WO2015087948A1 - Corps poreux en métal revêtu de matériau carboné, collecteur, électrode et dispositif d'accumulation d'énergie - Google Patents

Corps poreux en métal revêtu de matériau carboné, collecteur, électrode et dispositif d'accumulation d'énergie Download PDF

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WO2015087948A1
WO2015087948A1 PCT/JP2014/082776 JP2014082776W WO2015087948A1 WO 2015087948 A1 WO2015087948 A1 WO 2015087948A1 JP 2014082776 W JP2014082776 W JP 2014082776W WO 2015087948 A1 WO2015087948 A1 WO 2015087948A1
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Prior art keywords
porous body
carbon material
carbon
metal porous
metal
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PCT/JP2014/082776
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English (en)
Japanese (ja)
Inventor
奥野　一樹
細江　晃久
西村　淳一
弘太郎 木村
健吾 後藤
英彰 境田
隼一 本村
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住友電気工業株式会社
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Priority claimed from JP2014231336A external-priority patent/JP2017027654A/ja
Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Publication of WO2015087948A1 publication Critical patent/WO2015087948A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a carbon material-coated metal porous body, a current collector, an electrode, and an electricity storage device.
  • Power storage devices such as lithium ion secondary batteries, sodium ion secondary batteries, electric double layer capacitors, lithium ion capacitors and sodium ion capacitors are used for portable small electronic devices such as mobile phones and notebook personal computers, and hybrid electric vehicles (HEVs). ), And widely used as a power source for electric vehicles (EV). Further, as the functions of these devices are enhanced and the applications are expanded, further improvement in capacity is required.
  • a metal foil such as an aluminum foil is generally used as a current collector (support) to which a positive electrode material or a negative electrode material is attached.
  • a positive electrode active material such as lithium cobaltate (LiCoO 2 ) powder, a binder such as polyvinylidene fluoride (PVDF), carbon, and the like on both sides of an aluminum foil current collector
  • PVDF polyvinylidene fluoride
  • An electrode in which a positive electrode mixture layer containing a conductive additive such as powder is formed is used (for example, Patent Document 1).
  • Patent Document 2 proposes that a coating liquid that can form a film having excellent adhesion and solvent resistance on the surface of a metal material is used as an electrode for a battery or a capacitor.
  • the metal foil has a two-dimensional structure and is inferior to a porous structure current collector in terms of carrying active material and packing density.
  • the metal foil cannot be held so as to enclose the active material, the expansion and shrinkage of the active material cannot be suppressed, and the lifetime is not provided unless the filling amount is reduced.
  • the distance between the current collector and the active material becomes long, the utilization factor of the active material at a position away from the current collector is small, and the capacity density is also small.
  • metal foil is used in the shape of a porous body such as punching metal, screen punch, and expanded metal, it is also a substantially two-dimensional structure, and a significant improvement in capacity density cannot be expected.
  • it is desired to employ a three-dimensional structure having a higher porosity than the two-dimensional structure as a current collector.
  • the inventors of the present invention have eagerly searched for the purpose of increasing the output of the electricity storage device while increasing the capacