着する工程と、
　前記フィラメント状炭素膜及び前記金属の複合膜を前記支持体から分離する工程とを有する複合膜の製造方法が提供される。 According to the fourth aspect of the present invention, a step of producing a filamentous carbon film composed of filamentous carbon;
Depositing a metal on the filamentous carbon film supported on a support;
There is provided a method for producing a composite membrane comprising a step of separating the filamentous carbon membrane and the composite membrane of metal from the support.
　前記複合膜の製造方法の前記フィラメント状炭素膜を作製する工程において、網目構造を有する前記フィラメント状炭素膜を作製してよい。 In the step of producing the filamentous carbon film in the method for producing the composite film, the filamentous carbon film having a network structure may be produced.
　前記複合膜の製造方法の前記フィラメント状炭素膜を作製する工程が、前記フィラメント状炭素膜の厚さ方向に前記フィラメント状炭素が配向するように、前記フィラメント状炭素を形成することを含んでよい。さらに、前記フィラメント状炭素膜及び前記金属の複合膜を前記支持体から分離する工程の後に、前記フィラメント状炭素膜を収縮させて、前記フィラメント状炭素の束からなる前記フィラメント状炭素層の厚さ方向に直立した壁を形成する工程を含んでよい。 The step of producing the filamentous carbon film of the method for producing the composite film may include forming the filamentous carbon so that the filamentous carbon is oriented in a thickness direction of the filamentous carbon film. . Further, after the step of separating the filamentous carbon film and the metal composite film from the support, the filamentous carbon film is contracted to reduce the thickness of the filamentous carbon layer comprising the bundle of filamentous carbon. Forming a wall upright in the direction may be included.
　前記複合膜の製造方法は、前記フィラメント状炭素膜上に金属を蒸着する工程の前に、前記フィラメント状炭素膜を前記支持体により支持する工程を含んでよい。 The method for producing the composite film may include a step of supporting the filamentous carbon film by the support before the step of depositing a metal on the filamentous carbon film.
　前記複合膜の製造方法において、前記支持体を移動させながら、移動方向上流側で前記支持体上に前記フィラメント状炭素膜を作製し、前記移動方向の下流側で前記支持体上の前記フィラメント状炭素膜に前記金属を蒸着してもよい。 In the method for producing the composite membrane, the filament-like carbon membrane is produced on the support on the upstream side in the movement direction while moving the support, and the filament-like carbon on the support on the downstream side in the movement direction. The metal may be deposited on the carbon film.
　前記複合膜の製造方法は、前記フィラメント状炭素膜の前記金属を蒸着した面と反対の面上に活物質を付着させる工程をさらに有してもよい。 The method for producing the composite film may further include a step of attaching an active material on the surface of the filamentous carbon film opposite to the surface on which the metal is deposited.
　本発明の第５の態様に従えば、第４の態様の製造方法によって形成された複合膜が提供される。 According to the fifth aspect of the present invention, there is provided a composite film formed by the manufacturing method of the fourth aspect.
　本発明の第６の態様に従えば、第１、第２又は第５の態様の複合膜または第３の態様の機能性複合膜を有する電極が提供される。 According to the sixth aspect of the present invention, there is provided an electrode having the composite film of the first, second or fifth aspect or the functional composite film of the third aspect.
　本発明の第７の態様に従えば、第６の態様の電極を備える蓄電デバイスが提供される。 According to the seventh aspect of the present invention, an electricity storage device including the electrode of the sixth aspect is provided.
　本発明の第８の態様に従えば、金属層と、フィラメント状炭素の集合体だけを有し、前記フィラメント状炭素の集合体の一部が前記金属層中に含まれており、前記フィラメント状炭素の集合体の他部が前記金属層上で露出している自立した複合膜を製造するための装置であって、
　支持体を連続的に移動する移動機構と、
　前記移動方向上流側に設けられて前記支持体上に前記フィラメント状炭素の集合体を形成する集合体形成部と、
　前記移動方向下流側に設けられて前記フィラメント状炭素の集合体上に金属を蒸着する蒸着機構とを備える複合膜製造装置が提供される。 According to the eighth aspect of the present invention, only the metal layer and the filamentous carbon aggregate are included, and a part of the filamentous carbon aggregate is included in the metal layer, An apparatus for producing a self-supporting composite film in which the other part of the carbon aggregate is exposed on the metal layer,
A moving mechanism for continuously moving the support;
An assembly forming portion that is provided on the upstream side in the moving direction and forms an assembly of the filamentous carbon on the support;
There is provided a composite film manufacturing apparatus provided with a vapor deposition mechanism provided on the downstream side in the moving direction and vapor-depositing metal on the aggregate of filamentous carbon.
　前記複合膜製造装置は、前記移動機構が前記支持体を回転移動するロールを備えてもよい。 The composite film manufacturing apparatus may include a roll in which the moving mechanism rotates and moves the support.
　複合膜製造装置において、前記集合体形成部と前記蒸着機構を連続的に動作させることにより、長尺の複合膜を前記支持体上に形成し、該長尺の複合膜を前記支持体から連続的に剥離することによって前記長尺の複合膜を得てもよい。 In the composite film manufacturing apparatus, by continuously operating the assembly forming unit and the vapor deposition mechanism, a long composite film is formed on the support, and the long composite film is continuously formed from the support. Alternatively, the long composite film may be obtained by peeling off the film.
　本発明の複合膜の製造方法において、フィラメント状炭素膜上に金属を蒸着することにより、フィラメント状炭素膜に金属層の一部が入り込むため、フィラメント状炭素と前記金属とが共存する共存層が形成される。そのため、本発明の製造方法によって製造された複合膜は、フィラメント状炭素膜と金属層の間の電気抵抗が小さい。さらに、この複合膜のフィラメント状炭素膜の金属を蒸着した面と反対の面上にリチウムイオン電池の活物質として用いることができる材料を付着させた機能性複合膜は、リチウムイオン電池の電極として使用することができる。更に、各種二次電池や電気二重層キャパシタなどの蓄電デバイスの活物質を付着した複合膜は、蓄電デバイスの電極として使用することができる。本発明の複合膜を用いた電極は、集電体と活物質の間の電気抵抗が小さく、また、活物質がリチウムイオンを吸蔵及び放出して体積変化しても、集電体から剥離しにくい。そのため、本発明の複合膜及びその製造方法は、リチウムイオン電池等の蓄電デバイスの電極等の用途に好適に用いることができる。 In the composite film manufacturing method of the present invention, by depositing a metal on the filamentous carbon film, a part of the metal layer enters the filamentous carbon film. Therefore, there is a coexistence layer in which the filamentous carbon and the metal coexist. It is formed. Therefore, the composite film manufactured by the manufacturing method of the present invention has a small electrical resistance between the filamentous carbon film and the metal layer. Furthermore, a functional composite film in which a material that can be used as an active material of a lithium ion battery is attached to the surface of the composite film opposite to the metal-deposited surface of the filamentous carbon film is used as an electrode of a lithium ion battery. Can be used. Furthermore, a composite film to which an active material of an electricity storage device such as various secondary batteries or electric double layer capacitors is attached can be used as an electrode of the electricity storage device. The electrode using the composite film of the present invention has low electrical resistance between the current collector and the active material, and even if the active material occludes and releases lithium ions and changes its volume, it peels off from the current collector. Hateful. Therefore, the composite film and the manufacturing method thereof of the present invention can be suitably used for applications such as electrodes of power storage devices such as lithium ion batteries.
図１（ａ）は、第１実施形態の複合膜の概略断面図であり、図１（ｂ）、（ｃ）は第２実施形態の機能性複合膜の概略断面図である。FIG. 1A is a schematic cross-sectional view of the composite film of the first embodiment, and FIGS. 1B and 1C are schematic cross-sectional views of the functional composite film of the second embodiment. 図２（ａ）は、第３実施形態の複合膜の概略断面図であり、図２（ｂ）は図２（ａ）の複合膜の変形形態の概略断面図であり、図２（ｃ）、（ｄ）は第４実施形態の機能性複合膜の概略断面図である。2A is a schematic cross-sectional view of the composite film of the third embodiment, and FIG. 2B is a schematic cross-sectional view of a modified form of the composite film of FIG. 2A. FIG. (D) is a schematic sectional drawing of the functional composite film of 4th Embodiment. 図３は、複合膜の製造方法を示すフローチャートである。FIG. 3 is a flowchart showing a method for manufacturing the composite membrane. 図４（ａ）～（ｅ）は第１実施形態の複合膜及び第２実施形態の機能性複合膜の製造方法の各工程を概念的に示す図である。4 (a) to 4 (e) are diagrams conceptually showing each process of the manufacturing method of the composite film of the first embodiment and the functional composite film of the second embodiment. 図５（ａ）～（ｅ）は第３実施形態の複合膜及び第４実施形態の機能性複合膜の製造方法の各工程を概念的に示す図である。FIGS. 5A to 5E are diagrams conceptually showing each process of the method for producing the composite film of the third embodiment and the functional composite film of the fourth embodiment. 図６（ａ）は第１実施形態の複合膜を連続プロセスで製造するための装置の概略図であり、図６（ｂ）は第３実施形態の複合膜を連続プロセスで製造するための装置の概略図である。FIG. 6A is a schematic view of an apparatus for manufacturing the composite film of the first embodiment in a continuous process, and FIG. 6B is an apparatus for manufacturing the composite film of the third embodiment in a continuous process. FIG. 図７（ａ）、（ｂ）は実施例１のＣＮＴ－Ｃｕ複合膜を２つに分割した試料の平面ＳＥＭ写真を示し、図７（ｃ）～（ｅ）は比較例１のＣＮＴ－Ｃｕ複合膜を２つに分割した試料の平面ＳＥＭ写真を示す。FIGS. 7A and 7B show planar SEM photographs of the sample obtained by dividing the CNT-Cu composite film of Example 1 into two, and FIGS. 7C to 7E show the CNT-Cu of Comparative Example 1. FIG. The plane SEM photograph of the sample which divided the composite film into two is shown. 図８Ａは、実施例２のＣＮＴ膜の平面ＳＥＭ像を示す。FIG. 8A shows a planar SEM image of the CNT film of Example 2. FIG. 図８Ｂは、実施例２のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8B shows a planar SEM image of the CNT—Cu composite film of Example 2 as seen from the Cu side. 図８Ｃは、実施例３のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8C shows a planar SEM image of the CNT—Cu composite film of Example 3 viewed from the Cu side. 図８Ｄは、実施例４のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8D shows a planar SEM image of the CNT—Cu composite film of Example 4 as viewed from the Cu side. 図８Ｅは、実施例５のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8E shows a planar SEM image of the CNT—Cu composite film of Example 5 viewed from the Cu side. 図８Ｆは、実施例６のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8F shows a planar SEM image of the CNT—Cu composite film of Example 6 viewed from the Cu side. 図８Ｇは、実施例７のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8G shows a planar SEM image of the CNT—Cu composite film of Example 7 viewed from the Cu side. 図８Ｈは、実施例８のＣＮＴ－Ｃｕ複合膜のＣｕ側から見た平面ＳＥＭ像を示す。FIG. 8H shows a planar SEM image of the CNT—Cu composite film of Example 8 viewed from the Cu side. 図９は、実施例９で作製したＳｉ－ＣＮＴ－Ｃｕ複合膜の断面ＳＥＭ像を示す。FIG. 9 shows a cross-sectional SEM image of the Si—CNT—Cu composite film produced in Example 9. 図１０は実施例９及び比較例２の複合膜の充放電サイクル特性を示す。FIG. 10 shows the charge / discharge cycle characteristics of the composite films of Example 9 and Comparative Example 2. 図１１（ａ）は、実施例１０でＣＮＴ－Ｃｕ複合膜を基板から剥離する様子を示すデジタルカメラ写真であり、図１１（ｂ）～（ｄ）は実施例１０の自立したＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真である。FIG. 11A is a digital camera photograph showing a state in which the CNT—Cu composite film is peeled from the substrate in Example 10, and FIGS. 11B to 11D are self-supporting CNT—Cu composites of Example 10. It is a digital camera photograph of the film. 図１２（ａ）～（ｃ）は実施例１１の自立したＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真である。FIGS. 12A to 12C are digital camera photographs of the self-supporting CNT—Cu composite film of Example 11. FIG. 図１３Ａは実施例１２の自立したＣＮＴ－Ｃｕ複合膜の断面ＳＥＭ像である。FIG. 13A is a cross-sectional SEM image of the self-supporting CNT—Cu composite film of Example 12. 図１３Ｂは実施例１２でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜をＣｕ膜側から撮影したデジタルカメラ写真である。FIG. 13B is a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 12 taken from the Cu film side. 図１３Ｃは実施例１２でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜をＣＮＴ膜側から撮影したデジタルカメラ写真である。FIG. 13C is a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 12 taken from the CNT film side. 図１３Ｄは実施例１２でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜の網目構造を示す断面ＳＥＭ像である。13D is a cross-sectional SEM image showing a network structure of a CNT-Cu composite film obtained by shrinking a CNT vertical alignment film in Example 12. FIG. 図１３Ｅは実施例１２でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜の網目構造を示す平面ＳＥＭ像である。FIG. 13E is a planar SEM image showing the network structure of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 12. 図１４Ａは実施例１３で用いたＣｕ基板の表面のＳＥＭ像である。14A is an SEM image of the surface of the Cu substrate used in Example 13. FIG. 図１４Ｂは実施例１３の自立したＣＮＴ－Ｃｕ複合膜及びＣＮＴ－Ｃｕ複合膜を剥離した後の基板のデジタルカメラ写真であり、ＣＮＴ－Ｃｕ複合膜はＣＮＴ膜側から撮影されている。FIG. 14B is a digital camera photograph of the substrate after the CNT-Cu composite film and the CNT-Cu composite film of Example 13 were peeled off, and the CNT-Cu composite film was taken from the CNT film side. 図１４Ｃは実施例１３の自立したＣＮＴ－Ｃｕ複合膜の断面ＳＥＭ像である。FIG. 14C is a cross-sectional SEM image of the self-supporting CNT—Cu composite film of Example 13. 図１４Ｄは実施例１３でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜をＣＮＴ膜側から撮影したデジタルカメラ写真である。FIG. 14D is a digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 13 taken from the CNT film side. 図１４Ｅは実施例１３でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜の筋状構造を示す斜めＳＥＭ像である。FIG. 14E is an oblique SEM image showing the streak structure of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 13. 図１４Ｆは実施例１３でＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜の筋状構造を示す平面ＳＥＭ像である。FIG. 14F is a planar SEM image showing the streak structure of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film in Example 13. 図１５Ａは実施例１４の自立したＣＮＴ－Ａｌ複合膜及び残余のＣＮＴ膜のデジタルカメラ写真であり、ＣＮＴ－Ａｌ複合膜はＡｌ膜側から撮影されている。FIG. 15A is a digital camera photograph of the self-supporting CNT-Al composite film and the remaining CNT film of Example 14, and the CNT-Al composite film is taken from the Al film side. 図１５Ｂは実施例１４の自立したＣＮＴ－Ａｌ複合膜をＣＮＴ膜側から撮影したデジタルカメラ写真である。FIG. 15B is a digital camera photograph of the self-supporting CNT-Al composite film of Example 14 taken from the CNT film side. 図１５Ｃは実施例１４の自立したＣＮＴ－Ａｌ複合膜の平面ＳＥＭ像である。FIG. 15C is a planar SEM image of the self-supporting CNT—Al composite film of Example 14. 図１５Ｄは実施例１４の自立したＣＮＴ－Ａｌ複合膜の断面ＳＥＭ像である。FIG. 15D is a cross-sectional SEM image of the self-supported CNT—Al composite film of Example 14. 図１６Ａは実施例１５の自立したＣＮＴ－Ａｌ複合膜及びＣＮＴ－Ａｌ複合膜を剥離した後の基板のデジタルカメラ写真であり、ＣＮＴ－Ａｌ複合膜はＡｌ膜側から撮影されている。FIG. 16A is a digital camera photograph of the substrate after peeling the self-standing CNT-Al composite film and the CNT-Al composite film of Example 15, and the CNT-Al composite film was taken from the Al film side. 図１６Ｂは実施例１５の自立したＣＮＴ－Ａｌ複合膜をＣＮＴ膜側から撮影したデジタルカメラ写真であるFIG. 16B is a digital camera photograph of the self-standing CNT-Al composite film of Example 15 taken from the CNT film side. 図１６Ｃは実施例１５の自立したＣＮＴ－Ａｌ複合膜の平面ＳＥＭ像である。FIG. 16C is a planar SEM image of the self-supporting CNT—Al composite film of Example 15. 図１６Ｄは実施例１５の自立したＣＮＴ－Ａｌ複合膜の断面ＳＥＭ像である。FIG. 16D is a cross-sectional SEM image of the self-supporting CNT—Al composite film of Example 15. 図１７Ａは実施例１６の自立したＣＦ＋ＣＮＴ－Ａｌ複合膜及びＣＦ＋ＣＮＴ－Ａｌ複合膜を剥離した後の基板のデジタルカメラ写真であり、ＣＦ＋ＣＮＴ－Ａｌ複合膜はＡｌ膜側から撮影されている。FIG. 17A is a digital camera photograph of the substrate after peeling the self-supporting CF + CNT-Al composite film and CF + CNT-Al composite film of Example 16, and the CF + CNT-Al composite film is taken from the Al film side. 図１７Ｂは実施例１６の自立したＣＦ＋ＣＮＴ－Ａｌ複合膜をＣＮＴ膜側から撮影したデジタルカメラ写真であるFIG. 17B is a digital camera photograph of the self-supporting CF + CNT-Al composite film of Example 16 taken from the CNT film side. 図１７Ｃは実施例１６の自立したＣＦ＋ＣＮＴ－Ａｌ複合膜の平面ＳＥＭ像である。FIG. 17C is a planar SEM image of the self-supported CF + CNT-Al composite film of Example 16. 図１７Ｄは実施例１６の自立したＣＦ＋ＣＮＴ－Ａｌ複合膜の断面ＳＥＭ像である。FIG. 17D is a cross-sectional SEM image of the self-supporting CF + CNT-Al composite film of Example 16. 図１８Ａは実施例１７の垂直配向ＣＮＴ膜の断面ＳＥＭ像である。18A is a cross-sectional SEM image of the vertically aligned CNT film of Example 17. FIG. 図１８Ｂは実施例１７の自立したＣＮＴ－Ａｌ複合膜及びＣＮＴ－Ａｌ複合膜を剥離した後の基板のデジタルカメラ写真であり、ＣＮＴ－Ａｌ複合膜はＣＮＴ膜側から撮影されている。FIG. 18B is a digital camera photograph of the substrate after peeling the self-standing CNT-Al composite film and the CNT-Al composite film of Example 17, and the CNT-Al composite film was taken from the CNT film side. 図１８Ｃは実施例１７の自立したＣＮＴ－Ａｌ複合膜をＡｌ膜側から撮影したデジタルカメラ写真であるFIG. 18C is a digital camera photograph of the self-supported CNT-Al composite film of Example 17 taken from the Al film side. 図１８Ｄは実施例１７の自立したＣＮＴ－Ａｌ複合膜の断面ＳＥＭ像である。FIG. 18D is a cross-sectional SEM image of the self-supported CNT—Al composite film of Example 17. 図１９Ａは実施例１８の自立したＡＣ＋ＣＮＴ－Ａｌ複合膜をＡｌ膜側から撮影したデジタルカメラ写真であるFIG. 19A is a digital camera photograph of the self-supporting AC + CNT-Al composite film of Example 18 taken from the Al film side. 図１９Ｂは実施例１８の自立したＡＣ＋ＣＮＴ－Ａｌ複合膜の平面ＳＥＭ像である。FIG. 19B is a planar SEM image of the self-supporting AC + CNT-Al composite film of Example 18. 図１９Ｃは実施例１８の自立したＡＣ＋ＣＮＴ－Ａｌ複合膜の断面ＳＥＭ像である。FIG. 19C is a cross-sectional SEM image of the self-supported AC + CNT—Al composite film of Example 18. 図１９Ｄは実施例１８のＡＣ＋ＣＮＴ－Ａｌ複合膜のシート抵抗をＡｌ膜の換算膜厚に対してプロットしたグラフである。FIG. 19D is a graph plotting the sheet resistance of the AC + CNT-Al composite film of Example 18 against the equivalent film thickness of the Al film. 図１９Ｅは実施例１８のＡＣ＋ＣＮＴ複合膜及びＡＣ＋ＣＮＴ－Ａｌ複合膜を用いたサイクリックボルタンメトリにおける比容量の掃引レート依存性を示すグラフである。FIG. 19E is a graph showing the sweep rate dependence of the specific capacity in cyclic voltammetry using the AC + CNT composite film and the AC + CNT-Al composite film of Example 18. 図２０は、非導電性ポリマーからなるバインダーを使用した従来技術のリチウムイオン電池の電極の概略断面図である。FIG. 20 is a schematic cross-sectional view of an electrode of a prior art lithium ion battery using a binder made of a non-conductive polymer. 図２１は、Ｓｉの柱状構造体を有する従来技術のリチウムイオン電池の電極の概略断面図である。FIG. 21 is a schematic cross-sectional view of an electrode of a prior art lithium ion battery having a Si columnar structure.
　以下、本発明の複合膜及び複合膜の製造方法、及びその複合膜を用いた蓄電デバイスの実施形態について、図面を参照しながら説明する。 Hereinafter, embodiments of a composite film, a method for manufacturing the composite film, and a power storage device using the composite film of the present invention will be described with reference to the drawings.
［第１実施形態］
　第１実施形態の複合膜１００は、図１（ａ）に示すように、フィラメント状炭素の集合体であるフィラメント状炭素層（膜）２０と、金属から構成された金属層１０とだけから構成された自立膜であり、金属層１０の一部がフィラメント状炭素層２０の一部と重複している。このため、フィラメント状炭素と金属が共存する共存層（共存領域）６０が、金属層１０中またはフィラメント状炭素層２０中に存在している。すなわち、フィラメント状炭素膜２０は、フィラメント状炭素４２だけからなる第１層４０と、共存層６０とを有しており、金属層１０は、金属だけからなる第２層８０と共存層６０とを有する。複合膜１００は、第１層４０と共存層６０の間、及び共存層６０と第２層８０の間に別の層（中間層）を有さず、共存層６０が第１層４０と第２層８０の間の界面又は境界をなしている。フィラメント状炭素層２０に注目すれば、フィラメント状炭素膜２０の一方の面（フィラメント状炭素の集合体の一部）が金属層１０中に含まれており、フィラメント状炭素膜２０の他方の面（フィラメント状炭素の集合体２０の他部）が前記金属層１０上で露出している。なお、フィラメント状炭素膜２０は、フィラメント状炭素４２に加えて、活性炭等の粒状炭素を含んでいてもよい。すなわち、本願において「フィラメント状炭素層」、「フィラメント状炭素の集合体」、「フィラメント状炭素だけからなる第１層」は、フィラメント状炭素に加えて粒状の炭素を含んでよい。 [First Embodiment]
As shown in FIG. 1A, the composite film 100 of the first embodiment is composed of only a filamentous carbon layer (film) 20 that is an aggregate of filamentous carbon and a metal layer 10 made of metal. A part of the metal layer 10 overlaps with a part of the filamentous carbon layer 20. Therefore, a coexistence layer (coexistence region) 60 in which filamentous carbon and metal coexist exists in the metal layer 10 or the filamentous carbon layer 20. That is, the filamentous carbon film 20 includes the first layer 40 made of only the filamentous carbon 42 and the coexistence layer 60, and the metal layer 10 includes the second layer 80 made of only the metal and the coexistence layer 60. Have The composite film 100 does not have another layer (intermediate layer) between the first layer 40 and the coexistence layer 60 and between the coexistence layer 60 and the second layer 80. It forms an interface or boundary between the two layers 80. If attention is paid to the filamentous carbon layer 20, one side of the filamentous carbon film 20 (a part of the aggregate of filamentous carbon) is included in the metal layer 10, and the other side of the filamentous carbon film 20. (The other part of the aggregate 20 of filamentous carbon) is exposed on the metal layer 10. The filamentous carbon film 20 may contain granular carbon such as activated carbon in addition to the filamentous carbon 42. That is, in the present application, the “filamentous carbon layer”, “aggregate of filamentous carbon”, and “first layer made of only filamentous carbon” may contain granular carbon in addition to the filamentous carbon.
　なお、本発明に従う複合膜は、フィラメント状炭素だけからなる第１層４０と、フィラメント状炭素と金属が共存する共存層６０を有すればよく、図１（ａ）に示した金属だけからなる第２層８０は必須ではない。すなわち、金属層１０の全部がフィラメント状炭素層２０の一部と重複していてもよい。前述のように、第１実施形態の複合膜１００は、フィラメント状炭素４２だけからなる第１層４０及び共存層６０を含むフィラメント状炭素膜２０と、金属だけからなる第２層８０及び共存層６０とを含む金属層１０と有するので、最初に、第１層４０、第２層８０及び共存層６０について説明する。 The composite film according to the present invention only needs to have the first layer 40 made of only filamentous carbon and the coexistence layer 60 in which the filamentous carbon and metal coexist, and is made of only the metal shown in FIG. The second layer 80 is not essential. That is, all of the metal layer 10 may overlap with a part of the filamentous carbon layer 20. As described above, the composite film 100 of the first embodiment includes the filamentous carbon film 20 including the first layer 40 and the coexistence layer 60 made of only the filamentous carbon 42, the second layer 80 and the coexistence layer made of only the metal. First, the first layer 40, the second layer 80, and the coexistence layer 60 will be described.
＜第１層＞
　本実施形態の複合膜１００において、第１層４０は、導電性のフィラメント状炭素４２から、特にフィラメント状炭素４２の集合体から構成される。「フィラメント状炭素の集合体」とは、多数のフィラメント状炭素が空隙を保ちつつ重なり又は交差し合ってできている集合体であり、例えば、網目状や垂直配列型のような所定方向に配列した構造を含む。フィラメント状炭素４２として、カーボンナノチューブ（以下、適宜「ＣＮＴ」と略する）、気相成長炭素繊維に代表されるカーボンナノファイバー（以下、適宜「ＣＮＦ」と略する）、カーボンファイバー（以下、適宜「ＣＦ」と略する）等を用いることができるが、フィラメント状炭素４２は、ＣＮＴ、ＣＮＦ、またはこれらの混合物を含むことが好ましく、ＣＮＴを含むことがより好ましい。ＣＮＴとしては平均で１層以上３０層以下のグラフェン円筒から構成されるＣＮＴを用いることがより好ましい。ＣＮＴとしては、例えば、Ｃａｒｂｏｎ　４９（６），１９７２－１９７９（２０１１）、Ｃａｒｂｏｎ　８０，３３９－３５０（２０１４）等に記載の方法で合成したものを用いることができる。市販のＣＮＴ、ＣＮＦ及び／又はＣＦを用いてもよい。 <First layer>
In the composite film 100 of the present embodiment, the first layer 40 is composed of conductive filamentous carbon 42, in particular, an aggregate of filamentous carbon 42. “Aggregate of filamentous carbon” is an aggregate formed by overlapping or intersecting a large number of filamentous carbons while maintaining voids. For example, the filamentous carbon is arranged in a predetermined direction such as a mesh or vertical arrangement type. Including the structure. Examples of the filamentous carbon 42 include carbon nanotubes (hereinafter abbreviated as “CNT” as appropriate), carbon nanofibers represented by vapor-grown carbon fibers (hereinafter abbreviated as “CNF” as appropriate), carbon fibers (hereinafter, as appropriate). The filamentous carbon 42 preferably contains CNT, CNF, or a mixture thereof, and more preferably contains CNT. As the CNT, it is more preferable to use CNT composed of graphene cylinders having an average of 1 to 30 layers. As CNTs, for example, those synthesized by the method described in Carbon 49 (6), 1972-1979 (2011), Carbon 80, 339-350 (2014), etc. can be used. Commercially available CNT, CNF and / or CF may be used.
　図１（ａ）に示すように、フィラメント状炭素４２は、網目状の構造４４を形成している。網目構造４４は、３ｎｍ～１０００ｎｍの範囲内の大きさの網目（立体的な空隙）を含むことが好ましい。 As shown in FIG. 1A, the filamentous carbon 42 forms a network structure 44. The network structure 44 preferably includes a network (steric void) having a size within a range of 3 nm to 1000 nm.
＜第２層＞
　第２層８０は、金属から構成され、特に低抵抗な金属から構成されることが好ましい。複合膜１００をリチウムイオン電池の正極に用いる場合には、金属としてアルミニウム等を用いてよい。複合膜１００をリチウムイオン電池の負極に用いる場合には、金属として銅、ニッケル等を用いてよい。第２層８０の厚みは、用途に応じて任意の厚さにすることができるが、例えば本実施形態の複合膜１００をリチウムイオン電池の負極に用いる場合には、０．０３μｍ～３０μｍの範囲内であることが好ましく、１～１０μｍの範囲内にあるとより好ましい。第２層８０の厚みが１０μｍ以下であることにより、複合膜１００がより軽量化される。第２層８０の厚みが１μｍ以上であることにより、複合膜１００の抵抗をより小さくできる。 <Second layer>
The second layer 80 is made of a metal, and is particularly preferably made of a low resistance metal. When the composite film 100 is used for a positive electrode of a lithium ion battery, aluminum or the like may be used as a metal. When the composite film 100 is used for the negative electrode of a lithium ion battery, copper, nickel, or the like may be used as the metal. The thickness of the second layer 80 can be set to any thickness depending on the application. For example, when the composite film 100 of the present embodiment is used for the negative electrode of a lithium ion battery, the thickness is in the range of 0.03 μm to 30 μm. Is preferably within the range of 1 to 10 μm. When the thickness of the second layer 80 is 10 μm or less, the composite film 100 is further reduced in weight. When the thickness of the second layer 80 is 1 μm or more, the resistance of the composite film 100 can be further reduced.
＜共存層＞
　共存層６０は、フィラメント状炭素４２と金属が共存している層又は領域である。共存層６０の金属は、第２層８０を構成する金属と同様の金属である。すなわち、共存層６０は、第１層４０のフィラメント状炭素４２と第２層８０の金属が部分的に入り交じった構造を有している。このため、図１（ａ）に示すように、共存層６０は、第１層４０と同様に、フィラメント状炭素４２による網目構造４４を有し、該網目構造４４の網目（立体的な空隙）内に金属が入り込んでいる。網目構造４４は、３ｎｍ～１０００ｎｍの範囲内の大きさの網目を含んでよい。フィラメント状炭素４２との網目内に金属が入り込んでいることにより、フィラメント状炭素４２と金属が機械的及び電気的に接続される。 <Coexistence layer>
The coexistence layer 60 is a layer or region in which the filamentous carbon 42 and metal coexist. The metal of the coexistence layer 60 is the same metal as the metal constituting the second layer 80. That is, the coexistence layer 60 has a structure in which the filamentous carbon 42 of the first layer 40 and the metal of the second layer 80 are partially mixed. For this reason, as shown in FIG. 1A, the coexistence layer 60 has a network structure 44 of filamentous carbon 42 as in the first layer 40, and the network (three-dimensional voids) of the network structure 44. There is metal inside. The mesh structure 44 may include a mesh having a size in the range of 3 nm to 1000 nm. Since the metal has entered the mesh with the filamentous carbon 42, the filamentous carbon 42 and the metal are mechanically and electrically connected.
　後述する製造方法により複合膜１００を製造することにより、共存層６０の厚みを０．０１μｍ～１０μｍの範囲内とすることができる。共存層６０の厚みが前記範囲内である場合、第１層４０と第２層８０が十分に機械的及び電気的に接続される。 The thickness of the coexistence layer 60 can be set within the range of 0.01 μm to 10 μm by manufacturing the composite film 100 by the manufacturing method described later. When the thickness of the coexistence layer 60 is within the above range, the first layer 40 and the second layer 80 are sufficiently mechanically and electrically connected.
　本実施形態の複合膜１００において、上述の様にフィラメント状炭素４２の網目内に金属が入り込んでいることにより、非導電性材料からなるバインダーを用いることなくフィラメント状炭素と金属が機械的に接続される。また、フィラメント状炭素４２の網目内に金属が入り込んでいることによりフィラメント状炭素と金属が電気的にも接続されること、及び上述のように複合膜１００が非導電性材料からなるバインダーを含まないことから、本実施形態の複合膜１００は低抵抗である。さらに、フィラメント状炭素４２が金属から露出しているため、本実施形態の複合膜１００は表面積が大きい。それゆえ、本実施形態の複合膜１００は、リチウムイオン電池の電極の集電箔等として好適に用いることができる。 In the composite film 100 of the present embodiment, the metal enters the mesh of the filamentous carbon 42 as described above, so that the filamentous carbon and the metal are mechanically connected without using a binder made of a nonconductive material. Is done. Further, since the metal enters the mesh of the filamentous carbon 42, the filamentous carbon and the metal are also electrically connected, and the composite film 100 includes a binder made of a non-conductive material as described above. Therefore, the composite film 100 of this embodiment has a low resistance. Furthermore, since the filamentous carbon 42 is exposed from the metal, the composite film 100 of this embodiment has a large surface area. Therefore, the composite film 100 of the present embodiment can be suitably used as a current collector foil for an electrode of a lithium ion battery.
［第２実施形態］
　図１（ｂ）、（ｃ）に第１実施形態の自立した複合膜に活物質を付着させた機能性複合膜を示す。第２実施形態の機能性複合膜３００、４００は、図１（ａ）に示す第１実施形態の複合膜１００と同様の、フィラメント状炭素４２からなる第１層４０と、金属からなる第２層８０と、第１層４０と第２層８０の間に形成されたフィラメント状炭素４２と金属が共存する共存層６０とを有する複合膜を有する。機能性複合膜３００、４００は、第１実施形態の自立した複合膜と、さらに、第１層４０の共存層６０が形成された面と反対の面上において、フィラメント状炭素４２に付着している電極活物質（以下、適宜「活物質」という）３４を有する。すなわち、機能性複合膜３００、４００は、第１実施形態の複合膜１００の第１層４０を構成するフィラメント状炭素４２に活物質３４が付着した構成を有する。機能性複合膜３００、４００の第１層４０、第２層８０及び共存層６０は、第１実施形態の複合膜１００の第１層４０、第２層８０及び共存層６０と同様に構成されるので、その説明は省略する。 [Second Embodiment]
1B and 1C show a functional composite film in which an active material is attached to the self-supporting composite film of the first embodiment. The functional composite films 300 and 400 of the second embodiment are the same as the composite film 100 of the first embodiment shown in FIG. 1A, and the first layer 40 made of filamentous carbon 42 and the second made of metal. The composite film has a layer 80, a filamentary carbon 42 formed between the first layer 40 and the second layer 80, and a coexistence layer 60 in which a metal coexists. The functional composite films 300 and 400 adhere to the filamentous carbon 42 on the surface opposite to the surface on which the coexisting layer 60 of the first layer 40 is formed and the self-supporting composite film of the first embodiment. Electrode active material (hereinafter referred to as “active material” as appropriate) 34. That is, the functional composite films 300 and 400 have a configuration in which the active material 34 is attached to the filamentous carbon 42 that forms the first layer 40 of the composite film 100 of the first embodiment. The first layer 40, the second layer 80, and the coexistence layer 60 of the functional composite films 300, 400 are configured in the same manner as the first layer 40, the second layer 80, and the coexistence layer 60 of the composite film 100 of the first embodiment. Therefore, the description is omitted.
＜活物質＞
　活物質３４としては、種々の機能を有する物質を使用することができる。例えば機能性複合膜３００、４００をリチウムイオン電池の負極として用いる場合には、活物質３４としてリチウムイオンを吸蔵及び脱離できる材料、例えば、Ｓｉ、Ｓｉ酸化物、ＳｉとＳｉ以外の他金属元素を含むＳｉ複合酸化物、グラファイト、ハードカーボン、黒鉛、非晶質炭素などの炭素材料、Ｌｉ、Ｓｎ、ＡｌなどのＬｉと合金を形成する材料、ＳｎＯのようなＳｎ酸化物、ＳｎとＳｎ以外の他金属元素を含むＳｎ複合酸化物、チタン酸リチウム、Ｌｉ等を用いることができる。リチウムイオン電池の正極として用いる場合には、活物質３４としてＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４、ＬｉＦｅＰＯ４、Ｌｉ（Ｎｉ－Ｍｎ－Ｃｏ）Ｏ２、Ｓなどを用いることができる。これらは単独で用いても複数種を混合して用いることもできる。 <Active material>
As the active material 34, materials having various functions can be used. For example, when the functional composite films 300 and 400 are used as a negative electrode of a lithium ion battery, a material capable of inserting and extracting lithium ions as the active material 34, for example, Si, Si oxide, other metal elements other than Si and Si Si composite oxides containing, carbon materials such as graphite, hard carbon, graphite, and amorphous carbon, materials that form alloys with Li, such as Li, Sn, Al, Sn oxides such as SnO, other than Sn and Sn Sn composite oxides containing other metal elements, lithium titanate, Li, or the like can be used. When used as a positive electrode of a lithium ion battery, LiCoO 2 , LiMn 2 O 4 , LiFePO 4 , Li (Ni—Mn—Co) O 2 , S, or the like can be used as the active material 34. These may be used alone or in combination of two or more.
　「活物質３４がフィラメント状炭素に付着している」とは、活物質３４が第１層４０の共存層６０が形成された面と反対の面から第１層４０の網目構造４４の内部に活物質３４が入り込んでいる形態（図１（ｂ）参照）、及びフィラメント状炭素４２の表面を活物質３４が覆うように付着している形態（図１（ｃ）参照）を含む。また、機能性複合膜３００、４００が有する活物質３４の一部がフィラメント状炭素４２による網目構造４４に入り込んでいてもよいし、機能性複合膜３００、４００が有する活物質３４の全部がフィラメント状炭素４２による網目構造４４に入り込んでいてもよい。また、機能性複合膜３００、４００が有する活物質３４がフィラメント状炭素４２による網目構造４４の全体に入り込んでいて共存層６０と直接接していてもよいし、機能性複合膜３００、４００が有する活物質３４がフィラメント状炭素４２による網目構造４４の一部に入り込んでいて共存層６０と直接接していなくてもよい。 “The active material 34 is attached to the filamentous carbon” means that the active material 34 is inside the network structure 44 of the first layer 40 from the surface opposite to the surface on which the coexisting layer 60 of the first layer 40 is formed. It includes a form in which the active material 34 has entered (see FIG. 1B) and a form in which the active material 34 is attached so as to cover the surface of the filamentous carbon 42 (see FIG. 1C). Further, a part of the active material 34 included in the functional composite films 300 and 400 may enter the network structure 44 of the filamentous carbon 42, or all of the active material 34 included in the functional composite films 300 and 400 may be filaments. It may enter the network structure 44 of the carbon-like carbon 42. Further, the active material 34 included in the functional composite films 300 and 400 may enter the entire network structure 44 of the filamentous carbon 42 and may be in direct contact with the coexisting layer 60, or the functional composite films 300 and 400 may include the active material 34. The active material 34 does not need to be in direct contact with the coexistence layer 60 by entering a part of the network structure 44 of the filamentous carbon 42.
　機能性複合膜３００、４００をリチウムイオン電池に代表される二次電池の電極として用いた場合、活物質３４は充放電時のリチウムイオンの吸蔵及び放出に伴って大きく体積変化するが、活物質３４がフィラメント状炭素４２による網目構造４４に入り込んでいる、又は活物質３４がフィラメント状炭素４２の表面を覆うように付着しているため、フィラメント状炭素４２が撓むことにより活物質３４の体積変化を吸収（緩和）することができ、活物質３４が第１層４０から剥離することが防止される。 When the functional composite films 300 and 400 are used as electrodes of a secondary battery typified by a lithium ion battery, the active material 34 greatly changes in volume with the insertion and extraction of lithium ions during charge and discharge. 34 has entered the network structure 44 of the filamentous carbon 42, or the active material 34 is attached so as to cover the surface of the filamentous carbon 42, so that the volume of the active material 34 is deformed by the deflection of the filamentous carbon 42. The change can be absorbed (relaxed), and the active material 34 is prevented from peeling from the first layer 40.
　また、上述の様に、第１実施形態の複合膜１００は、フィラメント状炭素４２が金属から露出しているため、表面積が大きい。したがって、第１実施形態の複合膜１００の第１層４０を構成するフィラメント状炭素４２に活物質３４が付着した構成を有する本実施形態の機能性複合膜３００、４００は、活物質３４と第１層４０の接触面積が大きい（接触点が多い）。それゆえ、機能性複合膜３００、４００において、活物質３４とフィラメント状炭素４２から構成される第１層４０が機械的に良好に接続される。そのため、機能性複合膜３００、４００をリチウムイオン電池の電極として用いた場合、充放電時に活物質３４の体積が大きく変化しても、活物質３４が第１層４０から剥離しにくい。したがって、機能性複合膜３００、４００をリチウムイオン電池に代表される二次電池の電極として用いることにより、長寿命の二次電池を製造することができる。 Further, as described above, the composite film 100 of the first embodiment has a large surface area because the filamentous carbon 42 is exposed from the metal. Therefore, the functional composite films 300 and 400 of this embodiment having a configuration in which the active material 34 is attached to the filamentous carbon 42 constituting the first layer 40 of the composite film 100 of the first embodiment include the active material 34 and the first active material 34. The contact area of one layer 40 is large (many contact points). Therefore, in the functional composite films 300 and 400, the first layer 40 composed of the active material 34 and the filamentous carbon 42 is mechanically well connected. Therefore, when the functional composite films 300 and 400 are used as electrodes of a lithium ion battery, the active material 34 is unlikely to peel from the first layer 40 even if the volume of the active material 34 changes greatly during charging and discharging. Therefore, a long-life secondary battery can be manufactured by using the functional composite films 300 and 400 as electrodes of a secondary battery represented by a lithium ion battery.
　また、活物質３４と第１層４０の接触面積が大きいことにより、活物質３４とフィラメント状炭素４２から構成される第１層４０は電気的にも良好に接続される（接触抵抗が小さい）。さらに、本実施形態の機能性複合膜３００、４００において、第１実施形態の複合膜１００と同様に、フィラメント状炭素４２の網目内に金属が入り込んでいることにより、フィラメント状炭素４２と金属が、非導電性材料からなるバインダーを介することなく接続されている。そのため、フィラメント状炭素４２からなる第１層４０と金属は、低抵抗に接続される。それゆえ、本実施形態の機能性複合膜３００、４００において、活物質３４と金属は低抵抗に接続される。したがって、機能性複合膜３００、４００をリチウムイオン電池などの二次電池の電極として用いることにより、高容量のリチウムイオン電池のような二次電池を製造することができる。 Further, since the contact area between the active material 34 and the first layer 40 is large, the first layer 40 composed of the active material 34 and the filamentous carbon 42 is electrically connected well (the contact resistance is small). . Furthermore, in the functional composite films 300 and 400 of the present embodiment, as in the composite film 100 of the first embodiment, since the metal enters the mesh of the filamentous carbon 42, the filamentous carbon 42 and the metal are separated from each other. The connection is made without using a binder made of a non-conductive material. Therefore, the first layer 40 made of filamentary carbon 42 and the metal are connected with low resistance. Therefore, in the functional composite films 300 and 400 of the present embodiment, the active material 34 and the metal are connected with low resistance. Therefore, by using the functional composite films 300 and 400 as electrodes of a secondary battery such as a lithium ion battery, a secondary battery such as a high capacity lithium ion battery can be manufactured.
　機能性複合膜３００、４００は、上述のように活物質３４と第１層４０の接触面積が大きいため、バインダーを用いなくても活物質３４を第１層４０上に固定することができるが、図１（ｂ）に示す機能性複合膜３００において、活物質３４を第１層４０に固定するための非導電性ポリマーからなるバインダー（不図示）を含んでいてもよい。この場合、機能性複合膜３００はさらに、カーボンナノファイバー（ＣＮＦ）、カーボンブラック等からなる導電材（不図示）を含んでも良い。上述の様に第１層４０は導電性のフィラメント状炭素４２からなり、高い表面積を持っているため、活物質３４とフィラメント状炭素４２の接触面積が大きく、バインダーを添加しても十分な導電性を確保できる。また、導電材を添加することで、活物質３４からなる層が第１層４０よりも厚い場合にも活物質３４からなる層の垂直方向の導電性を十分に確保できる。また、導電材が第１層４０の網目に入り込むため活物質３４と第一層４０の間の導電性を十分に確保できる。 Since the functional composite films 300 and 400 have a large contact area between the active material 34 and the first layer 40 as described above, the active material 34 can be fixed on the first layer 40 without using a binder. In the functional composite film 300 shown in FIG. 1B, a binder (not shown) made of a non-conductive polymer for fixing the active material 34 to the first layer 40 may be included. In this case, the functional composite film 300 may further include a conductive material (not shown) made of carbon nanofiber (CNF), carbon black, or the like. As described above, the first layer 40 is composed of the conductive filamentous carbon 42 and has a high surface area. Therefore, the contact area between the active material 34 and the filamentous carbon 42 is large, and sufficient conductivity is obtained even when a binder is added. Can be secured. Further, by adding a conductive material, the conductivity in the vertical direction of the layer made of the active material 34 can be sufficiently secured even when the layer made of the active material 34 is thicker than the first layer 40. In addition, since the conductive material enters the network of the first layer 40, sufficient conductivity between the active material 34 and the first layer 40 can be ensured.
［第３実施形態］
　図２（ａ）に示すように、第３実施形態の複合膜１００ａは、上記第１実施形態の複合膜１００と同様に、フィラメント状炭素の集合体であるフィラメント状炭素（膜）２０ａと、金属から構成された金属層１０ａとだけから構成された自立膜であり、金属層１０の一部がフィラメント状炭素層２０ａの一部と重複している。このため、フィラメント状炭素と金属が共存する共存層（共存領域）６０ａが、金属層１０ａ中またはフィラメント状炭素層２０ａ中に存在している。すなわち、フィラメント状炭素膜２０ａは、フィラメント状炭素４２だけからなる第１層４０ａと、共存層６０ａとを有しており、金属層１０は、金属だけからなる第２層８０ａと共存層６０ａとを有する。複合膜１００ａは、第１層４０ａと共存層６０ａの間、及び共存層６０ａと第２層８０ａの間に別の層（中間層）を有さず、共存層６０ａが第１層４０ａと第２層８０ａの間の界面又は境界をなしている。フィラメント状炭素層２０ａに注目すれば、フィラメント状炭素膜２０の一方の面（フィラメント状炭素の集合体の一部）が金属層１０ａ中に含まれており、フィラメント状炭素膜２０ａの他方の面（フィラメント状炭素の集合体２０の他部）が前記金属層１０ａ上で露出している。 [Third Embodiment]
As shown in FIG. 2A, the composite film 100a of the third embodiment, like the composite film 100 of the first embodiment, is a filamentous carbon (film) 20a that is an aggregate of filamentous carbon, It is a self-supporting film comprised only from the metal layer 10a comprised from the metal, and a part of metal layer 10 has overlapped with a part of filamentous carbon layer 20a. For this reason, the coexistence layer (coexistence area | region) 60a in which filamentous carbon and a metal coexist exists in the metal layer 10a or the filamentous carbon layer 20a. That is, the filamentous carbon film 20a has a first layer 40a made only of the filamentous carbon 42 and a coexistence layer 60a, and the metal layer 10 has a second layer 80a made only of a metal and a coexistence layer 60a. Have The composite film 100a does not have another layer (intermediate layer) between the first layer 40a and the coexistence layer 60a, and between the coexistence layer 60a and the second layer 80a. It forms an interface or boundary between the two layers 80a. Paying attention to the filamentous carbon layer 20a, one surface of the filamentous carbon film 20 (part of the aggregate of filamentous carbon) is included in the metal layer 10a, and the other surface of the filamentous carbon film 20a. (The other part of the filament-like carbon aggregate 20) is exposed on the metal layer 10a.
　第３実施形態の複合膜１００ａは、図２（ａ）に示すように、第１層４０ａ及び共存層６０ａにおいて、フィラメント状炭素４２ａが第１層４０ａ及び共存層６０ａの厚み方向に配向（垂直配向）して、フィラメント状炭素４２ａの垂直配向構造４６が形成されている。垂直配向構造４６において、第２層８０ａの表面に垂直な方向に延在した複数のフィラメント状炭素４２ａが互いに空隙を有して隣接しており、共存層６０ａにおいて、該空隙内に金属が入り込んでいる。フィラメント状炭素４２ａの垂直配向構造４６は３ｎｍ～１０００ｎｍの範囲内の大きさの空隙を含んでよい。なお、複合膜１００ａの第１層４０ａ、第２層８０ａ及び共存層６０ａは、第１実施形態の複合膜１００の第１層４０、第２層８０及び共存層６０と同様の材料により構成されている。 In the composite film 100a of the third embodiment, as shown in FIG. 2A, in the first layer 40a and the coexistence layer 60a, the filamentous carbon 42a is oriented (perpendicular in the thickness direction of the first layer 40a and the coexistence layer 60a. The vertical alignment structure 46 of the filamentous carbon 42a is formed. In the vertical alignment structure 46, a plurality of filamentous carbons 42a extending in a direction perpendicular to the surface of the second layer 80a are adjacent to each other with a gap, and in the coexistence layer 60a, metal enters the gap. It is out. The vertical alignment structure 46 of the filamentous carbon 42a may include voids having a size in the range of 3 nm to 1000 nm. The first layer 40a, the second layer 80a, and the coexistence layer 60a of the composite film 100a are made of the same material as the first layer 40, the second layer 80, and the coexistence layer 60 of the composite film 100 of the first embodiment. ing.
　本実施形態の複合膜１００ａにおいて、上述の様に垂直配向したフィラメント状炭素４２ａの縦穴状の隙間に金属が入り込んでいることにより、非導電性材料からなるバインダーを用いることなくフィラメント状炭素と金属が機械的に接続される。また、フィラメント状炭素４２ａの網目内に金属が入り込んでいることによりフィラメント状炭素と金属が電気的にも接続されること、及び上述のように複合膜１００ａが非導電性材料からなるバインダーを含まないことから、本実施形態の複合膜１００ａは低抵抗である。さらに、フィラメント状炭素４２ａが金属から露出しているため、本実施形態の複合膜１００ａは表面積が大きい。それゆえ、第３実施形態の複合膜１００ａは、第１実施形態の複合膜１００と同様に、リチウムイオン電池等の蓄電デバイスの電極に使用される集電箔等として好適に用いることができる。 In the composite film 100a of the present embodiment, since the metal enters the vertical hole-like gaps of the filament-like carbon 42a vertically oriented as described above, the filament-like carbon and the metal can be used without using a binder made of a non-conductive material. Are mechanically connected. Further, since the metal enters the mesh of the filamentous carbon 42a, the filamentous carbon and the metal are also electrically connected, and the composite film 100a includes a binder made of a nonconductive material as described above. Therefore, the composite film 100a of this embodiment has a low resistance. Furthermore, since the filamentous carbon 42a is exposed from the metal, the composite film 100a of this embodiment has a large surface area. Therefore, like the composite film 100 of the first embodiment, the composite film 100a of the third embodiment can be suitably used as a current collector foil or the like used for an electrode of an electricity storage device such as a lithium ion battery.
　図２（ｂ）に、第３実施形態の複合膜１００ａの変形形態を示す。変形形態の複合膜１００ｂにおいて、垂直配向したフィラメント状炭素４２ｂは束となって第１層４０ｂ及び共存層６０ｂの厚み方向に直立した壁４１ｂを形成している。壁４１ｂは、第１層４０ｂ及び共存層６０ｂの厚み方向から見たときにランダムな網目構造４６ｂを形成している（図１３Ｅ参照）。網目構造４６ｂは、１～２００μｍの網目（空隙）を含んでよい。このような構造により、網目に種々の活物質を導入することができ、フィラメント状炭素が倒れにくく直立構造を維持し易くなり、性能に優れた蓄電デバイスの電極を作製できる。また、フィラメント状炭素の束からなる直立した壁は、一方向に規則的に並んだ筋状構造等の網目構造とは異なる任意の構造を形成してよい。 FIG. 2B shows a modification of the composite film 100a of the third embodiment. In the deformed composite film 100b, the vertically oriented filamentous carbon 42b is bundled to form a wall 41b that stands upright in the thickness direction of the first layer 40b and the coexistence layer 60b. The wall 41b forms a random network structure 46b when viewed from the thickness direction of the first layer 40b and the coexistence layer 60b (see FIG. 13E). The network structure 46b may include a network (void) of 1 to 200 μm. With such a structure, various active materials can be introduced into the mesh, the filamentous carbon is less likely to collapse, and an upright structure can be easily maintained, and an electrode of an electricity storage device with excellent performance can be manufactured. Further, the upright wall made of a bundle of filamentous carbon may form an arbitrary structure different from a network structure such as a streak structure regularly arranged in one direction.
［第４実施形態］
　図２（ｃ）、（ｄ）に示す機能性複合膜３００ａ、４００ａは、第３実施形態の自立した複合膜１００ａに活物質を付着させた機能性複合膜を示す。図２（ａ）に示す複合膜１００ａと同様に、フィラメント状炭素４２ａからなる第１層４０ａ、金属からなる第２層８０ａ、及び第１層４０ａと第２層８０ａの間に形成されたフィラメント状炭素４２ａと金属が共存する共存層６０ａを有する。機能性複合膜３００ａ、４００ａはさらに、第１層４０ａの共存層６０ａが形成された面と反対の面上において、フィラメント状炭素４２ａに付着している活物質３４ａを有する。すなわち、第４実施形態の機能性複合膜３００ａ、４００ａは、第３実施形態の複合膜１００ａの第１層４０ａを構成するフィラメント状炭素４２ａに活物質３４ａが付着した構成を有する。機能性複合膜３００ａ、４００ａの第１層４０ａ、第２層８０ａ及び共存層６０ａは、上記第３実施形態の機能性複合膜３００の第１層４０ａ、第２層８０ａ及び共存層６０ａと同様に構成され、機能性複合膜３００ａ、４００ａの活物質３４ａは上記第２実施形態の機能性複合膜３００、４００の活物質３４と同様に構成されるので、それらの詳細な説明は省略する。 [Fourth Embodiment]
The functional composite films 300a and 400a shown in FIGS. 2C and 2D are functional composite films in which an active material is attached to the self-supporting composite film 100a of the third embodiment. Similar to the composite film 100a shown in FIG. 2A, a first layer 40a made of filamentary carbon 42a, a second layer 80a made of metal, and a filament formed between the first layer 40a and the second layer 80a. A coexistence layer 60a in which the carbon-like carbon 42a and the metal coexist. The functional composite films 300a and 400a further have an active material 34a attached to the filamentous carbon 42a on the surface of the first layer 40a opposite to the surface on which the coexistence layer 60a is formed. That is, the functional composite films 300a and 400a of the fourth embodiment have a configuration in which the active material 34a is attached to the filamentous carbon 42a that constitutes the first layer 40a of the composite film 100a of the third embodiment. The first layer 40a, the second layer 80a and the coexistence layer 60a of the functional composite films 300a and 400a are the same as the first layer 40a, the second layer 80a and the coexistence layer 60a of the functional composite film 300 of the third embodiment. Since the active material 34a of the functional composite films 300a and 400a is configured similarly to the active material 34 of the functional composite films 300 and 400 of the second embodiment, detailed description thereof will be omitted.
　「活物質３４ａがフィラメント状炭素に付着している」とは、活物質３４ａが第１層４０ａの共存層６０ａが形成された面と反対の面から第１層４０ａの垂直配向構造４６の内部に活物質３４ａが入り込んだ形態（図２（ｃ）参照）、又はフィラメント状炭素４２ａの表面を活物質３４ａが覆うように付着している形態（図２（ｄ）参照）を含む。また、機能性複合膜３００ａ、４００ａが有する活物質３４ａの一部がフィラメント状炭素４２ａによる垂直配向構造４６に入り込んでいてもよいし、機能性複合膜３００ａ、４００ａが有する活物質３４ａの全部がフィラメント状炭素４２ａによる垂直配向構造４６に入り込んでいてもよい。また、機能性複合膜３００ａ、４００ａが有する活物質３４ａがフィラメント状炭素４２ａによる網目構造４４ａの全体に入り込んでいて共存層６０ａと直接接していてもよいし、機能性複合膜３００ａ、４００ａが有する活物質３４ａがフィラメント状炭素４２ａによる網目構造４４ａの一部に入り込んでいて共存層６０ａと直接接していなくてもよい。 “The active material 34a is attached to the filamentous carbon” means that the active material 34a is inside the vertical alignment structure 46 of the first layer 40a from the surface opposite to the surface on which the coexisting layer 60a of the first layer 40a is formed. In which the active material 34a enters (see FIG. 2 (c)), or the surface of the filamentous carbon 42a is attached so as to cover the active material 34a (see FIG. 2 (d)). Further, a part of the active material 34a included in the functional composite films 300a and 400a may enter the vertical alignment structure 46 of the filamentous carbon 42a, or the entire active material 34a included in the functional composite films 300a and 400a may be included. It may enter the vertical alignment structure 46 by the filamentous carbon 42a. Further, the active material 34a included in the functional composite films 300a and 400a may enter the entire network structure 44a of the filamentous carbon 42a and may be in direct contact with the coexistence layer 60a, or the functional composite films 300a and 400a may include the active material 34a. The active material 34a may enter a part of the network structure 44a of the filamentous carbon 42a and may not be in direct contact with the coexistence layer 60a.
　機能性複合膜３００ａ、４００ａをリチウムイオン電池の電極として用いた場合、活物質３４ａは充放電時のリチウムイオンの吸蔵及び放出に伴って大きく体積変化するが、活物質３４ａがフィラメント状炭素４２ａによる垂直配向構造４６に入り込んでいる、又は活物質３４ａがフィラメント状炭素４２ａの表面を覆うように付着しているため、フィラメント状炭素４２ａが撓むことで活物質３４ａの体積変化を吸収（緩和）することができ、活物質３４ａが第１層４０ａから剥離することが防止される。 When the functional composite films 300a and 400a are used as electrodes of a lithium ion battery, the active material 34a changes greatly in volume with the insertion and extraction of lithium ions during charging and discharging, but the active material 34a is made of filamentous carbon 42a. Since the vertical alignment structure 46 enters or the active material 34a adheres so as to cover the surface of the filamentous carbon 42a, the filamentous carbon 42a bends to absorb (relax) the volume change of the active material 34a. It is possible to prevent the active material 34a from peeling from the first layer 40a.
　また、上述の様に、第３実施形態の複合膜１００ａは、フィラメント状炭素４２ａが金属から露出しているため、表面積が大きい。したがって、第３実施形態の複合膜１００ａの第１層４０ａを構成するフィラメント状炭素４２ａに活物質３４ａが付着した構成を有する本実施形態の機能性複合膜３００ａ、４００ａは、活物質３４ａと第１層４０ａの接触面積が大きい（接触点が多い）。それゆえ、機能性複合膜３００ａ、４００ａにおいて、活物質３４ａとフィラメント状炭素４２ａから構成される第１層４０ａが機械的に良好に接続される。そのため、機能性複合膜３００ａ、４００ａをリチウムイオン電池に代表される電極として用いた場合、充放電時に活物質３４ａの体積が大きく変化しても、活物質３４ａが第１層４０ａから剥離しにくい。したがって、機能性複合膜３００ａ、４００ａをリチウムイオン電池などの蓄電デバイスの電極として用いることにより、長寿命の蓄電デバイスを製造することができる。 Also, as described above, the composite film 100a of the third embodiment has a large surface area because the filamentous carbon 42a is exposed from the metal. Therefore, the functional composite films 300a and 400a of the present embodiment having a configuration in which the active material 34a is attached to the filamentous carbon 42a constituting the first layer 40a of the composite film 100a of the third embodiment includes the active material 34a and the first active material 34a. The contact area of one layer 40a is large (many contact points). Therefore, in the functional composite films 300a and 400a, the first layer 40a composed of the active material 34a and the filamentous carbon 42a is mechanically well connected. Therefore, when the functional composite films 300a and 400a are used as electrodes typified by a lithium ion battery, even if the volume of the active material 34a changes greatly during charging and discharging, the active material 34a is difficult to peel from the first layer 40a. . Therefore, by using the functional composite films 300a and 400a as electrodes of an electricity storage device such as a lithium ion battery, a long-life electricity storage device can be manufactured.
　また、活物質３４ａと第１層４０ａの接触面積が大きいことにより、活物質３４ａとフィラメント状炭素４２ａから構成される第１層４０ａは電気的にも良好に接続される（接触抵抗が小さい）。さらに、本実施形態の機能性複合膜３００ａ、４００ａにおいて、第３実施形態の複合膜１００ａと同様に、フィラメント状炭素４２ａの垂直配向構造４６内に金属が入り込んでいることにより、フィラメント状炭素４２ａと金属が、非導電性材料からなるバインダーを介することなく接続されている。そのため、フィラメント状炭素４２ａからなる第１層４０ａと金属は、低抵抗に接続される。それゆえ、本実施形態の機能性複合膜３００ａ、４００ａにおいて、活物質３４ａと金属は低抵抗に接続される。更に、機能性複合膜３００ａ、４００ａにおいて、フィラメント状炭素４２ａが金属からなる第２層８０ａに対して垂直に配向しているため、フィラメント状炭素４２ａが最短距離で活物質３４ａを金属からなる第２層８０ａと繋げることができる。そのため、活物質３４ａの層が厚い場合も、活物質３４ａと第２層８０ａを低抵抗に接続できる。したがって、機能性複合膜３００ａ、４００ａをリチウムイオン電池で代表される二次電池の電極として用いることにより、高容量のリチウムイオン電池などの二次電池を製造することができる。 Further, since the contact area between the active material 34a and the first layer 40a is large, the first layer 40a composed of the active material 34a and the filamentous carbon 42a is electrically connected well (the contact resistance is small). . Furthermore, in the functional composite films 300a and 400a of the present embodiment, as in the composite film 100a of the third embodiment, the metal enters the vertical alignment structure 46 of the filamentous carbon 42a, whereby the filamentous carbon 42a. And the metal are connected without a binder made of a non-conductive material. Therefore, the first layer 40a made of filamentary carbon 42a and the metal are connected to a low resistance. Therefore, in the functional composite films 300a and 400a of the present embodiment, the active material 34a and the metal are connected with low resistance. Furthermore, in the functional composite films 300a and 400a, since the filamentous carbon 42a is oriented perpendicular to the second layer 80a made of metal, the filamentous carbon 42a has the shortest distance and the active material 34a is made of metal. It can be connected to the two layers 80a. Therefore, even when the layer of the active material 34a is thick, the active material 34a and the second layer 80a can be connected with low resistance. Therefore, a secondary battery such as a high-capacity lithium ion battery can be manufactured by using the functional composite films 300a and 400a as electrodes of a secondary battery represented by a lithium ion battery.
　機能性複合膜３００ａ、４００ａは、上述の様に活物質３４ａと第１層４０ａの接触面積が大きいため、バインダーを用いなくても活物質３４ａを第１層４０ａ上に固定することができるが、図２（ｃ）に示す機能性複合膜３００ａにおいて、活物質３４ａを第１層４０ａに固定するための非導電性ポリマーからなるバインダーを含んでいてもよい。この場合、機能性複合膜３００ａはさらに、カーボンナノファイバー（ＣＮＦ）、カーボンブラック等からなる導電材を含んでいても良い。上述の様に第１層４０ａは導電性のフィラメント状炭素４２ａからなり、高い表面積を持っているため、活物質３４ａとフィラメント状炭素４２ａの接触面積が大きく、バインダーを添加しても十分な導電性を確保できる。また、導電材を添加することで、活物質３４ａからなる層が第１層４０ａよりも厚い場合にも活物質３４ａからなる層の垂直方向の導電性を十分に確保できる。また、導電材が第１層４０ａの隙間に入り込むため活物質３４ａと第１層４０ａの間の導電性を十分に確保できる。 Since the functional composite films 300a and 400a have a large contact area between the active material 34a and the first layer 40a as described above, the active material 34a can be fixed on the first layer 40a without using a binder. In the functional composite film 300a shown in FIG. 2 (c), a binder made of a nonconductive polymer for fixing the active material 34a to the first layer 40a may be included. In this case, the functional composite film 300a may further include a conductive material made of carbon nanofiber (CNF), carbon black, or the like. As described above, the first layer 40a is made of the conductive filament carbon 42a and has a high surface area. Therefore, the contact area between the active material 34a and the filament carbon 42a is large, and sufficient conductivity can be obtained even if a binder is added. Can be secured. Further, by adding a conductive material, it is possible to sufficiently ensure the conductivity in the vertical direction of the layer made of the active material 34a even when the layer made of the active material 34a is thicker than the first layer 40a. In addition, since the conductive material enters the gap between the first layers 40a, the conductivity between the active material 34a and the first layer 40a can be sufficiently ensured.
　なお、第３実施形態の自立した複合膜１００ａに活物質を付着させる代わりに、変形形態の複合膜１００ｂに活物質を付着させて機能性複合膜を得ることもできる。 In addition, instead of attaching the active material to the self-supporting composite film 100a of the third embodiment, the functional composite film can be obtained by attaching the active material to the composite film 100b in a modified form.
［第１実施形態の複合膜及び第２実施形態の機能性複合膜の製造方法］
　上記第１実施形態の複合膜１００、及び第２実施形態の機能性複合膜３００、４００を製造する方法について説明する。本実施形態の製造方法は、図３に示すように、主に、フィラメント状炭素からなる膜（以下、適宜「フィラメント状炭素膜」という）を作製する工程Ｓ１と、作製したフィラメント状炭素膜を支持体（基板）により支持するフィラメント状炭素膜支持工程Ｓ２と、支持体に支持されたフィラメント状炭素膜上に金属を蒸着する金属蒸着工程Ｓ３と、フィラメント状炭素膜及び金属の複合膜を支持体から分離（剥離）する複合膜分離工程Ｓ４と、フィラメント状炭素膜の金属を蒸着した面と反対の面上に活物質を付着させる活物質付着工程Ｓ５とを有する。なお、本発明に従う複合膜の製造方法は、フィラメント状炭素膜支持工程Ｓ２及び活物質付着工程Ｓ５を有さなくてもよい。すなわち、本実施形態に従う複合膜の製造方法において、フィラメント状炭素膜支持工程Ｓ２及び活物質付着工程Ｓ５は随意の工程である。 [Method of Manufacturing Composite Film of First Embodiment and Functional Composite Film of Second Embodiment]
A method for manufacturing the composite film 100 of the first embodiment and the functional composite films 300 and 400 of the second embodiment will be described. As shown in FIG. 3, the manufacturing method of the present embodiment includes a step S1 for mainly producing a film made of filamentous carbon (hereinafter referred to as “filamentous carbon film” as appropriate), and the produced filamentous carbon film. Supporting a filamentous carbon film supporting step S2 supported by a support (substrate), a metal deposition step S3 for depositing metal on the filamentary carbon film supported by the support, and supporting a composite film of the filamentous carbon film and the metal A composite membrane separation step S4 for separating (separating) from the body, and an active material attaching step S5 for attaching an active material on the surface of the filamentous carbon film opposite to the surface on which the metal is deposited. In addition, the manufacturing method of the composite film according to this invention does not need to have filamentous carbon film support process S2 and active material adhesion process S5. That is, in the method for manufacturing a composite film according to the present embodiment, the filamentous carbon film supporting step S2 and the active material attaching step S5 are optional steps.
＜フィラメント状炭素膜作製工程Ｓ１＞
　フィラメント状炭素膜（フィラメント状炭素の集合体）は、例えば、スプレーコートやブレードコートにより、基板上にフィラメント状炭素の分散液を塗布・乾燥する方法、メンブレンフィルタを用いてフィラメント状炭素の分散液を濾過する方法等により形成することができる。 <Filamentary carbon film production step S1>
Filamentous carbon films (aggregates of filamentous carbon) are, for example, a method of applying and drying a dispersion of filamentous carbon on a substrate by spray coating or blade coating, a dispersion of filamentous carbon using a membrane filter It can form by the method of filtering.
　フィラメント状炭素の分散液は、界面活性剤の水溶液にＣＮＴ、ＣＮＦ等のフィラメント状炭素を加え、超音波分散させることにより調整することができる。界面活性剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム（ＳＤＢＳ）等を用いることができる。なお、市販のＣＮＴ分散液又はＣＮＦ分散液を用いてもよい。 The dispersion of filamentous carbon can be adjusted by adding filamentous carbon such as CNT or CNF to an aqueous solution of a surfactant and ultrasonically dispersing it. As the surfactant, for example, sodium dodecylbenzenesulfonate (SDBS) can be used. A commercially available CNT dispersion or CNF dispersion may be used.
　メンブレンフィルタを用いてフィラメント状炭素の分散液を濾過する方法によりフィラメント状炭素膜を形成する場合、図４（ａ）に示すように、メンブレンフィルタ１４０を用いてフィラメント状炭素分散液１２０を吸引濾過し、フィラメント状炭素を分散媒から分離することにより、メンブレンフィルタ１４０上にフィラメント状炭素膜２０を得ることができる。メンブレンフィルタ１４０としては、ＶＣＷＰフィルタ、ＰＴＦＥフィルタ、シリカ繊維フィルタ等を用いることができる。 When forming a filamentous carbon film by a method of filtering a filamentous carbon dispersion using a membrane filter, the filamentous carbon dispersion 120 is suction filtered using a membrane filter 140 as shown in FIG. The filamentous carbon film 20 can be obtained on the membrane filter 140 by separating the filamentous carbon from the dispersion medium. As the membrane filter 140, a VCWP filter, a PTFE filter, a silica fiber filter, or the like can be used.
　上記の方法によりフィラメント状炭素が絡み合った網目構造４４を有するフィラメント状炭素膜２０を形成することができる。上記の方法により形成したフィラメント状炭素膜２０の網目構造は、３ｎｍ～１０００ｎｍの範囲内の大きさの網目（立体的な空隙）を含むことができる。上記網目の大きさは概ねフィラメント状炭素の直径に相関して決まるが、更に分散液の粘度、フィルタの網目の大きさや表面の凹凸の程度、フィラメント状炭素膜の乾燥後の圧縮の有無などによって調整することができる。更に、有機溶媒に可溶なポリマー粒子とともにろ過してフィラメント状炭素膜を形成した後に、ポリマー粒子を溶媒で除去することによっても、網目の大きさを調整することができる。フィラメント状炭素膜２０がこのような大きさの網目を含むことにより、後述の金属蒸着工程Ｓ３において、金属がフィラメント状炭素膜２０内に入り込むことができる。 The filamentous carbon film 20 having the network structure 44 in which filamentous carbon is intertwined can be formed by the above method. The network structure of the filamentous carbon film 20 formed by the above method can include a network (steric void) having a size in the range of 3 nm to 1000 nm. The size of the mesh is generally determined in correlation with the diameter of the filamentous carbon, but further depends on the viscosity of the dispersion, the size of the mesh of the filter, the degree of unevenness of the surface, the presence or absence of compression after drying the filamentous carbon film, etc. Can be adjusted. Furthermore, the size of the mesh can also be adjusted by removing the polymer particles with a solvent after filtration with polymer particles soluble in an organic solvent to form a filamentous carbon film. Since the filamentous carbon film 20 includes a mesh having such a size, metal can enter the filamentous carbon film 20 in a metal vapor deposition step S3 described later.
＜フィラメント状炭素膜支持工程Ｓ２＞
　次いで、図４（ｂ）に示すように、メンブレンフィルタ１４０上に形成したフィラメント状炭素膜２０を基板（支持体）１６０上に支持させる（転写する）。基板１６０としては、ステンレス基板、ガラス基板、セラミックス基板、シリコン基板等を用いることができる。フィラメント状炭素膜２０は、例えば次のようにして基板１６０上に支持させることができる。基板１６０上にバインダーを塗布し、フィラメント状炭素膜２０と基板１６０上のバインダーを対向させて、フィラメント状炭素膜２０が形成されたメンブレンフィルタ１４０を基板１６０に押し付ける。バインダーを介してフィラメント状炭素膜４０が基板１６０に接着した後にメンブレンフィルタ１４０をフィラメント状炭素膜２０から剥がす。これらの操作により、フィラメント状炭素膜２０が基板１６０上に支持される。 <Filamentary carbon film support step S2>
Next, as shown in FIG. 4B, the filamentous carbon film 20 formed on the membrane filter 140 is supported (transferred) on the substrate (support) 160. As the substrate 160, a stainless steel substrate, a glass substrate, a ceramic substrate, a silicon substrate, or the like can be used. The filamentous carbon film 20 can be supported on the substrate 160 as follows, for example. A binder is applied onto the substrate 160, the filament carbon film 20 and the binder on the substrate 160 are made to face each other, and the membrane filter 140 on which the filament carbon film 20 is formed is pressed against the substrate 160. After the filamentous carbon film 40 adheres to the substrate 160 via the binder, the membrane filter 140 is peeled off from the filamentous carbon film 20. By these operations, the filamentous carbon film 20 is supported on the substrate 160.
　また、次の方法によりフィラメント状炭素膜２０を基板１６０上に支持させることもできる。フィラメント状炭素膜２０と基板１６０を対向させて、フィラメント状炭素膜２０が形成されたメンブレンフィルタ１４０を基板１６０に押し付ける。次いで、メンブレンフィルタ１４０をエタノールと水の混合溶液で濡らした後に乾燥させ、メンブレンフィルタ１４０をフィラメント状炭素膜２０から剥離する。これによりフィラメント状炭素膜２０を基板１６０上に支持させることができる。 Also, the filamentous carbon film 20 can be supported on the substrate 160 by the following method. The membrane filter 140 on which the filamentous carbon film 20 is formed is pressed against the substrate 160 with the filamentous carbon film 20 and the substrate 160 facing each other. Next, the membrane filter 140 is wetted with a mixed solution of ethanol and water and then dried, and the membrane filter 140 is peeled off from the filamentous carbon film 20. Thereby, the filamentous carbon film 20 can be supported on the substrate 160.
　更に、次の方法によりフィラメント状炭素膜２０を基板１６０上に支持させることもできる。フィラメント状炭素膜２０が形成されたメンブレンフィルタ１４０を純水に含浸する。すると、フィラメント状炭素膜２０のみが水面に浮かぶので、これを基板１６０で掬い取る。これによりフィラメント状炭素膜２０を基板１６０上に支持させることができる。基板１６０で掬い取る前に、加熱した純水でフィラメント状炭素膜２０を洗浄して、フィラメント状炭素膜２０に付着した界面活性剤を取り除いてもよい。 Furthermore, the filamentous carbon film 20 can be supported on the substrate 160 by the following method. The membrane filter 140 on which the filamentous carbon film 20 is formed is impregnated with pure water. Then, since only the filamentous carbon film 20 floats on the water surface, it is scooped by the substrate 160. Thereby, the filamentous carbon film 20 can be supported on the substrate 160. Before scrubbing with the substrate 160, the filamentous carbon film 20 may be washed with heated pure water to remove the surfactant attached to the filamentous carbon film 20.
　これらの方法により基板１６０上に支持したフィラメント状炭素膜２０を還元雰囲気下でアニールしてもよい。それにより、フィラメント状炭素膜２０に残留した界面活性剤を分解することができる。 The filamentous carbon film 20 supported on the substrate 160 by these methods may be annealed in a reducing atmosphere. Thereby, the surfactant remaining on the filamentous carbon film 20 can be decomposed.
　なお、上述したフィラメント状炭素膜作製工程Ｓ１において、ガラス繊維などの耐熱性をもつメンブレンフィルタを用いてフィラメント状炭素の分散液を濾過する方法によりフィラメント状炭素膜を作製する場合、メンブレンフィルタが基板（支持基板）を兼ねることができる。即ち、工程Ｓ１にてフィラメント状炭素をろ過してメンブレンフィルタ上に膜状にした後に、直ちに工程Ｓ３に入ることができる。また、フィラメント状炭素膜作製工程Ｓ１において、基板上に、スプレーコートやブレードコートでフィラメント状炭素の分散液を塗布・乾燥する方法によりフィラメント状炭素膜を作製する場合も、フィラメント状炭素膜支持工程Ｓ２を行うことなく、基板上に支持されたフィラメント状炭素膜を得ることができる。 In the above-described filamentous carbon film production step S1, when the filamentous carbon film is produced by a method of filtering a filamentous carbon dispersion using a heat resistant membrane filter such as glass fiber, the membrane filter is a substrate. It can also serve as a (supporting substrate). That is, after filtering the filamentous carbon in step S1 to form a film on the membrane filter, step S3 can be entered immediately. In the filamentous carbon film production step S1, the filamentous carbon film support step is also used when the filamentous carbon film is produced on the substrate by applying and drying the filamentous carbon dispersion by spray coating or blade coating. A filamentous carbon film supported on the substrate can be obtained without performing S2.
＜金属を蒸着する工程Ｓ３＞
　次いで、図４（ｃ）に示すように、基板１６０に支持されたフィラメント状炭素膜２０上に金属を蒸着する。それにより、図４（ｃ）に示すように、フィラメント状炭素膜２０上に金属層１０を形成することができる。 <Step S3 for depositing metal>
Next, as shown in FIG. 4C, a metal is deposited on the filamentous carbon film 20 supported by the substrate 160. Thereby, as shown in FIG. 4C, the metal layer 10 can be formed on the filamentous carbon film 20.
　金属の蒸着は、抵抗加熱蒸着、電子線蒸着、スパッタ、ＣＶＤ等の任意の蒸着法で行うことができる。金属の蒸着膜厚（形成される金属層の厚さ）は、用途に応じて任意の厚さにすることができるが、例えば本実施形態の製造方法により製造した複合膜をリチウムイオン電池の負極に用いる場合には、０．０３μｍ～３０μｍの範囲内であることが好ましく、１～１０μｍの範囲内にあるとより好ましい。 Metal vapor deposition can be performed by any vapor deposition method such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, and CVD. The vapor deposition thickness of the metal (thickness of the metal layer to be formed) can be set to any thickness depending on the application. For example, the composite film produced by the production method of the present embodiment is used as the negative electrode of the lithium ion battery. When it is used in the above, it is preferably in the range of 0.03 to 30 μm, more preferably in the range of 1 to 10 μm.
＜複合膜を基板から分離する工程Ｓ４＞
　次に、フィラメント状炭素膜２０及び金属層１０からなる複合膜１００を基板１６０から剥離する（図４（ｄ）参照）。フィラメント状炭素膜２０及び金属層１０は、例えばピンセットでフィラメント状炭素膜２０の外周部をつまみ、基板１６０から引き上げる方法等により、機械的に基板１６０から剥離することができる。すなわち、自立したフィラメント状炭素と金属の複合膜１００が得られる。こうして得られた複合膜１００は、図４（ｄ）に示すように、フィラメント状炭素膜２０の網目内に金属層１０の一部が入り込んだ（潜り込んだ）構造を有する。すなわち、得られた複合膜１００は、フィラメント状炭素からなる第１層４０と、金属からなる第２層８０と、第１層４０と第２層８０との間に形成された、フィラメント状炭素と金属とが共存する共存層６０とを有する。上記のような方法でフィラメント状炭素膜上に金属を蒸着することにより、フィラメント状炭素膜２０の表層から０．０１μｍ～１０μｍの範囲の深さまで金属を入り込ませることができる。すなわち、０．０１μｍ～１０μｍの範囲の厚さを有する共存層６０を形成することができる。 <Step S4 of separating the composite film from the substrate>
Next, the composite film 100 composed of the filamentous carbon film 20 and the metal layer 10 is peeled from the substrate 160 (see FIG. 4D). The filamentous carbon film 20 and the metal layer 10 can be mechanically separated from the substrate 160 by, for example, a method of picking the outer periphery of the filamentous carbon film 20 with tweezers and pulling it up from the substrate 160. That is, a self-supporting filamentous carbon and metal composite film 100 is obtained. The composite film 100 obtained in this way has a structure in which a part of the metal layer 10 has entered (sunk into) the mesh of the filamentous carbon film 20 as shown in FIG. That is, the obtained composite film 100 includes a filamentous carbon formed between the first layer 40 made of filamentous carbon, the second layer 80 made of metal, and the first layer 40 and the second layer 80. And a coexistence layer 60 in which a metal coexists. By depositing a metal on the filamentous carbon film by the method as described above, the metal can be penetrated from the surface layer of the filamentous carbon film 20 to a depth in the range of 0.01 μm to 10 μm. That is, the coexistence layer 60 having a thickness in the range of 0.01 μm to 10 μm can be formed.
＜活物質を付着させる工程Ｓ５＞
　上記工程から得られた自立した複合膜を所定の機能を持たせた機能性複合膜にする工程を説明する。上記のようにして得られた自立した複合膜１００に活物質（リチウムイオンを吸蔵及び脱離できる材料）３４を付着させる。図４（ｅ）に示すように、活物質３４がフィラメント状炭素膜２０の金属を蒸着した面と反対の面からフィラメント状炭素膜２０の網目構造４４の内部に入り込むように活物質３４を付着させてもよいし、フィラメント状炭素膜２０の表面を活物質３４が覆うように活物質３４を付着させてもよい。 <Step S5 for attaching an active material>
The process of making the self-supporting composite film obtained from the above process into a functional composite film having a predetermined function will be described. An active material (a material capable of inserting and extracting lithium ions) 34 is attached to the self-supporting composite film 100 obtained as described above. As shown in FIG. 4E, the active material 34 is attached so that the active material 34 enters the inside of the network structure 44 of the filamentous carbon film 20 from the surface opposite to the surface on which the metal of the filamentous carbon film 20 is deposited. The active material 34 may be attached so that the active material 34 covers the surface of the filamentous carbon film 20.
　例えば、粒子状の活物質にバインダー、導電材等を混ぜたペーストを作製し、これをフィラメント状炭素膜２０上に塗布した後乾燥させる方法により、図４（ｅ）に示すように活物質３４がフィラメント状炭素膜２０の網目構造４４の内部に入り込むように、活物質３４を付着させることができる。 For example, a paste in which a binder, a conductive material, and the like are mixed with a particulate active material is prepared, applied to the filamentous carbon film 20, and then dried, as shown in FIG. The active material 34 can be attached so that the gas enters the inside of the network structure 44 of the filamentous carbon film 20.
　また、活物質３４をフィラメント状炭素膜２０上に蒸着することにより、フィラメント状炭素膜２０の表面を活物質３４が覆うように、活物質３４を付着させることができる（図１（ｃ）参照）。蒸着源としては、Ｓｉ、Ｓｎ、ＳｎＯや、ＳｉないしＳｎと他の金属との混合物、Ｓ等を用いることができる。蒸着源には、不純物がドープされていてもよい。このような不純物としては、窒素、リン、アルミニウム、砒素、ホウ素、ガリウム、インジウム、酸素、炭素等の元素を挙げることができる。 Further, the active material 34 can be deposited by depositing the active material 34 on the filamentous carbon film 20 so that the active material 34 covers the surface of the filamentous carbon film 20 (see FIG. 1C). ). As a deposition source, Si, Sn, SnO, a mixture of Si or Sn and other metals, S, or the like can be used. The evaporation source may be doped with impurities. Examples of such impurities include elements such as nitrogen, phosphorus, aluminum, arsenic, boron, gallium, indium, oxygen, and carbon.
　以上のようにして、図１（ｂ）、（ｃ）、図４（ｅ）に示すように、フィラメント状炭素膜２０に活物質３４が付着した、フィラメント状炭素と金属と活物質からなる機能性複合膜３００、４００が得られる。得られた機能性複合膜３００、４００は、フィラメント状炭素からなる第１層４０と、金属からなる第２層８０と、第１層４０と第２層８０との間に形成された、フィラメント状炭素と金属とが共存する共存層６０を有し、さらに、第１層４０を構成するフィラメント状炭素４２に活物質３４が付着している。上記の方法で製造された機能性複合膜３００、４００は、活物質３４の一部又は全部がフィラメント状炭素膜２０の網目構造４４に入り込んだ構造、又は活物質３４がフィラメント状炭素４２の表面を覆うように付着している構造を有することができる。 As described above, as shown in FIGS. 1B, 1C, and 4E, the active material 34 adheres to the filamentous carbon film 20, and the function composed of filamentous carbon, metal, and active material. Conductive composite films 300 and 400 are obtained. The obtained functional composite films 300 and 400 are filaments formed between the first layer 40 made of filamentary carbon, the second layer 80 made of metal, and the first layer 40 and the second layer 80. The active material 34 is attached to the filamentous carbon 42 constituting the first layer 40. The functional composite films 300 and 400 manufactured by the above method have a structure in which part or all of the active material 34 enters the network structure 44 of the filamentous carbon film 20, or the active material 34 has a surface of the filamentous carbon 42. It can have a structure attached so that it may cover.
　上記では、複合膜の製造方法をバッチ式のプロセスを例に挙げて説明したが、生産効率を考慮した連続式のプロセスを用いていてもよい。例えば、上記工程Ｓ１～Ｓ４を図６（ａ）に示した複合膜の製造装置１５０を用いて連続的に行うことができる。以下に、製造装置１５０を用いて第１実施形態の複合膜１００を製造する方法を説明する。図６（ａ）に示す装置１５０は、主に、駆動ローラ５２ａと従動ローラ５２ｂからなるローラ対５２と、ローラ対５２に掛け渡されて移動する無端の搬送ベルト５４と、搬送ベルト５４の上方に設置された供給器５６と、搬送ベルト５４を介して供給器５６の下方に設置された吸引濾過機６３と、供給器５６の搬送方向下流側であって且つ搬送ベルト５４の下方に設置された蒸着器５８とを備える。搬送ベルト５４は、耐熱性とメンブレンフィルタ機能を有する網目状のベルトである。供給器５６は前述の工程Ｓ１で調製されたフィラメント状炭素の分散液５１を搬送ベルト５４に供給し、吸引濾過機６３により搬送ベルト５４上の分散体を吸引するとともにフィラメント状炭素の集合体を搬送ベルト５４上に残留させる。蒸着器５８は、蒸着源として金属片を内部に収容するボートを備え、フィラメント状炭素の集合体に金属を蒸着させる。 In the above, the manufacturing method of the composite film has been described by taking a batch process as an example, but a continuous process in consideration of production efficiency may be used. For example, the above steps S1 to S4 can be continuously performed using the composite film manufacturing apparatus 150 shown in FIG. Below, the method to manufacture the composite film 100 of 1st Embodiment using the manufacturing apparatus 150 is demonstrated. The apparatus 150 shown in FIG. 6A mainly includes a roller pair 52 including a driving roller 52a and a driven roller 52b, an endless conveying belt 54 that moves across the roller pair 52, and an upper portion of the conveying belt 54. A suction filter 63 installed below the feeder 56 via the conveyor belt 54, and downstream of the feeder 56 in the conveyance direction and below the conveyor belt 54. The vapor deposition device 58 is provided. The conveyor belt 54 is a mesh belt having heat resistance and a membrane filter function. The supply unit 56 supplies the filamentous carbon dispersion 51 prepared in the above-described step S <b> 1 to the conveyor belt 54, sucks the dispersion on the conveyor belt 54 by the suction filter 63, and collects the aggregate of filamentous carbon. It remains on the conveyor belt 54. The vapor deposition device 58 includes a boat that accommodates metal pieces therein as a vapor deposition source, and deposits metal on an aggregate of filamentous carbon.
　この装置１５０を用いた連続式製造プロセスを説明する。駆動ローラ５２ａが矢印の回転方向に回転して搬送ベルト５４が移動し始めると、供給器５６からフィラメント状炭素の分散液５１が搬送ベルト５４上に所定量で連続的に供給され、吸引濾過機６３と搬送ベルト５４により分散液の液体分が濾過されて搬送ベルト５４上に固形分としてのフィラメント状炭素の集合体５３が形成される。次いで、フィラメント状炭素の集合体５３が搬送ベルト５４により下流の蒸着器５８と対向する位置まで搬送されると、蒸着器５８によって加熱溶融された蒸着源からの金属がフィラメント状炭素の集合体５３の表面に付着する。こうしてフィラメント状炭素の集合体５３の一面に金属５５が付着した複合膜５９が得られる。この複合膜５９は、連続膜であるため、複合膜５９の搬送方向前端が従動ローラ５２ｂで巻き上げられるときに、その前端に従動ローラの接線方向（水平方向）の引張力を与えることにより、順次、搬送ベルト５４から外れて長尺の自立した複合膜５９（複合連続膜）が得られる。この長尺の自立した複合膜５９を適宜ローラなどに巻き取って回収し、管理することができる。 A continuous manufacturing process using this apparatus 150 will be described. When the driving roller 52a rotates in the direction indicated by the arrow and the conveyor belt 54 starts to move, the filament-like carbon dispersion 51 is continuously supplied from the supply device 56 onto the conveyor belt 54 in a predetermined amount. The liquid component of the dispersion liquid is filtered by 63 and the conveyor belt 54 to form a filamentous carbon aggregate 53 as a solid component on the conveyor belt 54. Next, when the filamentous carbon aggregate 53 is conveyed to a position facing the downstream vapor deposition unit 58 by the conveyance belt 54, the metal from the vapor deposition source heated and melted by the vapor deposition unit 58 becomes the filamentous carbon aggregate 53. Adhere to the surface. Thus, a composite film 59 in which the metal 55 is attached to one surface of the filamentous carbon aggregate 53 is obtained. Since the composite film 59 is a continuous film, when the front end in the conveyance direction of the composite film 59 is wound up by the driven roller 52b, the tensile force in the tangential direction (horizontal direction) of the driven roller at the front end is sequentially applied. Thus, a long and self-supporting composite film 59 (composite continuous film) is obtained by removing from the conveyor belt 54. The long self-supporting composite film 59 can be appropriately wound around a roller and collected and managed.
　この具体例では、供給器５６、吸引濾過機６３及び搬送ベルト５４がフィラメント状炭素の集合体形成部として機能したが、スプレーコータやブレードコータのようなコータと乾燥器を用いてもよい。この場合、分散液をコータで搬送ベルト上に塗布して、塗布した分散液を乾燥器で乾燥することができ、搬送ベルトはフィルタ機能を有する必要はない。また、複合膜５９の前端に従動ローラ５２ｂの接線方向（水平方向）の引張力を与えて搬送ベルト５４から剥離（分離）するための剥離ローラのような機構を設けてもよい。 In this specific example, the feeder 56, the suction filter 63, and the conveyor belt 54 functioned as the filament-like carbon aggregate forming unit, but a coater such as a spray coater or a blade coater and a dryer may be used. In this case, the dispersion liquid can be applied onto the conveyor belt with a coater, and the applied dispersion liquid can be dried with a dryer, and the conveyor belt need not have a filter function. Further, a mechanism such as a peeling roller for separating (separating) from the conveying belt 54 by applying a tensile force in the tangential direction (horizontal direction) of the driven roller 52b of the front end of the composite film 59 may be provided.
　更に、搬送ベルト５４が駆動ローラ５２を兼ねることもできる。即ち搬送ベルトの代わりに円筒を用い、円筒を回転させながら、その上部にてフィラメント状炭素を連続的に付着し、下部にて付着したフィラメント状炭素に金属を蒸着すると、連続的に剥がして回収することができる。網目状のシートで構成した円筒を用いた際は、吸引ろ過によりフィラメント状炭素の分散液からフィラメント状炭素の集合体を形成することができる。穴の無いシートで構成した円筒を用いた際はスプレーコータやブレードコータを用いて、フィラメント状炭素の分散液からフィラメント状炭素の集合体を形成することができる。この円筒１つにて、搬送ベルト５４と駆動ローラ５２ａ、５２ｂを兼ねることとなる。 Furthermore, the conveyance belt 54 can also serve as the driving roller 52. In other words, a cylinder is used instead of the conveyor belt, and while rotating the cylinder, filamentary carbon is continuously deposited on the upper part, and metal is deposited on the filamentous carbon deposited on the lower part. can do. When a cylinder composed of a mesh-like sheet is used, an aggregate of filamentous carbon can be formed from a dispersion of filamentous carbon by suction filtration. When a cylinder composed of a sheet without holes is used, an aggregate of filamentous carbon can be formed from a dispersion of filamentous carbon using a spray coater or a blade coater. One cylinder serves as both the conveyor belt 54 and the driving rollers 52a and 52b.
［第３実施形態及び第４実施形態の複合膜の製造方法］
　上記第３実施形態の複合膜１００ａ及び第４実施形態の機能性複合膜３００ａ、４００ａを製造する方法について説明する。複合膜１００ａ、及び機能性複合膜３００ａ、４００ａの製造方法は、主に、フィラメント状炭素からなる膜（フィラメント状炭素膜）を作製する工程Ｓ１と、支持体（基板）に支持されたフィラメント状炭素膜上に金属を蒸着する工程Ｓ３と、フィラメント状炭素膜及び金属の複合膜を支持体から分離する工程Ｓ４と、フィラメント状炭素膜の金属を蒸着した面と反対の面上に活物質を付着させる工程Ｓ５とを有する。なお、本実施形態に従う複合膜の製造方法は、活物質付着工程Ｓ５を有さなくてもよい。 [Method for Producing Composite Film of Third Embodiment and Fourth Embodiment]
A method for manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment will be described. The manufacturing method of the composite film 100a and the functional composite films 300a and 400a mainly includes a step S1 for producing a film made of filamentous carbon (filamentous carbon film), and a filament shape supported by a support (substrate). Step S3 for depositing metal on the carbon film, Step S4 for separating the filamentary carbon film and the metal composite film from the support, and an active material on the surface of the filamentous carbon film opposite to the surface on which the metal is deposited. And attaching step S5. In addition, the manufacturing method of the composite film according to this embodiment does not need to have active material adhesion process S5.
＜フィラメント状炭素膜を作製する工程Ｓ１＞
　上記第１実施形態の複合膜１００及び第２実施形態の機能性複合膜３００、４００の製造方法の実施形態では、フィラメント状炭素膜作製工程Ｓ１において、網目構造を有するフィラメント状炭素膜を形成したが、第３実施形態の複合膜１００ａ及び第４実施形態の機能性複合膜３００ａ、４００ａの製造方法では、フィラメント状炭素がフィラメント状炭素膜の厚み方向に配向（垂直配向）したフィラメント状炭素膜を形成する。 <Step S1 for producing filamentary carbon film>
In the embodiment of the manufacturing method of the composite film 100 of the first embodiment and the functional composite films 300 and 400 of the second embodiment, the filamentous carbon film having a network structure is formed in the filamentous carbon film manufacturing step S1. However, in the method of manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment, the filamentous carbon film in which filamentous carbon is oriented (vertically oriented) in the thickness direction of the filamentous carbon film. Form.
　フィラメント状炭素の垂直配向膜は、例えば、図５（ａ）に示すようにフィラメント状炭素を合成するための触媒となる粒子４８を表面に形成した基板（支持体）１６０ａを、反応器に配置し、基板１６０ａを加熱しながら反応器内に原料ガスを流通させることによって作製することができる。触媒としてはＦｅ、Ｃｏ、Ｎｉ等が、触媒担体としてはＳｉ、Ａｌ、Ｍｇの酸化物等を用いることができる。原料ガスとしてはアセチレン、エチレン、エタノール、メタン等を用いることができる。このようにして、図５（ｂ）に示すように、フィラメント状炭素４２ａが垂直に配向した構造４６を有するフィラメント状炭素膜２０ａを基板１６０ａ上に形成することができる。本フィラメント状炭素膜を作製する工程Ｓ１によって作製されたフィラメント状炭素膜２０ａは基板１６０ａに支持されているため、本製造方法は、作製したフィラメント状炭素膜を基板上に支持する工程Ｓ２を有さなくてよい。 In the vertical alignment film of filamentous carbon, for example, as shown in FIG. 5 (a), a substrate (support) 160a on which particles 48 as a catalyst for synthesizing filamentary carbon are formed is disposed in a reactor. Then, the substrate 160a can be produced by circulating the source gas in the reactor while heating. Fe, Co, Ni, etc. can be used as the catalyst, and Si, Al, Mg oxides, etc. can be used as the catalyst carrier. As the source gas, acetylene, ethylene, ethanol, methane or the like can be used. In this manner, as shown in FIG. 5B, the filamentous carbon film 20a having the structure 46 in which the filamentous carbon 42a is vertically oriented can be formed on the substrate 160a. Since the filamentous carbon film 20a produced by the step S1 for producing the filamentous carbon film is supported by the substrate 160a, the manufacturing method includes the step S2 for supporting the produced filamentary carbon film on the substrate. You don't have to.
＜金属を蒸着する工程Ｓ３＞
　第３実施形態の複合膜１００ａ及び第４実施形態の機能性複合膜３００ａ、４００ａの製造方法における金属を蒸着する工程Ｓ３は、上記複合膜１００及び機能性複合膜３００、４００の製造方法の工程Ｓ３と同様にして行うことができるため、詳細な説明は省略する。本工程Ｓ３によりフィラメント状炭素膜２０ａ上に金属層１０ａを形成することができる。このとき、図５（ｃ）に示すように、フィラメント状炭素膜２０ａの各フィラメント状炭素４２ａの間の空隙に金属層１０ａの一部が入り込んでいる（潜り込んでいる）。 <Step S3 for depositing metal>
Step S3 for depositing metal in the method of manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment is a process of the method of manufacturing the composite film 100 and the functional composite films 300 and 400. Since it can be performed in the same manner as S3, detailed description is omitted. By this step S3, the metal layer 10a can be formed on the filamentous carbon film 20a. At this time, as shown in FIG. 5 (c), a part of the metal layer 10a has entered (submitted) into the gaps between the filamentous carbons 42a of the filamentous carbon film 20a.
＜複合膜を基板から分離する工程Ｓ４＞
　第３実施形態の複合膜１００ａ、及び第４実施形態の機能性複合膜３００ａ、４００ａの製造方法における複合膜を基板から分離する工程Ｓ４は、上記複合膜１００、及び機能性複合膜３００、４００の製造方法の工程Ｓ４と同様にして行うことができるため、詳細な説明は省略する。フィラメント状炭素膜２０ａ及び金属層１０ａからなる複合膜１００ａを基板１６０ａから剥離すると、図５（ｄ）に示すように、フィラメント状炭素膜２０ａの各フィラメント状炭素４２ａの間の空隙に金属層１０ａの一部が入り込んだ（潜り込んだ）構造を有する複合膜１００ａが得られる。すなわち、得られた複合膜１００ａは、フィラメント状炭素４２ａからなる第１層４０ａと、金属からなる第２層８０ａと、第１層４０ａと第２層８０ａとの間に形成された、フィラメント状炭素４２ａと金属とが共存する共存層６０ａとを有する。 <Step S4 of separating the composite film from the substrate>
Step S4 of separating the composite film from the substrate in the method of manufacturing the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment includes the composite film 100 and the functional composite films 300 and 400. Since it can carry out similarly to process S4 of this manufacturing method, detailed description is abbreviate | omitted. When the composite film 100a composed of the filamentous carbon film 20a and the metal layer 10a is peeled from the substrate 160a, as shown in FIG. 5D, the metal layer 10a is formed in the gap between the filamentous carbons 42a of the filamentous carbon film 20a. As a result, a composite film 100a having a structure in which a part of the film has entered (submerged) is obtained. That is, the obtained composite film 100a has a filament-like shape formed between the first layer 40a made of filamentous carbon 42a, the second layer 80a made of metal, and the first layer 40a and the second layer 80a. It has a coexistence layer 60a in which carbon 42a and metal coexist.
＜活物質を付着させる工程Ｓ５＞
　第３実施形態の複合膜１００ａ及び第４実施形態の機能性複合膜３００ａ、４００ａの製造方法における活物質を付着させる工程Ｓ５は、上記複合膜１００、機能性複合膜３００、４００の製造方法の工程Ｓ５と同様にして行うことができるため、詳細な説明は省略する。 <Step S5 for attaching an active material>
The step S5 of attaching the active material in the manufacturing method of the composite film 100a of the third embodiment and the functional composite films 300a and 400a of the fourth embodiment is the method of manufacturing the composite film 100 and the functional composite films 300 and 400. Since it can carry out similarly to process S5, detailed description is abbreviate | omitted.
　本工程Ｓ５において、例えば、粒子状の活物質にバインダー、導電材等を混ぜたペーストを作製し、これをフィラメント状炭素膜２０ａ上に塗布した後乾燥させる方法により、図５（ｅ）に示すように、活物質３４ａがフィラメント状炭素膜２０ａの垂直配向構造４６の内部に入り込むように、活物質３４ａを付着させることができる。 In this step S5, for example, a paste is prepared by mixing a particulate active material with a binder, a conductive material, etc., and this is applied onto the filamentous carbon film 20a and then dried, as shown in FIG. 5 (e). Thus, the active material 34a can be attached so that the active material 34a enters the inside of the vertical alignment structure 46 of the filamentous carbon film 20a.
　また、活物質３４ａをフィラメント状炭素膜２０ａ上に蒸着することにより、フィラメント状炭素膜２０ａの表面を活物質３４ａが覆うように、活物質３４ａを付着させることができる（図２（ｄ）参照）。 Further, by depositing the active material 34a on the filamentous carbon film 20a, the active material 34a can be attached so that the active material 34a covers the surface of the filamentous carbon film 20a (see FIG. 2D). ).
　以上のようにして、図２（ｃ）、（ｄ）、図５（ｅ）に示すように、フィラメント状炭素膜２０ａに活物質３４ａが付着した、フィラメント状炭素と金属と活物質からなる機能性複合膜３００ａ、４００ａが得られる。得られた機能性複合膜３００ａ、４００ａは、フィラメント状炭素からなる第１層４０ａと、金属からなる第２層８０ａと、第１層４０ａと第２層８０ａとの間に形成された、フィラメント状炭素４２ａと金属とが共存する共存層６０ａとを有し、さらに、さらに、第１層４０ａを構成するフィラメント状炭素４２ａに活物質３４ａが付着している。上記の方法で製造された機能性複合膜３００ａ、４００ａは、活物質３４ａの一部又は全部がフィラメント状炭素膜２０ａの垂直配向構造４６に入り込んだ構造、又は活物質３４ａがフィラメント状炭素４２ａの表面を覆うように付着している構造を有することができる。 As described above, as shown in FIGS. 2C, 2D, and 5E, the active material 34a is attached to the filamentous carbon film 20a, and the function is composed of filamentous carbon, metal, and active material. Composite films 300a and 400a are obtained. The obtained functional composite films 300a and 400a are filaments formed between the first layer 40a made of filamentary carbon, the second layer 80a made of metal, and the first layer 40a and the second layer 80a. The active carbon 34a is attached to the filamentous carbon 42a constituting the first layer 40a. The functional composite films 300a and 400a manufactured by the above method have a structure in which part or all of the active material 34a enters the vertical alignment structure 46 of the filamentous carbon film 20a, or the active material 34a is made of the filamentous carbon 42a. It can have a structure attached to cover the surface.
　なお、工程Ｓ４において複合膜１００ａを基板１６０ａから分離した後に、フィラメント状炭素の垂直配向膜を収縮させて、フィラメント状炭素４２ｂの壁４１ｂからなるランダムな網目構造４６ｂを有するフィラメント状炭素膜２０ｂを形成してもよい（図２（ｂ）参照）。フィラメント状炭素４２ｂの壁４１ｂからなる網目構造４６ｂは、次のようにして形成することができる。例えば、フィラメント状炭素の垂直配向膜をエタノール等の溶媒蒸気に曝してフィラメント炭素膜上に溶媒を凝縮させた後に、凝縮した溶媒を乾燥させることによって、溶媒の表面張力でフィラメント状炭素膜２０ａが収縮してフィラメント状炭素４２ｂの壁４１ｂからなる網目構造４６ｂが形成される。網目構造４６ｂの網目の大きさは、例えばフィラメント状炭素４２ｂの垂直配向膜の高さを変えることによって制御することができる。フィラメント状炭素の垂直配向膜の高さは、例えば、フィラメント状炭素膜作製工程Ｓ１においてフィラメント状炭素を合成する時間を変えることによって制御することができる。また、工程Ｓ１においてフィラメント状炭素の合成に用いる基板１６０ａの表面のテクスチャ（凹凸）によりフィラメント状炭素の壁が形成する構造を制御することができる。ゆえに、上記網目構造とは異なる任意の構造の形成も可能である。例えば、工程Ｓ１において基板１６０ａとして一方向に延在する筋状（ライン状）のテクスチャが表面に形成された基板を用いてフィラメント状炭素の垂直配向膜を形成し、工程Ｓ４において複合膜１００ａを基板１６０ａから分離した後に、フィラメント状炭素の垂直配向膜を収縮させることにより、フィラメント状炭素の壁が一方向に規則的に並んだ筋状構造を形成することができる。 In addition, after separating the composite film 100a from the substrate 160a in step S4, the filamentary carbon vertical alignment film is contracted to form a filamentous carbon film 20b having a random network structure 46b composed of the walls 41b of the filamentous carbon 42b. You may form (refer FIG.2 (b)). The network structure 46b composed of the walls 41b of the filamentous carbon 42b can be formed as follows. For example, by exposing the filamentary carbon vertical alignment film to a solvent vapor such as ethanol to condense the solvent on the filament carbon film, and then drying the condensed solvent, the filamentous carbon film 20a is formed by the surface tension of the solvent. The network structure 46b which consists of the wall 41b of the filament-like carbon 42b is shrunk and formed. The mesh size of the mesh structure 46b can be controlled, for example, by changing the height of the vertical alignment film of the filamentous carbon 42b. The height of the filamentary carbon vertical alignment film can be controlled, for example, by changing the time for synthesizing the filamentous carbon in the filamentous carbon film manufacturing step S1. In addition, the structure formed by the filamentous carbon walls can be controlled by the texture (unevenness) of the surface of the substrate 160a used for synthesizing the filamentous carbon in step S1. Therefore, it is possible to form an arbitrary structure different from the network structure. For example, a vertical alignment film of filamentous carbon is formed using a substrate having a streaky (line-like) texture extending in one direction on the surface as the substrate 160a in step S1, and the composite film 100a is formed in step S4. After separating from the substrate 160a, the filamentary carbon vertical alignment film is contracted to form a streak structure in which filamentary carbon walls are regularly arranged in one direction.
　次に、本実施形態における工程Ｓ１～Ｓ４を、図６（ｂ）に示した複合膜の製造装置１７０を用いて連続的に行い、第３実施形態の複合膜１００ａを製造する方法を説明する。図６（ｂ）に示す装置１７０は、主に、駆動ローラ５２ａと従動ローラ５２ｂからなるローラ対５２と、ローラ対５２に掛け渡されて移動する無端の搬送ベルト５４ａと、搬送ベルト５４ａの上方に設置されたスパッタ装置７１と、その搬送方向下流側に設置されたＣＶＤ装置７３と、ＣＶＤ装置７３の搬送方向下流側であって且つ搬送ベルト５４ａの下方に設置された蒸着器５８とを備える。スパッタ装置７１は、フィラメント状炭素を合成するためのＦｅなどの触媒７４を支持体としての搬送ベルト５４に付着させる。搬送ベルトにＡｌ２Ｏ３などの触媒担体を付着した上でＦｅなどの触媒７４を付着させるとなお良い。ＣＶＤ装置７３は、触媒７４上でフィラメント状炭素を合成して成長させるためにアセチレンなどの合成用ガスを触媒に供給する。ＣＶＤ装置７３としてはシャワーヘッド構造のノズルを備えたＣＶＤ装置が好適である。なお、この例の搬送ベルト５４ａは、図６（ａ）に示した装置で用いた搬送ベルト５４と異なり、フィルタ機能を備える必要はない。 Next, a method of manufacturing the composite film 100a of the third embodiment by performing the steps S1 to S4 in the present embodiment continuously using the composite film manufacturing apparatus 170 shown in FIG. 6B will be described. . The apparatus 170 shown in FIG. 6 (b) mainly includes a roller pair 52 composed of a driving roller 52a and a driven roller 52b, an endless conveying belt 54a that moves across the roller pair 52, and an upper portion of the conveying belt 54a. , A CVD device 73 installed on the downstream side in the transport direction, and a vapor deposition device 58 installed on the downstream side in the transport direction of the CVD device 73 and below the transport belt 54a. . The sputtering apparatus 71 attaches a catalyst 74 such as Fe for synthesizing filamentary carbon to a conveyor belt 54 as a support. It is more preferable that a catalyst carrier such as Al 2 O 3 is attached to the transport belt and then a catalyst 74 such as Fe is attached. The CVD apparatus 73 supplies a synthesis gas such as acetylene to the catalyst in order to synthesize and grow filamentous carbon on the catalyst 74. As the CVD apparatus 73, a CVD apparatus provided with a nozzle having a shower head structure is suitable. Note that the transport belt 54a in this example does not need to have a filter function, unlike the transport belt 54 used in the apparatus shown in FIG.
　この装置１７０を用いた連続式製造プロセスを説明する。駆動ローラ５２ａが矢印の回転方向に回転して搬送ベルト５４が移動し始めると、スパッタ装置７１から触媒７４が搬送ベルト５４ａ上に連続的に付着される。次いで、付着された触媒７４に、ＣＶＤ装置７３によりフィラメント状炭素合成用ガスが吹き付けられるとフィラメント状炭素が合成されて垂直方向に配列したフィラメント状炭素の集合体７５が形成される。この集合体７５が搬送ベルト５４ａにより下流の蒸着器５８と対向する位置まで搬送されると、蒸着器５８によって加熱溶融された蒸着源の金属５５が集合体７５に付着する。こうしてフィラメント状炭素の集合体の一面に金属５５が付着した複合膜７９が得られる。この複合膜７９は、連続膜であるため、複合膜５９の搬送方向前端が従動ローラ５２ｂで巻き上げられるときに、その前端に従動ローラの接線方向（水平方向）の引張力を与えることにより、順次、搬送ベルト５４ａから外れて長尺の自立した複合膜７９（複合連続膜）が得られる。 A continuous manufacturing process using this apparatus 170 will be described. When the driving roller 52a rotates in the direction of the arrow and the conveying belt 54 starts to move, the catalyst 74 is continuously attached from the sputtering device 71 onto the conveying belt 54a. Next, when a filamentous carbon synthesis gas is blown onto the attached catalyst 74 by the CVD device 73, the filamentous carbon is synthesized and a filamentous carbon aggregate 75 arranged in the vertical direction is formed. When the aggregate 75 is conveyed to a position facing the downstream vapor deposition device 58 by the conveyance belt 54 a, the deposition source metal 55 heated and melted by the vapor deposition device 58 adheres to the aggregate 75. In this way, a composite film 79 in which the metal 55 is adhered to one surface of the filamentous carbon aggregate is obtained. Since the composite film 79 is a continuous film, when the front end in the transport direction of the composite film 59 is wound up by the driven roller 52b, a tensile force in the tangential direction (horizontal direction) of the driven roller at the front end is sequentially applied. Then, a long and self-supporting composite film 79 (composite continuous film) is obtained by separating from the transport belt 54a.
　更に、搬送ベルト５４ａが駆動ローラ５２を兼ねることもできる。即ち搬送ベルトの代わりに円筒を用い、円筒を回転させながら、円筒表面に触媒を付着し、フィラメント状炭素を合成し、金属を蒸着し、連続的に剥がして回収することができる。この円筒１つにて、搬送ベルト５４ａと駆動ローラ５２ａ、５２ｂを兼ねることとなる。また、複合膜７９の前端に従動ローラ５２ｂの接線方向（水平方向）の引張力を与えて搬送ベルト５４ａから剥離（分離）するための剥離ローラのような機構を設けてもよい。 Furthermore, the conveyance belt 54 a can also serve as the driving roller 52. That is, a cylinder is used instead of the conveyor belt, and while rotating the cylinder, the catalyst is attached to the surface of the cylinder, the filamentous carbon is synthesized, the metal is vapor-deposited, and continuously peeled and recovered. The single cylinder serves as both the conveying belt 54a and the driving rollers 52a and 52b. Further, a mechanism such as a peeling roller for separating (separating) from the conveying belt 54a by applying a tensile force in the tangential direction (horizontal direction) of the driven roller 52b at the front end of the composite film 79 may be provided.
［蓄電デバイス］
　上記実施形態及び変形形態の複合膜１００、１００ａ、１００ｂ、及び機能性複合膜３００、４００、３００ａ、４００ａは、リチウムイオン電池に代表される二次電池などの電気化学蓄電デバイスにおける電極として好適に使用できる。以下、上記実施形態の機能性複合膜３００を電極として有するリチウムイオン電池を例に挙げて説明する。 [Power storage device]
The composite membranes 100, 100a, 100b and the functional composite membranes 300, 400, 300a, 400a of the above-described embodiments and modifications are suitable as electrodes in an electrochemical storage device such as a secondary battery typified by a lithium ion battery. Can be used. Hereinafter, a lithium ion battery having the functional composite film 300 of the above embodiment as an electrode will be described as an example.
　リチウムイオン電池は、セパレータ、負極、セパレータ及び正極を積層又は積層・巻回することにより得られる電極群を、電池缶などの電池ケース内に収納した後、電解液を電池ケース内に注入して製造することができる。 In a lithium ion battery, an electrode group obtained by laminating or laminating and winding a separator, a negative electrode, a separator, and a positive electrode is housed in a battery case such as a battery can, and then an electrolyte is injected into the battery case. Can be manufactured.
　正極として、アルミニウムからなる第２層８０を有する複合膜３００を用いることができる。この場合、フィラメント状炭素４２からなる第１層４０、アルミニウムからなる第２層８０、及びフィラメント状炭素４２とアルミニウムの共存層６０（すなわち、フィラメント状炭素膜２０及び金属層１０）が集電体として働く。 As the positive electrode, the composite film 300 having the second layer 80 made of aluminum can be used. In this case, the first layer 40 made of filamentous carbon 42, the second layer 80 made of aluminum, and the coexisting layer 60 of filamentous carbon 42 and aluminum (that is, the filamentous carbon film 20 and the metal layer 10) are current collectors. Work as.
　負極として、銅又はニッケルからなる第２層８０を有する複合膜３００を用いることができる。この場合、フィラメント状炭素４２からなる第１層４０、銅又はニッケルからなる第２層８０、及びフィラメント状炭素４２と銅又はニッケルの共存層６０（すなわち、フィラメント状炭素膜２０及び金属層１０）が集電体として働く。 As the negative electrode, the composite film 300 having the second layer 80 made of copper or nickel can be used. In this case, the first layer 40 made of filamentous carbon 42, the second layer 80 made of copper or nickel, and the coexisting layer 60 of the filamentous carbon 42 and copper or nickel (that is, the filamentous carbon film 20 and the metal layer 10). Works as a current collector.
　上記のように形成した電極を２枚用い、金属層１０同士を対向させて重ね合わせると、リチウムイオン電池を高容量化できてより好適である。更に、電極２枚を重ね合わせる際に、少なくとも一方の金属層１０の表面にバインダーを塗布した上で重ね合わせて接着すると、電極の強度が向上するため、より好適である。なお、バインダーは金属層に両側を挟まれているため劣化しにくく、また金属層の面内方向の導電も阻害しない。 It is more preferable to use two electrodes formed as described above and overlap the metal layers 10 so as to face each other because the capacity of the lithium ion battery can be increased. Furthermore, when two electrodes are overlapped, it is more preferable to apply a binder on the surface of at least one metal layer 10 and then bond them together to improve the strength of the electrodes. In addition, since the binder is sandwiched on both sides by the metal layer, the binder is not easily deteriorated and does not inhibit the in-plane conductivity of the metal layer.
　電極群の形状としては、例えば、該電極群を巻回の軸と垂直方向に切断したときの断面が、円、楕円、長方形、角がとれたような長方形等となるような形状を挙げることができる。また、電池ケースの形状としては、例えば、ペーパー型、コイン型、円筒型、角型などの形状を挙げることができる。 Examples of the shape of the electrode group include 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, or the like. Can do. In addition, examples of the shape of the battery case include a paper shape, a coin shape, a cylindrical shape, and a square shape.
　セパレータは、任意のものでよく、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、フッ素樹脂などの材質からなる多孔質膜、不織布、織布などの形態を有する膜にし得る。 The separator may be of any type, and may be, for example, a film having a form of a porous film made of a material such as a polyolefin resin such as polyethylene or polypropylene, or a fluororesin, a nonwoven fabric, or a woven fabric.
　電解液は、任意のものでよく、市場で入手できるものを使用してよい。電解液は、通常、電解質および有機溶媒を含有し、例えばヘキサフルオロリン酸リチウム（ＬｉＰＦ６）などのリチウム塩からなる電解質をプロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）などの有機溶媒に溶解させて得られる。 Any electrolytic solution may be used, and commercially available one may be used. The electrolyte usually contains an electrolyte and an organic solvent. For example, an electrolyte made of a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) is converted into propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), It is obtained by dissolving in an organic solvent such as ethyl methyl carbonate (EMC).
　本実施形態のリチウムイオン電池の電極として用いられる複合膜３００は、上述の様に、充放電時に活物質３４の体積が大きく変化しても、活物質３４が第１層４０から剥離しにくいという利点と、活物質３４と金属の間の電気抵抗が小さいという利点がある。したがって、複合膜３００を電極として用いた本実施形態のリチウムイオン電池は、長寿命であり、高容量である。 As described above, the composite film 300 used as the electrode of the lithium ion battery of the present embodiment is that the active material 34 is difficult to peel from the first layer 40 even if the volume of the active material 34 changes greatly during charging and discharging. There is an advantage that the electric resistance between the active material 34 and the metal is small. Therefore, the lithium ion battery of this embodiment using the composite film 300 as an electrode has a long life and a high capacity.
　本実施形態では電極として上記第２実施形態の複合膜３００を用いたが、リチウムイオン電池の電極は、上記実施形態及び変形形態の複合膜１００、１００ａ、１００ｂ又は機能性複合膜３００ａを用いて製造することもできる。それにより製造されるリチウムイオン電池も、高容量で長寿命となる。 In this embodiment, the composite film 300 of the second embodiment is used as an electrode. However, the electrode of the lithium ion battery uses the composite film 100, 100a, 100b or the functional composite film 300a of the above-described embodiment and the modified embodiment. It can also be manufactured. The lithium ion battery produced thereby also has a high capacity and a long life.
　なお、本発明に係る複合膜及び機能性複合膜は、リチウムイオン電池のような蓄電デバイスの電極に限らず、様々な形態の蓄電デバイスの電極としても適用可能であり、材料の組み合わせに応じて正極としても負極としても適用可能である。例えば、複合膜のフィラメント状炭素からなる層の上に活性炭などの電極活物質を付着して、電気二重層キャパシタの電極（正極、負極を問わない）としても適用可能である。あるいは、フィラメント状炭素からなる層の上に、黒鉛などの電極活物質を付着して、リチウムイオンキャパシタの電極（正極、負極を問わない）としても適用可能である。本出願において、「蓄電デバイス」とは、繰り返し充放電可能なデバイスを意図し、リチウムイオン電池等の二次電池、電気二重層キャパシタやリチウムイオンキャパシタ等のキャパシタを含む意である。 Note that the composite film and the functional composite film according to the present invention are not limited to the electrode of an electricity storage device such as a lithium ion battery, but can also be applied as an electrode of an electricity storage device in various forms, depending on the combination of materials. It is applicable as both a positive electrode and a negative electrode. For example, an electrode active material such as activated carbon is attached on the layer made of filamentous carbon of the composite film, and can be applied as an electrode of an electric double layer capacitor (whether positive electrode or negative electrode). Alternatively, an electrode active material such as graphite is attached on the layer made of filamentous carbon, and can be applied as an electrode (a positive electrode or a negative electrode) of a lithium ion capacitor. In this application, the “storage device” means a device that can be repeatedly charged and discharged, and includes a secondary battery such as a lithium ion battery, a capacitor such as an electric double layer capacitor and a lithium ion capacitor.
　以下、本発明の複合膜及びその製造方法を実施例及び比較例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the composite membrane of the present invention and the production method thereof will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
　実施例１
　０．５ｗｔ％ＳＤＢＳ水溶液４０ｍＬにフィラメント状炭素としてＣＮＴ（名城ナノカーボン製ｅＤＩＰＳ）４ｍｇを加え、超音波分散装置（ＶＥＬＶＯ社製ＣＬＥＡＲ　ＶＳ－５０Ｒ）を用いて出力３０Ｗ、周波数４５ｋｈｚで２時間分散処理を行うことによりＣＮＴ分散液を得た。ＣＮＴ分散液１０ｍＬを孔径０．１μｍのメンブレンフィルタ（ミリポア社製ＶＣＷＰ）を用いて減圧ろ過し、メンブレンフィルタ上に厚さ約２０μｍのＣＮＴ膜を作製した。 Example 1
4 mg of CNT (eDIPS made by Meijo Nanocarbon) is added to 40 mL of 0.5 wt% SDBS aqueous solution as filamentous carbon, and dispersed for 2 hours at an output of 30 W and a frequency of 45 kHz using an ultrasonic dispersion device (CLEAR VS-50R made by VELVO). To obtain a CNT dispersion. 10 mL of the CNT dispersion was filtered under reduced pressure using a membrane filter having a pore size of 0.1 μm (VCWP manufactured by Millipore) to produce a CNT film having a thickness of about 20 μm on the membrane filter.
　ＣＮＴ膜が形成されたメンブレンフィルタをビーカー内で純水に含浸することにより、ＣＮＴ膜とメンブレンフィルタを分離させた。ＣＮＴ膜に付着しているＳＤＢＳをすすぐために、ビーカー内の純水をヒーターで１００℃に加熱した。次いで、水面に浮かんだＣＮＴ膜を熱酸化膜付きＳｉ基板（以降、単に「基板」と称する）で掬い取った。これらの操作により、ＣＮＴ膜を基板上に支持した。 The membrane filter with the CNT film formed was impregnated with pure water in a beaker to separate the CNT film and the membrane filter. In order to rinse the SDBS adhering to the CNT film, pure water in the beaker was heated to 100 ° C. with a heater. Next, the CNT film floating on the water surface was scraped off with a Si substrate with a thermal oxide film (hereinafter simply referred to as “substrate”). By these operations, the CNT film was supported on the substrate.
　次いで、基板上のＣＮＴ膜に、以下のようにしてＣｕを蒸着した。蒸着チャンバー内に、８０ｍｍ×６ｍｍのタングステンボートを設置し、この上に、Ｃｕ片（ニラコ社Ｃｕ１１１４８７、純度９９．９％）を載置し、これを蒸着源とした。なお、Ｃｕ片は加熱することにより融解してボート上に広がるため、蒸着源のサイズは、３０ｍｍ×６ｍｍ程度となる。タングステンボートにＣＮＴ膜が平行に対向するように基板を配置した。このとき、蒸着源－ＣＮＴ膜間距離は、３５ｍｍとした。基板はＣＮＴ膜面を下に向け、中央に１８ｍｍ角の開口部を有する石英ガラス板製のステージにのせ、上面からＰＧ／ＰＢＮヒーターで約４００℃に加熱した。チャンバー内をターボポンプで１０－４Ｐａ台まで減圧した。５８８Ｗでタングステンボートに通電しタングステンボートを約１７９０℃まで加熱することによりＣｕ片を融解させ、８０秒間Ｃｕの蒸着を行った。蒸着中の基板温度は、４００℃であった。以上の操作により、基板上のＣＮＴ膜上にＣｕ膜が形成された。蒸着前後の試料の重量変化の値を基板面積と銅の密度で除することによって求めたＣｕ膜厚を換算膜厚とする。本実施例では、換算膜厚が約１０μｍとなるよう実験を行った。 Next, Cu was deposited on the CNT film on the substrate as follows. An 80 mm × 6 mm tungsten boat was installed in the vapor deposition chamber, and a Cu piece (Nilaco Corp. Cu111487, purity 99.9%) was placed thereon, which was used as a vapor deposition source. Since the Cu piece is melted by heating and spreads on the boat, the size of the vapor deposition source is about 30 mm × 6 mm. The substrate was placed so that the CNT film faced the tungsten boat in parallel. At this time, the distance between the evaporation source and the CNT film was set to 35 mm. The substrate was placed on a quartz glass plate stage having an 18 mm square opening at the center with the CNT film surface facing down, and heated to about 400 ° C. with a PG / PBN heater from the top. The inside of the chamber was depressurized to a level of 10 −4 Pa with a turbo pump. By energizing the tungsten boat at 588 W and heating the tungsten boat to about 1790 ° C., the Cu piece was melted and Cu was deposited for 80 seconds. The substrate temperature during vapor deposition was 400 ° C. By the above operation, a Cu film was formed on the CNT film on the substrate. Let Cu film thickness calculated | required by remove | dividing the value of the weight change of the sample before and behind vapor deposition by the board | substrate area and the density of copper be a conversion film thickness. In this example, an experiment was performed so that the equivalent film thickness was about 10 μm.
　以上のようにして、基板上のＣＮＴ膜にＣｕが蒸着された複合膜（ＣＮＴ－Ｃｕ複合膜）を得た。その後、ピンセットにてＣＮＴ－Ｃｕ複合膜を基板から剥離し、自立したＣＮＴ－Ｃｕ複合膜を得た。 As described above, a composite film (CNT-Cu composite film) in which Cu was deposited on the CNT film on the substrate was obtained. Thereafter, the CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film.
　得られたＣＮＴ－Ｃｕ複合膜を二つに引き裂き、走査型電子顕微鏡（ＳＥＭ、Ｈｉｔａｃｈｉ製Ｓ－４８００）で観察したところ、低倍率では裂け目近くではＣＮＴ膜がＣｕ膜から剥がれているように見えた（図７（ａ）参照）が、より高倍率で観察すると、毛羽立ったＣＮＴが無数にＣｕ膜上に付着していた（図７（ｂ）参照）。このことから、ＣＮＴとＣｕが機械的に良好に接続されていることがわかった。 The obtained CNT-Cu composite film was torn into two and observed with a scanning electron microscope (SEM, Hitachi S-4800). At low magnification, the CNT film appeared to peel off from the Cu film near the tear. However, when observed at a higher magnification, countless fluffy CNTs adhered to the Cu film (see FIG. 7B). From this, it was found that CNT and Cu were mechanically well connected.
　比較例１
　ＣＮＴを４ｍｇ、１０ｍＬのＮ－メチルピロリドンに加えて、超音波分散装置（ＶＥＬＶＯ社製ＣＬＥＡＲ　ＶＳ－５０Ｒ）を用いて出力４０Ｗ、周波数４５ｋｈｚで１時間分散処理した後、ＰＶＤＦを０．４ｍｇ加えて撹拌しペーストを作製した。このペースト１ｍＬを厚さ１０μｍの電着銅箔（ニラコ社Ｃｕ１１３１７３、純度９９．９％）上に塗布し、２００℃、０．０１Ｔｏｒｒにて１時間乾燥させた。得られた複合膜を基板から機械的に剥離し、二つに引き裂いた。裂け目付近をＳＥＭ観察したところ、低倍率では裂け目近くでＣＮＴ膜が剥がれているように見えた（図７（ｃ）参照）。中倍率で観察すると、リボン状に結着したＣＮＴがＣｕに付着している部分と、ＣＮＴが見られない部分があった（図７（ｄ）参照）。更に高倍率で観察するとＣＮＴがＣｕから完全に除去されている部分があることが分かった（図７（ｅ）参照）。このことから、バインダーでＣＮＴとＣｕを接着できるものの、強度が弱いため、ＣＮＴがＣｕから完全に剥がれることがあり、更にバインダーによりＣＮＴが束状に結着して表面積を減らすことも分かった。 Comparative Example 1
CNT was added to 4 mg and 10 mL of N-methylpyrrolidone, and after dispersion treatment for 1 hour at an output of 40 W and a frequency of 45 kHz using an ultrasonic dispersion device (CLEAR VS-50R manufactured by VELVO), 0.4 mg of PVDF was added. A paste was prepared by stirring. 1 mL of this paste was applied onto a 10 μm thick electrodeposited copper foil (Niraco Cu113173, purity 99.9%) and dried at 200 ° C. and 0.01 Torr for 1 hour. The resulting composite film was mechanically peeled from the substrate and torn into two. SEM observation of the vicinity of the fissure revealed that the CNT film was peeled off near the fissure at low magnification (see FIG. 7C). When observed at a medium magnification, there were a portion where CNTs bound in a ribbon shape adhered to Cu and a portion where CNTs were not seen (see FIG. 7D). When observed at a higher magnification, it was found that there was a part where CNT was completely removed from Cu (see FIG. 7 (e)). From this, it was found that although CNT and Cu can be bonded with a binder, the strength is weak, so that CNT may be completely peeled off from Cu, and the binder binds CNTs in a bundle shape to reduce the surface area.
　実施例２
　ＣＮＴ分散液のろ過量を０．３ｍＬとした以外は実施例１と同様にして、基板上に支持されたＣＮＴ膜を作製した。得られたＣＮＴ膜の平面構造をＳＥＭにて観察したところ、ＣＮＴが絡み合った網目構造が形成されていた（図８Ａ参照）。 Example 2
A CNT film supported on a substrate was produced in the same manner as in Example 1 except that the filtration amount of the CNT dispersion was 0.3 mL. When the planar structure of the obtained CNT film was observed with an SEM, a network structure in which CNTs were intertwined was formed (see FIG. 8A).
　次いで、Ｃｕの蒸着時にタングステンボートを４６２Ｗで約１６４０℃まで加熱し蒸着時間を１秒とした以外は実施例１と同様にして、基板上のＣＮＴ膜上にＣｕ膜を形成した。実施例１と同様にして求めたＣｕ膜厚（換算膜厚）は０．０３３μｍであった。 Next, a Cu film was formed on the CNT film on the substrate in the same manner as in Example 1 except that the tungsten boat was heated to about 1640 ° C. at 462 W during Cu deposition and the deposition time was 1 second. The Cu film thickness (converted film thickness) obtained in the same manner as in Example 1 was 0.033 μm.
　以上のようにして得られたＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｂに示す。なお、図８Ｂの平面ＳＥＭ像は、図８Ａの平面ＳＥＭ像よりも高倍率である。図８Ｂの平面ＳＥＭ像から、ＣＮＴの網目構造の中に粒子状のＣｕが潜り込んでいる様子が観察された。このことから、ＣＮＴとＣｕが共存する共存層が形成されたことがわかった。 FIG. 8B shows a planar SEM image of the CNT-Cu composite film obtained as described above. Note that the planar SEM image in FIG. 8B has a higher magnification than the planar SEM image in FIG. 8A. From the planar SEM image of FIG. 8B, it was observed that particulate Cu was embedded in the CNT network structure. From this, it was found that a coexistence layer in which CNT and Cu coexist was formed.
　実施例３
　Ｃｕの蒸着時にタングステンボートを５７６Ｗで約１７８０℃まで加熱し蒸着時間を３秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。蒸着により形成したＣｕ膜の換算膜厚は０．１４μｍであった。本実施例で作製したＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｃに示す。なお、図８Ｃの平面ＳＥＭ像は、図８Ａの平面ＳＥＭ像よりも高倍率である。図８Ｃの平面ＳＥＭ像から、ＣＮＴの網目構造の中に粒子状のＣｕが潜り込んでいる様子が観察された。このことから、ＣＮＴとＣｕが共存する共存層が形成されたことがわかった。 Example 3
A CNT—Cu composite film was produced in the same manner as in Example 2 except that the tungsten boat was heated to about 1780 ° C. at 576 W during Cu deposition and the deposition time was 3 seconds. The converted film thickness of the Cu film formed by vapor deposition was 0.14 μm. A planar SEM image of the CNT—Cu composite film produced in this example is shown in FIG. 8C. Note that the planar SEM image in FIG. 8C has a higher magnification than the planar SEM image in FIG. 8A. From the planar SEM image of FIG. 8C, it was observed that the particulate Cu was embedded in the CNT network structure. From this, it was found that a coexistence layer in which CNT and Cu coexist was formed.
　実施例４
　Ｃｕの蒸着時にタングステンボートを５５０Ｗで約１７５０℃まで加熱し蒸着時間を４秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。蒸着により形成したＣｕ膜の換算膜厚は０．３８μｍであった。本実施例で作製したＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｄに示す。平面ＳＥＭ像から、Ｃｕが連続膜に近くなっており、Ｃｕ上に少量のＣＮＴが見られたことから、網目構造の最表面近くまでＣｕが堆積されていることがわかった。 Example 4
A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1750 ° C. at 550 W during Cu deposition and the deposition time was 4 seconds. The converted film thickness of the Cu film formed by vapor deposition was 0.38 μm. FIG. 8D shows a planar SEM image of the CNT—Cu composite film produced in this example. From the planar SEM image, Cu was close to a continuous film, and a small amount of CNT was seen on Cu, indicating that Cu was deposited to the vicinity of the outermost surface of the network structure.
　実施例５
　Ｃｕの蒸着時にタングステンボートを５２８Ｗで約１７２０℃まで加熱し蒸着時間を８秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。蒸着により形成したＣｕ膜の換算膜厚は１．３６μｍであった。本実施例で作製したＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｅに示す。ＣＮＴ膜上にＣｕの連続膜が形成されていることがわかった。 Example 5
A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1720 ° C. at 528 W during Cu deposition and the deposition time was 8 seconds. The converted film thickness of the Cu film formed by vapor deposition was 1.36 μm. FIG. 8E shows a planar SEM image of the CNT—Cu composite film produced in this example. It was found that a continuous film of Cu was formed on the CNT film.
　実施例６
　Ｃｕの蒸着時にタングステンボートを５２５Ｗで約１７２０℃まで加熱し蒸着時間を２４秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。蒸着により形成したＣｕ膜の換算膜厚は４．９７μｍであった。本実施例で作製したＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｆに示す。ＣＮＴ膜上にＣｕの連続膜が形成されていることがわかった。 Example 6
A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1720 ° C. at 525 W during Cu deposition and the deposition time was 24 seconds. The converted film thickness of the Cu film formed by vapor deposition was 4.97 μm. A planar SEM image of the CNT-Cu composite film produced in this example is shown in FIG. 8F. It was found that a continuous film of Cu was formed on the CNT film.
　実施例７
　Ｃｕの蒸着時にタングステンボートを６００Ｗで約１８１０℃まで加熱し蒸着時間を６０秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。蒸着により形成したＣｕ膜の換算膜厚は６．０８μｍであった。本実施例で作製したＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｇに示す。ＣＮＴ膜上にＣｕの連続膜が形成されていることがわかった。 Example 7
A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1810 ° C. at 600 W during Cu deposition and the deposition time was 60 seconds. The converted film thickness of the Cu film formed by vapor deposition was 6.08 μm. A planar SEM image of the CNT-Cu composite film produced in this example is shown in FIG. 8G. It was found that a continuous film of Cu was formed on the CNT film.
　実施例８
　Ｃｕの蒸着時にタングステンボートを５３８Ｗで約１７４０℃まで加熱し蒸着時間を８０秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。蒸着により形成したＣｕ膜の換算膜厚は１７．９７μｍであった。本実施例で作製したＣＮＴ－Ｃｕ複合膜の平面ＳＥＭ像を図８Ｈに示す。ＣＮＴ膜上にＣｕの連続膜が形成されていることがわかった。 Example 8
A CNT—Cu composite film was produced in the same manner as in Example 2 except that the tungsten boat was heated to about 1740 ° C. at 538 W during the deposition of Cu and the deposition time was set to 80 seconds. The converted film thickness of the Cu film formed by vapor deposition was 17.97 μm. A planar SEM image of the CNT-Cu composite film produced in this example is shown in FIG. 8H. It was found that a continuous film of Cu was formed on the CNT film.
　実施例２～８の平面ＳＥＭ観察結果から、ＣＮＴ膜上にＣｕを成膜すると、Ｃｕ堆積量が少ない初期の間はＣＮＴ膜内にＣｕが入り込んで共存層が形成され、さらに成膜を続けると、ＣｕがＣＮＴ膜の表面まで堆積された後、ＣＮＴとＣｕの共存層上にＣｕの連続膜が形成されることがわかった。 From the planar SEM observation results of Examples 2 to 8, when Cu was formed on the CNT film, Cu entered the CNT film during the initial period when the amount of deposited Cu was small, and a coexistence layer was formed. After Cu was deposited to the surface of the CNT film, it was found that a continuous film of Cu was formed on the coexisting layer of CNT and Cu.
　実施例９
　ＣＮＴ分散液のろ過量を３ｍＬとし、Ｃｕの蒸着時にタングステンボートを５２８Ｗで約１７２０℃まで加熱し蒸着時間を８０秒とした以外は実施例１と同様にして、ＣＮＴ－Ｃｕ複合膜を得た。次いで、ＣＮＴ－Ｃｕ複合膜を基板から機械的に剥離し、ＣＮＴ－Ｃｕ複合膜のＣＮＴ膜上に以下のようにしてＳｉを蒸着した。蒸着チャンバー内に、２ｍｍ×４ｍｍの蒸発部を８個有するカーボンボートを設置し、この上に、表面に付着した有機物及び酸化物を５～１０％のＨＦ溶液を用いて除去したＳｉ片（純度９９．９９９９％以上）を載置し、これを蒸着源とした。Ｓｉ片は、加熱することにより融解してボート上に広がるため、蒸着源のサイズは、約５０ｍｍ２となる。タングステンボートにＣＮＴ膜が平行に対向するようにＣＮＴ－Ｃｕ複合膜を配置した。このとき、蒸着源－ＣＮＴ膜間距離は、４５ｍｍとした。ＣＮＴ－Ｃｕ複合膜はセラミックヒーターと空冷管で温度制御可能な銅性ブロックの表面に密着させて固定した。チャンバー内をロータリーポンプで１Ｐａまで減圧し、その後アルゴンガスを１０ｓｃｃｍで導入し、チャンバー内の圧力を１３．３Ｐａ（０．１Ｔｏｒｒ）にした。圧力が一定になった後、温度制御機構を用いてＣＮＴ－Ｃｕ複合膜を３００℃に加熱した。カーボンボートに通電して１３００Ｗでカーボンボートを２０００℃以上まで加熱することによりＳｉ片を融解させ、２０秒間Ｓｉの蒸着を行った。蒸着中のＣＮＴ－Ｃｕ複合膜の温度は、３００℃であった。 Example 9
A CNT-Cu composite film was obtained in the same manner as in Example 1 except that the filtration amount of the CNT dispersion was 3 mL, and the tungsten boat was heated to about 1720 ° C. at 528 W during Cu deposition, and the deposition time was 80 seconds. . Next, the CNT-Cu composite film was mechanically peeled from the substrate, and Si was deposited on the CNT film of the CNT-Cu composite film as follows. A carbon boat having eight evaporation sections of 2 mm × 4 mm is installed in the vapor deposition chamber, and an organic substance and oxide adhering to the surface are removed on this using a 5 to 10% HF solution (purity) 99.9999% or more) was placed and used as a deposition source. Since the Si piece is melted by heating and spreads on the boat, the size of the deposition source is about 50 mm 2 . The CNT-Cu composite film was disposed so that the CNT film faced the tungsten boat in parallel. At this time, the distance between the deposition source and the CNT film was 45 mm. The CNT-Cu composite film was fixed in close contact with the surface of a copper block whose temperature can be controlled with a ceramic heater and an air-cooled tube. The pressure in the chamber was reduced to 1 Pa with a rotary pump, and then argon gas was introduced at 10 sccm, and the pressure in the chamber was set to 13.3 Pa (0.1 Torr). After the pressure became constant, the CNT-Cu composite film was heated to 300 ° C. using a temperature control mechanism. By energizing the carbon boat and heating the carbon boat at 1300 W to 2000 ° C. or higher, the Si piece was melted and Si was deposited for 20 seconds. The temperature of the CNT—Cu composite film during vapor deposition was 300 ° C.
　以上のようにして、ＣＮＴ膜の一方の面にＣｕが堆積され、もう一方の面にＳｉが堆積された複合膜（Ｓｉ－ＣＮＴ－Ｃｕ複合膜）を得た。 As described above, a composite film (Si-CNT-Cu composite film) in which Cu was deposited on one surface of the CNT film and Si was deposited on the other surface was obtained.
　得られたＳｉ－ＣＮＴ－Ｃｕ複合膜の断面構造をＳＥＭにて観察したところ、毛羽立ったＣＮＴを覆うようにＳｉが形成されていることが確認された（図９参照）。 When the cross-sectional structure of the obtained Si—CNT—Cu composite film was observed with an SEM, it was confirmed that Si was formed so as to cover the fluffy CNT (see FIG. 9).
　比較例２
　厚さ１０μｍの電着銅箔（ニラコ社Ｃｕ１１３１７３、純度９９．９％）上に、実施例９と同様の条件でＳｉを蒸着し、Ｃｕ－Ｓｉ複合膜を作製した。 Comparative Example 2
On the electrodeposited copper foil having a thickness of 10 μm (Niraco Cu113173, purity 99.9%), Si was deposited under the same conditions as in Example 9 to prepare a Cu—Si composite film.
＜充放電特性評価＞
　２０３２型コインセル内の両端に、実施例９のＳｉ－ＣＮＴ－Ｃｕ複合膜を負極として、Ｌｉ金属を正極として配置した。電極間にセパレータ（ポリプロピレンメンブレン）を挿入し、エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）の混合溶媒（体積比率１：１）にビニレンカーボネートを１ｗｔ％、ＬｉＣｌＯ４を１ｍｏｌ／Ｌの割合で溶解させた電解液を注液した上で、３ＭＰａでプレスして密封しコインセルを作製した。 <Charge / discharge characteristics evaluation>
On both ends of the 2032 type coin cell, the Si—CNT—Cu composite film of Example 9 was used as a negative electrode, and Li metal was used as a positive electrode. A separator (polypropylene membrane) is inserted between the electrodes, and 1 wt% of vinylene carbonate and 1 mol / L of LiClO 4 are dissolved in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1). After pouring the electrolyte solution made, it was pressed and sealed at 3 MPa to produce a coin cell.
　作製したコインセルを、走査電位０．００５～１．２Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）、放電レート０．１Ｃ～１０Ｃ（１Ｃ＝４Ａ／ｇＳｉ）で充放電サイクルを繰り返し、放電容量の変化を調べた。 The manufactured coin cell was repeatedly charged and discharged at a scanning potential of 0.005 to 1.2 V (vs. Li / Li +) and a discharge rate of 0.1 C to 10 C (1 C = 4 A / g Si ) to examine changes in the discharge capacity. It was.
　同様に、比較例２の複合膜を負極として用いて、コインセルを作製し、充放電サイクル試験を行い、放電容量の変化を調べた。 Similarly, a coin cell was prepared using the composite film of Comparative Example 2 as a negative electrode, a charge / discharge cycle test was performed, and changes in the discharge capacity were examined.
　実施例９と比較例２の複合膜の、充放電サイクル試験の結果を図１０に示す。実施例９のＳｉ－ＣＮＴーＣｕ複合膜を負極として用いた場合では、初回の放電容量が３３６０ｍＡｈ／ｇＳｉ、７０サイクル後の放電容量が２１４０ｍＡｈ／ｇＳｉであったのに対し、比較例２のＣｕ－Ｓｉ複合膜を負極として用いた場合は、初回の放電容量が２０００ｍＡｈ／ｇＳｉと低く、２０－４０サイクルで放電容量が急速に劣化し、７０サイクル後の放電容量が５２０ｍＡｈ／ｇＳｉとなった。この結果から、実施例９のＳｉ－ＣＮＴーＣｕ複合膜においては、立毛したＣＮＴを覆うようにＳｉが付着しているために、ＳｉとＣＮＴの接触面積が大きく、それにより、Ｓｉが複合膜から剥離することが抑止されていると考えられる。 The result of the charge / discharge cycle test of the composite film of Example 9 and Comparative Example 2 is shown in FIG. When the Si—CNT—Cu composite film of Example 9 was used as the negative electrode, the initial discharge capacity was 3360 mAh / g Si and the discharge capacity after 70 cycles was 2140 mAh / g Si , whereas Comparative Example 2 When the Cu—Si composite film is used as the negative electrode, the initial discharge capacity is as low as 2000 mAh / g Si , the discharge capacity rapidly deteriorates in 20-40 cycles, and the discharge capacity after 70 cycles is 520 mAh / g Si. It became. From this result, in the Si—CNT—Cu composite film of Example 9, since Si adheres so as to cover the raised CNTs, the contact area between Si and CNT is large, and thus Si is composite film. It is thought that peeling from the surface is suppressed.
　実施例１０
　イソプロパノール２０ｍＬにＣＮＴを２．５ｍｇ添加して超音波にて分散することによりＣＮＴ分散液の調整を行い、孔径０．５μｍのミリポア社製ＰＴＦＥをメンブレンフィルタとして用いて分散液を２０ｍＬろ過した以外は、実施例１と同様にして基板上に支持されたＣＮＴ膜を作製した。次いで、Ｃｕの蒸着時にタングステンボートを４４０Ｗで約１６１０℃まで加熱し蒸着時間を３秒とした以外は実施例１と同様にして、基板上のＣＮＴ膜上にＣｕ膜を形成した。得られたＣＮＴ－Ｃｕ複合膜のＣＮＴ膜厚は３７μｍ、Ｃｕ膜厚は０．０３１μｍであった。 Example 10
CNT dispersion was adjusted by adding 2.5 mg of CNT to 20 mL of isopropanol and dispersing with ultrasonic waves, except that 20 mL of the dispersion was filtered using PTFE manufactured by Millipore with a pore size of 0.5 μm as a membrane filter. In the same manner as in Example 1, a CNT film supported on a substrate was produced. Next, a Cu film was formed on the CNT film on the substrate in the same manner as in Example 1 except that the tungsten boat was heated to about 1610 ° C. at 440 W during the deposition of Cu and the deposition time was set to 3 seconds. The obtained CNT—Cu composite film had a CNT film thickness of 37 μm and a Cu film thickness of 0.031 μm.
　得られたＣＮＴ－Ｃｕ複合膜をピンセットにて基板から剥離し、自立したＣＮＴ－Ｃｕ複合膜を得た。ＣＮＴ－Ｃｕ複合膜の基板からの剥離は、ピンセットを用いて容易に行うことができた（図１１（ａ）参照）。基板から剥離した後のＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真を図１１（ｂ）～（ｄ）に示す。本実施例で作製したＣＮＴ－Ｃｕ複合膜において、Ｃｕ自体は０．０３１μｍと一般の銅箔の数百分の１の厚さしかなく、自立性がないが、ＣＮＴ膜に自立性があるため、複合膜としては自立膜させることができた。リチウムイオン電池の負極にはＣｕ箔が一般的に用いられるが、Ｃｕ箔が重いことが問題となっている。単位面積あたりの重さは市販Ｃｕ箔と比べ、本実施例のＣＮＴ膜で１／１０程度、Ｃｕ蒸着膜で１／５００程度まで軽量化できた。 The obtained CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film. Peeling of the CNT-Cu composite film from the substrate could be easily performed using tweezers (see FIG. 11A). FIGS. 11B to 11D show digital camera photographs of the CNT-Cu composite film after peeling from the substrate. In the CNT-Cu composite film produced in this example, Cu itself is 0.031 μm, which is only one hundredth of the thickness of a general copper foil, and is not self-supporting, but the CNT film is self-supporting. As a composite membrane, it was possible to make it a self-supporting membrane. Although Cu foil is generally used for the negative electrode of a lithium ion battery, it is problematic that the Cu foil is heavy. The weight per unit area was reduced to about 1/10 for the CNT film of this example and about 1/500 for the Cu vapor deposition film, compared to the commercially available Cu foil.
　実施例１１
　Ｃｕの蒸着時にタングステンボートを５２５Ｗで約１７２０℃まで加熱し蒸着時間を２４秒とした以外は実施例２と同様にして、ＣＮＴ－Ｃｕ複合膜を作製した。ＣＮＴ膜の厚さは約１．５μｍであった。蒸着により形成したＣｕ膜の換算膜厚は４．９７μｍであった。 Example 11
A CNT—Cu composite film was prepared in the same manner as in Example 2 except that the tungsten boat was heated to about 1720 ° C. at 525 W during Cu deposition and the deposition time was 24 seconds. The thickness of the CNT film was about 1.5 μm. The converted film thickness of the Cu film formed by vapor deposition was 4.97 μm.
　得られたＣＮＴ－Ｃｕ複合膜をピンセットにて基板から剥離し、自立したＣＮＴ－Ｃｕ複合膜を得た。得られたＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真を図１２（ａ）～（ｃ）に示す。ＣＮＴ膜が約１．５μｍと薄くても、Ｃｕ膜自体が自立性を有しているため、ＣＮＴ－Ｃｕ複合膜を自立膜として得ることができた。リチウムイオン電池の負極にはＣｕ箔が一般的に用いられるが、Ｃｕ箔が重いことが問題となっている。単位面積あたりの重さは市販Ｃｕ箔と比べ、本実施例のＣＮＴ膜で１／５０程度、Ｃｕ蒸着膜で１／３程度まで軽量化できた。 The obtained CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film. Digital camera photographs of the obtained CNT-Cu composite film are shown in FIGS. 12 (a) to 12 (c). Even when the CNT film was as thin as about 1.5 μm, since the Cu film itself was self-supporting, a CNT-Cu composite film could be obtained as a self-supporting film. Although Cu foil is generally used for the negative electrode of a lithium ion battery, it is problematic that the Cu foil is heavy. The weight per unit area was reduced to about 1/50 for the CNT film of this example and about 1/3 for the Cu vapor deposition film, compared to the commercially available Cu foil.
　実施例１２
　熱酸化膜付きＳｉ基板（以降、単に「基板」と称する）に、ＲＦマグネトロンスパッタリングでＡｌを平均膜厚１５ｎｍ堆積し、大気暴露によりＡｌを酸化してＡｌ２Ｏ３膜を形成した。更にその上にＲＦマグネトロンスパッタリングでＦｅを平均膜厚１ｎｍで積層し、触媒付基板を準備した。この基板を石英ガラス製円管型反応器に設置し、１０．６ｖｏｌ％Ｈ２／５３ｐｐｍｖＨ２Ｏ／Ａｒの混合ガスの流通下で８００℃にて１０分間還元した後、０．１５ｖｏｌ％Ｃ２Ｈ２／１０％Ｈ２／５０ｐｐｍｖＨ２Ｏ／Ａｒの混合ガスを５分間流通し、厚さ１０μｍの単層ＣＮＴ垂直配向膜を得た。 Example 12
Al was deposited with an average film thickness of 15 nm by RF magnetron sputtering on a Si substrate with a thermal oxide film (hereinafter simply referred to as “substrate”), and Al was oxidized by exposure to the atmosphere to form an Al 2 O 3 film. Furthermore, Fe was laminated with an average film thickness of 1 nm by RF magnetron sputtering to prepare a substrate with a catalyst. After the substrate was placed in a quartz glass circular tubular reactor and reduced for 10 minutes at 800 ° C. in flowing under a mixed gas of 10.6vol% H 2 / 53ppmvH 2 O / Ar, 0.15vol% C 2 a mixed gas of H 2/10% H 2 / 50ppmvH 2 O / Ar circulated 5 minutes to obtain a single-layer CNT vertical alignment film with a thickness of 10 [mu] m.
　次いで、１００ｍｍ×１５ｍｍのタングステンボートを用い、蒸着源としてＣｕ片（ニラコ社Ｃｕ１１３１７３、純度９９．９％）を用い、タングステンボートを５００Ｗで約１７１０℃まで加熱し、蒸着時間を６０秒とした以外は実施例１におけるＣｕの蒸着と同様にして、ＣＮＴ膜上にＣｕを蒸着した。それにより、基板上の単層ＣＮＴ垂直配向膜上にＣｕ膜が形成された。なお、Ｃｕ片は加熱することにより融解してボート上に広がるため、蒸着源のサイズは、４０ｍｍ×１０ｍｍ程度であった。また、蒸着により形成したＣｕ膜の換算膜厚は１１μｍであった。 Then, using a 100 mm × 15 mm tungsten boat, using a Cu piece (Nilaco Cu113173, purity 99.9%) as a deposition source, heating the tungsten boat to about 1710 ° C. at 500 W, and setting the deposition time to 60 seconds In the same manner as Cu deposition in Example 1, Cu was deposited on the CNT film. Thereby, a Cu film was formed on the single-walled CNT vertical alignment film on the substrate. In addition, since the Cu piece was melted by heating and spread on the boat, the size of the vapor deposition source was about 40 mm × 10 mm. The equivalent film thickness of the Cu film formed by vapor deposition was 11 μm.
　以上のようにして、ＣＮＴ－Ｃｕ複合膜を得た。その後、ピンセットにてＣＮＴ－Ｃｕ複合膜を基板から剥離し、自立したＣＮＴ－Ｃｕ複合膜を得た。得られたＣＮＴ－Ｃｕ複合膜の断面ＳＥＭ像を図１３Ａに示す。垂直配向したＣＮＴ膜上にＣｕの連続膜が形成されていることがわかった。 Thus, a CNT-Cu composite film was obtained. Thereafter, the CNT-Cu composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Cu composite film. A cross-sectional SEM image of the obtained CNT-Cu composite film is shown in FIG. 13A. It was found that a continuous film of Cu was formed on the vertically aligned CNT film.
　更に、ＣＮＴ側を下側に向けエタノール蒸気に曝し、ＣＮＴ上にエタノールを凝縮させた後に乾燥させることで、表面張力によりＣＮＴ垂直配向膜を収縮させた。ＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真を図１３Ｂ、１３Ｃに示し、断面ＳＥＭ像を図１３Ｄに、平面ＳＥＭ像を図１３Ｅに示す。図１３ＢにはＣｕ膜側からみたＣＮＴ－Ｃｕ複合膜が示されており、図１３ＣにはＣＮＴ膜側からみたＣＮＴ－Ｃｕ複合膜が示されている。Ｃｕ薄膜上にＣＮＴの壁がランダムに１０～２０μｍの間隔をおいて直立した網目構造が得られた。なお、ＣＮＴの合成時間を変えることでＣＮＴ垂直配向膜の高さを１０～１２０μｍに変化させた以外は同様の操作を行うことで、ＣＮＴ壁の間隔を６～４２μｍと広範囲に変えることもできた。 Furthermore, the CNT vertical alignment film was shrunk by surface tension by exposing it to ethanol vapor with the CNT side facing down, condensing ethanol on the CNT, and then drying. A digital camera photograph of the CNT-Cu composite film in which the CNT vertical alignment film is contracted is shown in FIGS. 13B and 13C, a cross-sectional SEM image is shown in FIG. 13D, and a planar SEM image is shown in FIG. 13E. FIG. 13B shows a CNT-Cu composite film viewed from the Cu film side, and FIG. 13C shows a CNT-Cu composite film viewed from the CNT film side. A network structure was obtained in which the CNT walls were standing upright at intervals of 10 to 20 μm on the Cu thin film. The interval between CNT walls can be changed over a wide range from 6 to 42 μm by performing the same operation except that the height of the CNT vertical alignment film is changed to 10 to 120 μm by changing the CNT synthesis time. It was.
　実施例１３
　Ｃｕ板（ニラコ社Ｃｕ１１３３２１、純度９９．９６％）（以降、単に「Ｃｕ基板」と称する）を用意した。Ｃｕ基板の表面のＳＥＭ像を図１４Ａに示す。Ｃｕ基板は表面に一方向に延在する筋状のテクスチャ（凹凸）を有していた。凹凸の平均ピッチは約９μｍであった。Ｃｕ基板に、ＲＦマグネトロンスパッタリングでＴａを平均膜厚３０ｎｍ、Ａｌ２Ｏ３を平均膜厚５０ｎｍ、Ｆｅを平均膜厚１ｎｍで堆積し、触媒付Ｃｕ基板を準備した。この基板を石英ガラス製円管型反応器に設置し、１０．６ｖｏｌ％Ｈ２／５３ｐｐｍｖＨ２Ｏ／Ａｒの混合ガスの流通下で８００℃にて１０分間還元した後、０．１５ｖｏｌ％Ｃ２Ｈ２／１０％Ｈ２／５０ｐｐｍｖＨ２Ｏ／Ａｒの混合ガスを１０分間流通し、厚さ８．５μｍの単層ＣＮＴ垂直配向膜を得た。 Example 13
A Cu plate (Niraco Cu113321, purity 99.96%) (hereinafter simply referred to as “Cu substrate”) was prepared. An SEM image of the surface of the Cu substrate is shown in FIG. 14A. The Cu substrate had a streak texture (unevenness) extending in one direction on the surface. The average pitch of the irregularities was about 9 μm. A Cu substrate with a catalyst was prepared by depositing Ta with an average film thickness of 30 nm, Al 2 O 3 with an average film thickness of 50 nm, and Fe with an average film thickness of 1 nm on a Cu substrate by RF magnetron sputtering. After the substrate was placed in a quartz glass circular tubular reactor and reduced for 10 minutes at 800 ° C. in flowing under a mixed gas of 10.6vol% H 2 / 53ppmvH 2 O / Ar, 0.15vol% C 2 a mixed gas of H 2/10% H 2 / 50ppmvH 2 O / Ar circulated for 10 minutes to obtain a single-layer CNT vertical alignment film having a thickness of 8.5 .mu.m.
　次いで、実施例１２におけるＣｕの蒸着と同様にして、ＣＮＴ膜上にＣｕを蒸着した。それにより、Ｃｕ基板上の単層ＣＮＴ垂直配向膜上にＣｕ膜が形成された。蒸着により形成したＣｕ膜の換算膜厚は１１μｍであった。 Next, Cu was deposited on the CNT film in the same manner as the Cu deposition in Example 12. Thereby, a Cu film was formed on the single-walled CNT vertical alignment film on the Cu substrate. The converted film thickness of the Cu film formed by vapor deposition was 11 μm.
　以上のようにして、ＣＮＴ－Ｃｕ複合膜を得た。その後、ピンセットにてＣＮＴ－Ｃｕ複合膜をＣｕ基板から剥離し、自立したＣＮＴ－Ｃｕ複合膜を得た。得られたＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真を図１４Ｂに、断面ＳＥＭ像を図１４Ｃに示す。図１４Ｂの左側にはＣＮＴ－Ｃｕ複合膜を剥離した後のＣｕ基板が示されており、右側にはＣＮＴ膜側からみたＣＮＴ－Ｃｕ複合膜が示されている。これらの図から垂直配向したＣＮＴ膜上にＣｕの連続膜が形成されていることがわかった。 Thus, a CNT-Cu composite film was obtained. Thereafter, the CNT-Cu composite film was peeled from the Cu substrate with tweezers to obtain a self-supporting CNT-Cu composite film. A digital camera photograph of the obtained CNT-Cu composite film is shown in FIG. 14B, and a cross-sectional SEM image is shown in FIG. 14C. The left side of FIG. 14B shows the Cu substrate after the CNT-Cu composite film is peeled off, and the right side shows the CNT-Cu composite film as viewed from the CNT film side. From these figures, it was found that a continuous film of Cu was formed on the vertically aligned CNT film.
　更に、ＣＮＴ側を下側に向けエタノール蒸気に曝し、ＣＮＴ上にエタノールを凝縮させた後に乾燥させることで、表面張力によりＣＮＴ垂直配向膜を収縮させた。ＣＮＴ垂直配向膜を収縮させたＣＮＴ－Ｃｕ複合膜のデジタルカメラ写真を図１４Ｄに示し、斜めＳＥＭ像を図１４Ｅに、平面ＳＥＭ像を図１４Ｆに示す。Ｃｕ薄膜上にＣＮＴの壁が一方向に規則的に並んだ筋状構造が得られた。壁の高さは５～７μｍであった。なお、ＣＮＴの合成時間を変えることでＣＮＴ垂直配向膜の高さを９～６４μｍに変化させた以外は同様の操作を行うことで、ＣＮＴ壁の間隔を１０～６４μｍと広範囲に変えることもできた。 Furthermore, the CNT vertical alignment film was shrunk by surface tension by exposing it to ethanol vapor with the CNT side facing down, condensing ethanol on the CNT, and then drying. A digital camera photograph of the CNT-Cu composite film obtained by shrinking the CNT vertical alignment film is shown in FIG. 14D, an oblique SEM image is shown in FIG. 14E, and a planar SEM image is shown in FIG. 14F. A streak structure in which the CNT walls were regularly arranged in one direction on the Cu thin film was obtained. The wall height was 5-7 μm. The interval between CNT walls can be changed over a wide range from 10 to 64 μm by performing the same operation except that the height of the CNT vertical alignment film is changed to 9 to 64 μm by changing the CNT synthesis time. It was.
　実施例１４
　エタノール３０ｍＬにフィラメント状炭素として、Ｃａｒｂｏｎ　８０，３３９－３５０（２０１４）に記載の流動層法にて製造した数層ＣＮＴ２ｍｇを加え、超音波分散装置を用いて出力９０Ｗ、周波数４５ｋｈｚで４０分間分散処理を行うことによりＣＮＴ分散液を得た。ＣＮＴ分散液３０ｍＬを孔径０．１μｍのメンブレンフィルタを用いて減圧ろ過し、メンブレンフィルタ上に厚さ約３０μｍのＣＮＴ膜を作製した。 Example 14
Add 2 mg of several CNTs produced by the fluidized bed method described in Carbon 80, 339-350 (2014) as filamentous carbon to 30 mL of ethanol, and disperse for 40 minutes at an output of 90 W and a frequency of 45 kHz using an ultrasonic dispersing device. To obtain a CNT dispersion. 30 mL of the CNT dispersion liquid was filtered under reduced pressure using a membrane filter having a pore size of 0.1 μm to produce a CNT film having a thickness of about 30 μm on the membrane filter.
　ＣＮＴ膜が形成されたメンブレンフィルタから、ピンセットを用いてＣＮＴ膜とメンブレンフィルタを分離させ、ＣＮＴ自立膜を得た。このＣＮＴ膜をエタノールに濡れたまま基板上にのせ、乾燥することで、ＣＮＴ膜を基板上に支持した。ＣＮＴ膜のシート抵抗は５Ω／ｓｑであった。 The CNT film and the membrane filter were separated from the membrane filter on which the CNT film was formed using tweezers to obtain a CNT self-supporting film. The CNT film was supported on the substrate by placing the CNT film on the substrate while being wetted with ethanol and drying. The sheet resistance of the CNT film was 5Ω / sq.
　次いで、蒸着源としてＡｌ片（ニラコ社Ａｌ０１１４８７、純度９９．９９％）を用い、基板の加熱温度を約１５０℃とし、タングステンボートを５５０Ｗで約１７００℃まで加熱し、蒸着時間を１０秒とした以外は実施例１２におけるＣｕの蒸着と同様にして、基板上のＣＮＴ膜上にＡｌ膜を蒸着した。蒸着により形成されたＡｌ膜の換算膜厚は６．３μｍであった。 Next, an Al piece (Nilaco Al011487, purity 99.99%) was used as the deposition source, the substrate heating temperature was about 150 ° C., the tungsten boat was heated to about 1700 ° C. at 550 W, and the deposition time was 10 seconds. Except for the above, an Al film was deposited on the CNT film on the substrate in the same manner as Cu deposition in Example 12. The converted film thickness of the Al film formed by vapor deposition was 6.3 μm.
　以上のようにして、基板上のＣＮＴ膜にＡｌが蒸着された複合膜（ＣＮＴ－Ａｌ複合膜）を得た。その後、ピンセットにてＣＮＴ－Ａｌ複合膜を基板から剥離し、自立したＣＮＴ－Ａｌ複合膜を得た。なお、剥離により基板上に支持したＣＮＴ膜の一部がＡｌ側に転写された。残りのＣＮＴ膜は、基板との接着力が小さいために基板から剥がれた。得られたＣＮＴ－Ａｌ複合膜のデジタルカメラ写真を図１５Ａ、１５Ｂに、平面ＳＥＭ像を図１５Ｃに、断面ＳＥＭ像を図１５Ｄに示す。図１５Ａの左側にはＡｌ膜側からみたＣＮＴ－Ａｌ複合膜が示されており、右側にはＣＮＴ－Ａｌ複合膜を剥離した後の基板から外れた残余のＣＮＴ膜が示されている。図１５ＢにはＣＮＴ膜側からみたＣＮＴ－Ａｌ複合膜が示されている。これらの図が示すように、ＣＮＴとＡｌのみからなりながら、両者が良好に接続された複合膜が得られた。また、ＣＮＴ－Ａｌ複合膜のシート抵抗は０．０１１Ω／ｓｑであり、ＣＮＴ膜単体と比べて低抵抗化した。また、図１５ＡからわかるようにＣＮＴ－Ａｌ複合膜を剥離した後の残余のＣＮＴは膜構造を維持していた。このＣＮＴ膜を再度、基板に保持してＡｌ等の金属を成膜して剥離することで新たに別のＣＮＴ－Ａｌ複合膜を得ることができる。すなわち、基板上に支持したＣＮＴ膜から繰り返しＣＮＴ－Ａｌ複合膜を得ることができる。 As described above, a composite film (CNT-Al composite film) in which Al was deposited on the CNT film on the substrate was obtained. Thereafter, the CNT-Al composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Al composite film. Part of the CNT film supported on the substrate by the transfer was transferred to the Al side. The remaining CNT film was peeled off from the substrate because of its low adhesive strength with the substrate. A digital camera photograph of the obtained CNT-Al composite film is shown in FIGS. 15A and 15B, a planar SEM image is shown in FIG. 15C, and a cross-sectional SEM image is shown in FIG. 15D. The left side of FIG. 15A shows the CNT-Al composite film seen from the Al film side, and the right side shows the remaining CNT film removed from the substrate after the CNT-Al composite film is peeled off. FIG. 15B shows the CNT-Al composite film viewed from the CNT film side. As shown in these figures, a composite film was obtained in which both were composed of CNT and Al but were well connected. The sheet resistance of the CNT-Al composite film was 0.011 Ω / sq, which was lower than that of the CNT film alone. Further, as can be seen from FIG. 15A, the remaining CNTs after peeling the CNT-Al composite film maintained the film structure. Another CNT-Al composite film can be newly obtained by holding the CNT film on the substrate again and forming a metal such as Al and peeling it off. That is, a CNT-Al composite film can be repeatedly obtained from the CNT film supported on the substrate.
　実施例１５
　エタノールに代えて０．５ｗｔ％ＳＤＢＳ水溶液を用いた以外は実施例１４と同様にしてＣＮＴ分散液を得た。ＣＮＴ分散液を３０００ｒｐｍで６０ｍｉｎ遠心分離し、上澄み液を分取した。上澄み液０．５ｍＬに純水２０ｍＬを加え、孔径０．１μｍのメンブレンフィルタを用いて減圧ろ過し、メンブレンフィルタ上に厚さ約０．１～０．１５μｍのＣＮＴ膜を作製した。 Example 15
A CNT dispersion was obtained in the same manner as in Example 14 except that 0.5 wt% SDBS aqueous solution was used instead of ethanol. The CNT dispersion was centrifuged at 3000 rpm for 60 minutes, and the supernatant was collected. 20 mL of pure water was added to 0.5 mL of the supernatant and filtered under reduced pressure using a membrane filter having a pore size of 0.1 μm to produce a CNT film having a thickness of about 0.1 to 0.15 μm on the membrane filter.
　ＣＮＴ膜が形成されたメンブレンフィルタをビーカー内で純水に含浸することにより、ＣＮＴ膜とメンブレンフィルタを分離させた。次いで、水面に浮かんだＣＮＴ膜を基板で掬い取った。これらの操作により、ＣＮＴ膜を基板上に支持した。更に、石英ガラス管の中にＣＮＴ膜付基板を設置し、Ａｒ希釈の４ｖｏｌ％Ｈ２流通下、８００℃に２０分間保持し、ＣＮＴ膜に付着しているＳＤＢＳを分解・除去した。 The membrane filter on which the CNT film was formed was impregnated with pure water in a beaker to separate the CNT film and the membrane filter. Next, the CNT film floating on the water surface was scraped off with a substrate. By these operations, the CNT film was supported on the substrate. Further, a substrate with a CNT film was placed in a quartz glass tube, and kept at 800 ° C. for 20 minutes under a flow of 4 vol% H 2 diluted with Ar to decompose and remove SDBS adhering to the CNT film.
　次いで、基板をＰＧ／ＰＢＮヒーターで約３５０℃に加熱し、タングステンボートを５００Ｗで約１７００℃まで加熱し蒸着時間を３０秒とした以外は実施例１４におけるＡｌの蒸着と同様にして、基板上のＣＮＴ膜上にＡｌ膜を蒸着した。蒸着により形成されたＡｌ膜の換算膜厚は５．２μｍであった。 Next, the substrate was heated to about 350 ° C. with a PG / PBN heater, the tungsten boat was heated to about 1700 ° C. with 500 W, and the deposition time was 30 seconds. An Al film was deposited on the CNT film. The converted film thickness of the Al film formed by vapor deposition was 5.2 μm.
　以上のようにして、ＣＮＴ－Ａｌ複合膜を得た。その後、ピンセットにてＣＮＴ－Ａｌ複合膜を基板から剥離し、自立したＣＮＴ－Ａｌ複合膜を得た。得られたＣＮＴ－Ａｌ複合膜のデジタルカメラ写真を図１６Ａ、１６Ｂに、平面ＳＥＭ像を図１６Ｃに、断面ＳＥＭ像を図１６Ｄに示す。図１６Ａの左側にはＣＮＴ－Ａｌ複合膜を剥離した後の基板が示されており、右側にはＡｌ膜側からみたＣＮＴ－Ａｌ複合膜が示されている。図１６ＢにはＣＮＴ膜側からみたＣＮＴ－Ａｌ複合膜が示されている。これらの図が示すように、ＣＮＴとＡｌのみからなりながら、両者が良好に接続された複合膜が得られた。厚さ０．１～０．１５μｍのＣＮＴ膜単体では薄すぎるため自立しないが、Ａｌと複合化することで自立させることができ、更に０．０１１Ω／ｓｑの低抵抗化を実現した。 Thus, a CNT-Al composite film was obtained. Thereafter, the CNT-Al composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Al composite film. A digital camera photograph of the obtained CNT-Al composite film is shown in FIGS. 16A and 16B, a planar SEM image is shown in FIG. 16C, and a cross-sectional SEM image is shown in FIG. 16D. The left side of FIG. 16A shows the substrate after the CNT-Al composite film is peeled off, and the right side shows the CNT-Al composite film as viewed from the Al film side. FIG. 16B shows a CNT-Al composite film viewed from the CNT film side. As shown in these figures, a composite film was obtained in which both were composed of CNT and Al but were well connected. A single CNT film having a thickness of 0.1 to 0.15 μm is too thin to be self-supporting, but it can be made self-supporting by being combined with Al, and a low resistance of 0.011 Ω / sq has been realized.
　実施例１６
　フィラメント状炭素として数層ＣＮＴ０．１ｍｇと気相成長炭素繊維（ＣＦ）（昭和電工社製ＶＧＣＦ）０．９ｍｇを用いた以外は実施例１４と同様にしてフィラメント状炭素分散液の減圧ろ過を行い、メンブレンフィルタ上に厚さ約１３μｍのＣＦとＣＮＴの混合物からなる複合膜（ＣＦ＋ＣＮＴ複合膜）を作製した。 Example 16
Filamentous carbon dispersion was filtered under reduced pressure in the same manner as in Example 14 except that 0.1 mg of several layers of CNT and 0.9 mg of vapor grown carbon fiber (CF) (VGCF manufactured by Showa Denko KK) were used as the filamentous carbon. On the membrane filter, a composite film (CF + CNT composite film) made of a mixture of CF and CNT having a thickness of about 13 μm was produced.
　ＣＦ＋ＣＮＴ複合膜をピンセットを用いてメンブレンフィルタから分離し、基板上に支持した。 The CF + CNT composite membrane was separated from the membrane filter using tweezers and supported on the substrate.
　次いで、実施例１５におけるＡｌの蒸着と同様にして、基板上のＣＦ＋ＣＮＴ複合膜上にＡｌ膜を蒸着した。蒸着により形成されたＡｌ膜の換算膜厚は５．８μｍであった。 Next, an Al film was deposited on the CF + CNT composite film on the substrate in the same manner as the Al deposition in Example 15. The converted film thickness of the Al film formed by vapor deposition was 5.8 μm.
　以上のようにして、基板上のＣＦ＋ＣＮＴ複合膜にＡｌが蒸着された複合膜（ＣＦ＋ＣＮＴ－Ａｌ複合膜）を得た。その後、ピンセットにてＣＦ＋ＣＮＴ－Ａｌ複合膜を基板から剥離し、自立したＣＦ＋ＣＮＴ－Ａｌ複合膜を得た。得られたＣＦ＋ＣＮＴ－Ａｌ複合膜のデジタルカメラ写真を図１７Ａ、１７Ｂに、平面ＳＥＭ像を図１７Ｃに、断面ＳＥＭ像を図１７Ｄに示す。図１７Ａの左側にはＣＦ＋ＣＮＴ－Ａｌ複合膜を剥離した後の基板が示されており、右側にはＡｌ膜側からみたＣＦ＋ＣＮＴ－Ａｌ複合膜が示されている。図１７ＢにはＣＦ＋ＣＮＴ複合膜側からみたＣＦ＋ＣＮＴ－Ａｌ複合膜が示されている。これらの図が示すように、ＣＦ、ＣＮＴ及びＡｌのみからなりながら、互いに良好に接続された複合膜が得られた。ＣＦ単体ではＣＦ間の付着力が低すぎるため自立しないが、ＣＮＴとＡｌと複合化することで自立させることができ、更に０．０１０Ω／ｓｑの低抵抗化を実現した。 As described above, a composite film (CF + CNT-Al composite film) in which Al was deposited on the CF + CNT composite film on the substrate was obtained. Thereafter, the CF + CNT-Al composite film was peeled from the substrate with tweezers to obtain a self-supporting CF + CNT-Al composite film. A digital camera photograph of the obtained CF + CNT-Al composite film is shown in FIGS. 17A and 17B, a planar SEM image is shown in FIG. 17C, and a cross-sectional SEM image is shown in FIG. 17D. The left side of FIG. 17A shows the substrate after the CF + CNT-Al composite film is peeled off, and the right side shows the CF + CNT-Al composite film as viewed from the Al film side. FIG. 17B shows a CF + CNT-Al composite film viewed from the CF + CNT composite film side. As shown in these figures, a composite film composed of only CF, CNT, and Al and well connected to each other was obtained. CF alone does not stand by itself because the adhesion force between CFs is too low, but it can be made self-supporting by combining with CNT and Al, and further a low resistance of 0.010 Ω / sq has been realized.
　実施例１７
　実施例１２と同様にしてＣＮＴの合成を行い、厚さ６μｍの単層ＣＮＴ垂直配向膜を基板上に形成した。単層ＣＮＴ垂直配向膜の断面ＳＥＭ像を図１８Ａに示す。 Example 17
CNT was synthesized in the same manner as in Example 12, and a single-walled CNT vertical alignment film having a thickness of 6 μm was formed on the substrate. A cross-sectional SEM image of the single-walled CNT vertical alignment film is shown in FIG. 18A.
　次いで、タングステンボートを５２０Ｗで約１７００℃まで加熱した以外は実施例１５と同様にして、基板上のＣＮＴ膜上にＡｌ膜を蒸着した。蒸着により形成されたＡｌ膜の換算膜厚は５．０μｍであった。 Next, an Al film was deposited on the CNT film on the substrate in the same manner as in Example 15 except that the tungsten boat was heated to about 1700 ° C. at 520 W. The converted film thickness of the Al film formed by vapor deposition was 5.0 μm.
　以上のようにして、ＣＮＴ－Ａｌ複合膜を得た。その後、ピンセットにてＣＮＴ－Ａｌ複合膜を基板から剥離し、自立したＣＮＴ－Ａｌ複合膜を得た。得られたＣＮＴ－Ａｌ複合膜のデジタルカメラ写真を図１８Ｂ、１８Ｃに、断面ＳＥＭ像を図１８Ｄに示す。図１８Ｂの左側にはＣＮＴ－Ａｌ複合膜を剥離した後の基板が示されており、右側にはＣＮＴ膜側からみたＣＮＴ－Ａｌ複合膜が示されている。図１８ＣにはＡｌ膜側からみたＣＮＴ－Ａｌ複合膜が示されている。これらの図が示すように、ＣＮＴとＡｌのみからなりながら、両者が良好に接続された複合膜が得られた。厚さ６μｍのＣＮＴ垂直配向膜単体では垂直配向性と薄さのため自立しないが、Ａｌと複合化することで自立させることができ、更に０．０１３Ω／ｓｑの低抵抗化を実現した。 Thus, a CNT-Al composite film was obtained. Thereafter, the CNT-Al composite film was peeled from the substrate with tweezers to obtain a self-supporting CNT-Al composite film. A digital camera photograph of the obtained CNT-Al composite film is shown in FIGS. 18B and 18C, and a cross-sectional SEM image is shown in FIG. 18D. The substrate after the CNT-Al composite film is peeled off is shown on the left side of FIG. 18B, and the CNT-Al composite film viewed from the CNT film side is shown on the right side. FIG. 18C shows a CNT-Al composite film viewed from the Al film side. As shown in these figures, a composite film was obtained in which both were composed of CNT and Al but were well connected. A single CNT vertical alignment film having a thickness of 6 μm is not self-supporting because of its vertical alignment and thinness, but it can be made self-supporting by compounding with Al, and a low resistance of 0.013 Ω / sq has been realized.
　実施例１８
　フィラメント状炭素として０．５ｍｇの数層ＣＮＴを用いた以外は実施例１４と同様にしてＣＮＴ分散液を得た。また、エタノール３０ｍＬに活性炭粒子（ＡＣ）（クラレ化学社製ＹＰ－８０Ｆ）４．５ｍｇを加え、超音波分散装置を用いて出力９０Ｗ、周波数４５ｋｈｚで４０分間分散処理を行うことによりＡＣ分散液を得た。この二つの分散液を混合することで、ＡＣ及びＣＮＴを質量比９：１で含有する分散液（ＡＣ＋ＣＮＴ混合分散液）６０ｍＬを得た。ＡＣ＋ＣＮＴ混合分散液を孔径５μｍのメンブレンフィルタ（ミリポア社製ＪＭＷＰ）を用いて減圧ろ過し、メンブレンフィルタ上に厚さ約７０μｍのＡＣとＣＮＴの混合物からなる複合膜（ＡＣ＋ＣＮＴ複合膜）を作製した。 Example 18
A CNT dispersion was obtained in the same manner as in Example 14 except that 0.5 mg of several-layer CNT was used as the filamentous carbon. Moreover, activated carbon particles (AC) (YP-80F manufactured by Kuraray Chemical Co., Ltd.) (4.5 mg) was added to ethanol (30 mL), and the dispersion liquid was subjected to dispersion treatment at an output of 90 W and a frequency of 45 kHz for 40 minutes using an ultrasonic dispersion device. Obtained. By mixing these two dispersions, 60 mL of a dispersion (AC + CNT mixed dispersion) containing AC and CNT at a mass ratio of 9: 1 was obtained. The AC + CNT mixed dispersion was filtered under reduced pressure using a membrane filter (JMWP manufactured by Millipore) having a pore size of 5 μm, and a composite film (AC + CNT composite film) made of a mixture of AC and CNT having a thickness of about 70 μm was formed on the membrane filter.
　ＡＣ＋ＣＮＴ複合膜をピンセットを用いてメンブレンフィルタから分離し、１５０℃で２時間乾燥させた後、基板上に支持した。 The AC + CNT composite membrane was separated from the membrane filter using tweezers, dried at 150 ° C. for 2 hours, and then supported on the substrate.
　次いで、蒸着源としてＡｌ片（ニラコ社Ａｌ０１１４８７、純度９９．９９％）を用い、基板の加熱温度を約１５０℃とし、チャンバー内の圧力を１×１０－３Ｐａとし、タングステンボートを１１０Ｗで約１７００℃まで加熱し、蒸着時間を１０秒とした以外は実施例１におけるＣｕの蒸着と同様にしてＡＣ＋ＣＮＴ複合膜上にＡｌを蒸着した。本実施例では、蒸着時のＡｌ源の原料量を１０，２０，３０，４０ｍｇと４通りに変えることで、換算膜厚が０．３，０．５，０．８，１．７μｍと４通りのＡｌ膜が得られた。 Then, an Al piece (Niraco Al011487, purity 99.99%) was used as a deposition source, the substrate heating temperature was about 150 ° C., the pressure in the chamber was 1 × 10 −3 Pa, and the tungsten boat was about 110 W. Al was vapor-deposited on the AC + CNT composite film in the same manner as the Cu vapor deposition in Example 1 except that the temperature was raised to 1700 ° C. and the vapor deposition time was 10 seconds. In this example, the amount of Al source material during vapor deposition was changed to four types of 10, 20, 30, 40 mg, so that the equivalent film thickness was 0.3, 0.5, 0.8, 1.7 μm and 4 A street Al film was obtained.
　以上のようにして、基板上のＡＣ＋ＣＮＴ複合膜にＡｌが蒸着された複合膜（ＡＣ＋ＣＮＴ－Ａｌ複合膜）を得た。その後、ピンセットにてＡＣ＋ＣＮＴ－Ａｌ複合膜を基板から剥離し、自立したＣＦ＋ＣＮＴ－Ａｌ複合膜を得た。得られたＡＣ＋ＣＮＴ－Ａｌ複合膜のデジタルカメラ写真を図１９Ａに、平面ＳＥＭ像を図１９Ｂに、断面ＳＥＭ像を図１９Ｃに示す。図１９ＡにはＡｌ膜側からみたＡＣ＋ＣＮＴ－Ａｌ複合膜が示されている。これらの図が示すように、ＡＣ、ＣＮＴ及びＡｌのみからなりながら、互いに良好に接続された複合膜が得られた。ＡＣ単体ではＡＣ間の付着力が低すぎるため自立しないが、ＣＮＴとＡｌと複合化することで自立させることができた。ＡＣ＋ＣＮＴ－Ａｌ複合膜のシート抵抗は、Ａｌ膜の換算膜厚が０．３，０．５，０．８，１．７μｍの場合、それぞれ０．２４，０．１４，０．０７３，０．０３６Ω／ｓｑであった（図１９Ｄ参照）。 Thus, a composite film (AC + CNT-Al composite film) in which Al was deposited on the AC + CNT composite film on the substrate was obtained. Thereafter, the AC + CNT-Al composite film was peeled from the substrate with tweezers to obtain a self-supporting CF + CNT-Al composite film. A digital camera photograph of the obtained AC + CNT-Al composite film is shown in FIG. 19A, a planar SEM image is shown in FIG. 19B, and a cross-sectional SEM image is shown in FIG. 19C. FIG. 19A shows an AC + CNT-Al composite film viewed from the Al film side. As shown in these figures, a composite film composed of only AC, CNT, and Al and well connected to each other was obtained. AC alone does not stand by itself because the adhesion between ACs is too low, but it can be made independent by combining CNT and Al. The sheet resistance of the AC + CNT-Al composite film is 0.24, 0.14, 0.073, 0.003 when the equivalent film thickness of the Al film is 0.3, 0.5, 0.8, and 1.7 μm, respectively. It was 036Ω / sq (see FIG. 19D).
　更に、ＡＣ＋ＣＮＴ複合膜、及びＡｌ膜の換算膜厚が０．３，０．５，０．８，１．７μｍであるＡＣ＋ＣＮＴ－Ａｌ複合膜を作用極、ＡＣ－ＣＮＴ膜を対極、Ａｇ／ＡｇＣｌ電極を参照極とし、１Ｍ　Ｎａ２ＳＯ４水溶液中で、サイクリックボルタンメトリを行った。掃引電位範囲は－１．０～０．６Ｖとし、掃引レートは５～１０００ｍＶ／ｓとした。図１９Ｅに比容量の掃引レート依存性を示す。ＡＣ＋ＣＮＴ膜は、低走査速度５ｍＶ／ｓにて１０８Ｆ／ｇ（電極総質量ＡＣ＋ＣＮＴ基準）の高容量を示したが、高走査速度２００ｍＶ／ｓでは１５Ｆ／ｇと容量が大きく低下した。一方で、換算膜厚０．８μｍのＡｌを蒸着したＡＣ＋ＣＮＴ－Ａｌ複合膜は、低走査速度５ｍＶ／ｓにて１１６Ｆ／ｇ（電極総質量ＡＣ＋ＣＮＴ＋Ａｌ基準）の高容量を示し、高走査速度２００ｍＶ／ｓでも８６Ｆ／ｇと高容量を維持した。Ａｌとの複合化により、ＡＣ＋ＣＮＴ複合膜のレート特性が飛躍的に向上した。 Furthermore, the AC + CNT-Al composite film and the AC + CNT-Al composite film having an equivalent film thickness of 0.3, 0.5, 0.8, 1.7 μm are used as the working electrode, the AC-CNT film as the counter electrode, and Ag / AgCl. Using the electrode as a reference electrode, cyclic voltammetry was performed in a 1M Na 2 SO 4 aqueous solution. The sweep potential range was −1.0 to 0.6 V, and the sweep rate was 5 to 1000 mV / s. FIG. 19E shows the sweep rate dependence of the specific capacity. The AC + CNT film showed a high capacity of 108 F / g (based on the total electrode mass AC + CNT) at a low scanning speed of 5 mV / s, but the capacity greatly decreased to 15 F / g at a high scanning speed of 200 mV / s. On the other hand, the AC + CNT-Al composite film on which Al with a converted film thickness of 0.8 μm is deposited exhibits a high capacity of 116 F / g (total electrode mass AC + CNT + Al standard) at a low scanning speed of 5 mV / s, and a high scanning speed of 200 mV / s. Even in s, the high capacity of 86 F / g was maintained. By combining with Al, the rate characteristics of the AC + CNT composite film were dramatically improved.
　以上、本発明を実施形態により説明してきたが、本発明の複合膜及びその製造方法は上記実施形態に限定されず、特許請求の範囲に記載した技術的思想の範囲内で適宜改変することができる。例えば、第１実施形態及び第３実施形態の複合膜を連続的に製造する装置を、それぞれ、図６（ａ）及び（ｂ）に示した装置を例に挙げて説明したが、それらは一具体例にすぎず、種々の変更および改良を行うことができる。例えば、図６（ａ）及び（ｂ）に示した装置では、搬送装置として搬送ベルトが掛け渡されたロール対を用いて、搬送ベルトを周回させたが、搬送ベルトを直線状または曲線状あるいは任意の形状の製造ラインで製造現場を通過させるように配置してもよい。また、搬送装置として搬送ベルトやロール対を用いる代わりに、ドラム（単独のロール）を用いることができる。この場合、ドラムの表面をフィラメント状炭素の集合体が形成される支持体とすることができ、ドラムの周囲にフィラメント状炭素の集合体を形成する機構や金属を蒸着させる機構を設置することができる。さらに、図６（ａ）及び（ｂ）に示した装置の搬送方向下流側に活物質を付与するための蒸着装置や供給器を設置することで、第２実施形態及び第４実施形態の複合膜を連続的に製造する装置に改造することができる。 As mentioned above, although this invention was demonstrated by embodiment, the composite film of this invention and its manufacturing method are not limited to the said embodiment, It can change suitably within the range of the technical idea described in the claim. it can. For example, the apparatuses for continuously producing the composite membranes of the first embodiment and the third embodiment have been described by taking the apparatus shown in FIGS. 6A and 6B as an example. It is only a specific example, and various changes and improvements can be made. For example, in the apparatus shown in FIGS. 6A and 6B, the conveyance belt is circulated using a pair of rolls around which the conveyance belt is stretched as the conveyance apparatus. However, the conveyance belt is linear or curved or You may arrange | position so that a manufacturing site may be passed by the manufacturing line of arbitrary shapes. Moreover, a drum (single roll) can be used instead of using a conveyor belt or a roll pair as the conveyor. In this case, the surface of the drum can be a support on which an aggregate of filamentous carbon is formed, and a mechanism for forming an aggregate of filamentous carbon or a mechanism for depositing metal can be installed around the drum. it can. Furthermore, by installing a vapor deposition apparatus and a supply device for applying an active material on the downstream side in the transport direction of the apparatus shown in FIGS. 6A and 6B, the composite of the second embodiment and the fourth embodiment is provided. It can be retrofitted into a device that continuously produces membranes.
　本発明の複合膜は、低抵抗であり、活物質が体積変化しても集電体から剥離しにくいという利点を有する。そのため、本発明の複合膜を、リチウムイオン電池の電極に適用することにより、リチウムイオン電池の高容量化、高寿命化が実現される。 The composite film of the present invention has an advantage that it has low resistance and is difficult to peel from the current collector even if the volume of the active material changes. Therefore, by applying the composite film of the present invention to an electrode of a lithium ion battery, it is possible to increase the capacity and life of the lithium ion battery.
　１０　金属層、　２０　フィラメント状炭素膜
　３４　活物質、　４０　第１層、　４２　フィラメント状炭素
　４４　網目構造、　４６　垂直配向構造、　５２　ローラ対
　５４、５４ａ　搬送ベルト、　５６　供給器、　５８　蒸着器
　６０　共存層、　６３　吸引濾過機、　７１　スパッタ装置
　７３　ＣＶＤ装置、　７４　触媒、　８０　第２層、１００　複合膜
　３００、４００　機能性複合膜、１５０、１７０　複合膜の製造装置 DESCRIPTION OF SYMBOLS 10 Metal layer, 20 Filament-like carbon film 34 Active material, 40 1st layer, 42 Filament-like carbon 44 Network structure, 46 Vertical alignment structure, 52 Roller pair 54, 54a Conveyor belt, 56 Feeder, 58 Evaporator 60 Coexistence layer , 63 Suction filter, 71 Sputter device 73 CVD device, 74 Catalyst, 80 Second layer, 100 Composite membrane 300, 400 Functional composite membrane, 150, 170 Composite membrane manufacturing device

Claims (23)

  1. 　フィラメント状炭素から構成されたフィラメント状炭素層と、
    　金属から構成された金属層とだけからなり、
    　前記金属層の一部または全部が前記フィラメント状炭素層の一部と重複して、前記フィラメント状炭素と前記金属が共存する共存領域を有することを特徴とする自立した複合膜。     A filamentous carbon layer composed of filamentous carbon;
    It consists only of a metal layer composed of metal,
    A self-supporting composite film, wherein a part or all of the metal layer overlaps with a part of the filamentous carbon layer and has a coexistence region where the filamentous carbon and the metal coexist.
  2. 　前記金属層の一部が前記フィラメント状炭素層の一部と重複している請求項１に記載の複合膜。 The composite film according to claim 1, wherein a part of the metal layer overlaps a part of the filamentous carbon layer.
  3. 　前記フィラメント状炭素層が網目構造を有し、
    　前記共存領域において、前記網目構造の網目内に前記金属が入り込んでいる請求項１又は２に記載の複合膜。     The filamentous carbon layer has a network structure;
    3. The composite film according to claim 1, wherein in the coexistence region, the metal enters the mesh of the mesh structure.
  4. 　前記フィラメント状炭素層が前記フィラメント状炭素層の厚み方向に前記フィラメント状炭素が配向した垂直配向構造を有し、
    　前記共存領域において、前記垂直配向構造の前記フィラメント状炭素間の空隙に前記金属が入り込んでいる請求項１又は２に記載の複合膜。     The filamentous carbon layer has a vertical alignment structure in which the filamentous carbon is aligned in the thickness direction of the filamentous carbon layer,
    3. The composite film according to claim 1, wherein in the coexistence region, the metal enters a gap between the filamentous carbons of the vertical alignment structure.
  5. 　前記フィラメント状炭素が束となって、前記フィラメント状炭素層の厚み方向に直立した壁を形成する請求項４に記載の複合膜。 The composite film according to claim 4, wherein the filamentous carbon is bundled to form an upright wall in the thickness direction of the filamentous carbon layer.
  6. 　金属から構成される金属層と
    　フィラメント状炭素の集合体とだけからなり、
    　前記フィラメント状炭素の集合体の一部が前記金属層中に含まれており、
    　前記フィラメント状炭素の集合体の他部が前記金属層上で露出していることを特徴とする自立した複合膜。     It consists only of a metal layer composed of metal and an aggregate of filamentous carbon,
    A part of the aggregate of filamentous carbon is included in the metal layer,
    A self-supporting composite film, wherein the other part of the aggregate of filamentous carbon is exposed on the metal layer.
  7. 　前記フィラメント状炭素がカーボンナノチューブを含む請求項１～６のいずれか一項に記載の複合膜。 The composite film according to any one of claims 1 to 6, wherein the filamentous carbon includes carbon nanotubes.
  8. 　前記金属がＣｕ、Ａｌ又はＮｉである請求項１～７のいずれか一項に記載の複合膜。 The composite film according to any one of claims 1 to 7, wherein the metal is Cu, Al, or Ni.
  9. 　請求項１～８のいずれか一項に記載の複合膜と、
    　前記フィラメント状炭素に付着した活物質とを有する機能性複合膜。     A composite membrane according to any one of claims 1 to 8,
    A functional composite film having an active material attached to the filamentous carbon.
  10. 　フィラメント状炭素から構成されたフィラメント状炭素膜を作製する工程と、
    　支持体に支持された前記フィラメント状炭素膜上に金属を蒸着する工程と、
    　前記フィラメント状炭素膜及び前記金属の複合膜を前記支持体から分離する工程とを有する複合膜の製造方法。     Producing a filamentous carbon film composed of filamentous carbon;
    Depositing a metal on the filamentary carbon film supported by a support;
    Separating the filamentous carbon film and the metal composite film from the support.
  11. 　前記フィラメント状炭素膜を作製する工程において、網目構造を有する前記フィラメント状炭素膜を作製する請求項１０に記載の複合膜の製造方法。 The method for producing a composite film according to claim 10, wherein in the step of producing the filamentous carbon film, the filamentous carbon film having a network structure is produced.
  12. 　前記フィラメント状炭素膜を作製する工程が、前記フィラメント状炭素膜の厚さ方向に前記フィラメント状炭素が配向するように、前記フィラメント状炭素を形成することを含む請求項１０に記載の複合膜の製造方法。 11. The composite film according to claim 10, wherein the step of producing the filamentous carbon film includes forming the filamentous carbon so that the filamentous carbon is oriented in a thickness direction of the filamentous carbon film. Production method.
  13. 　さらに、前記フィラメント状炭素膜及び前記金属の複合膜を前記支持体から分離する工程の後に、前記フィラメント状炭素膜を収縮させて、前記フィラメント状炭素の束からなる前記フィラメント状炭素層の厚さ方向に直立した壁を形成する工程を含む請求項１２に記載の複合膜の製造方法。 Further, after the step of separating the filamentous carbon film and the metal composite film from the support, the filamentous carbon film is contracted to reduce the thickness of the filamentous carbon layer comprising the bundle of filamentous carbon. The manufacturing method of the composite film of Claim 12 including the process of forming the wall upright in the direction.
  14. 　前記フィラメント状炭素膜上に金属を蒸着する工程の前に、前記フィラメント状炭素膜を前記支持体により支持する工程を含むことを含む請求項１０～１３のいずれか一項に記載の複合膜の製造方法。 The composite film according to any one of claims 10 to 13, further comprising a step of supporting the filamentous carbon film by the support before the step of depositing a metal on the filamentous carbon film. Production method.
  15. 　前記支持体を移動させながら、移動方向上流側で前記支持体上に前記フィラメント状炭素膜を作製し、前記移動方向の下流側で前記支持体上の前記フィラメント状炭素膜に前記金属を蒸着する請求項１０～１３のいずれか一項に記載の複合膜の製造方法。 While moving the support, the filamentous carbon film is formed on the support on the upstream side in the movement direction, and the metal is deposited on the filamentous carbon film on the support on the downstream side in the movement direction. The method for producing a composite membrane according to any one of claims 10 to 13.
  16. 　前記フィラメント状炭素膜の前記金属を蒸着した面と反対の面上に活物質を付着させる工程をさらに有する請求項１０～１５のいずれか一項に記載の複合膜の製造方法。 The method of manufacturing a composite film according to any one of claims 10 to 15, further comprising a step of attaching an active material to a surface of the filamentous carbon film opposite to a surface on which the metal is deposited.
  17. 　請求項１０～１６のいずれか一項に記載の製造方法によって形成された複合膜。 A composite film formed by the production method according to any one of claims 10 to 16.
  18. 　請求項１～８または１７のいずれか一項に記載の複合膜を有する電極。 An electrode having the composite film according to any one of claims 1 to 8 or 17.
  19. 　請求項９に記載の機能性複合膜を有する電極。 An electrode having the functional composite film according to claim 9.
  20. 　請求項１８又は１９に記載の電極を備える蓄電デバイス。 An electricity storage device comprising the electrode according to claim 18 or 19.
  21. 　金属層と、フィラメント状炭素の集合体だけからなり、前記フィラメント状炭素の集合体の一部が前記金属層中に含まれており、前記フィラメント状炭素の集合体の他部が前記金属層上で露出している自立した複合膜を製造するための装置であって、
    　支持体を連続的に移動する移動機構と、
    　前記移動方向上流側に設けられて前記支持体上に前記フィラメント状炭素の集合体を形成する集合体形成部と、
    　前記移動方向下流側に設けられて前記フィラメント状炭素の集合体上に金属を蒸着する蒸着機構とを備える複合膜製造装置。     It consists only of a metal layer and an aggregate of filamentous carbon, a part of the aggregate of filamentous carbon is included in the metal layer, and the other part of the aggregate of filamentous carbon is on the metal layer. An apparatus for producing a self-supporting composite membrane exposed at
    A moving mechanism for continuously moving the support;
    An assembly forming portion that is provided on the upstream side in the moving direction and forms an assembly of the filamentous carbon on the support;
    An apparatus for producing a composite film, comprising: a vapor deposition mechanism that is provided on the downstream side in the movement direction and deposits metal on the filamentary carbon aggregate.
  22. 　前記移動機構が前記支持体を回転移動するロールを備える請求項２１に記載の複合膜製造装置。 The composite film manufacturing apparatus according to claim 21, wherein the moving mechanism includes a roll that rotates and moves the support.
  23. 　前記集合体形成部と前記蒸着機構を連続的に動作させることにより、長尺の複合膜を前記支持体上に形成し、該長尺の複合膜を前記支持体から連続的に剥離することによって前記長尺の複合膜を得る請求項２１または２２に記載の複合膜製造装置。 By continuously operating the assembly forming part and the vapor deposition mechanism, a long composite film is formed on the support, and the long composite film is continuously peeled from the support. The composite film manufacturing apparatus according to claim 21 or 22, wherein the long composite film is obtained.
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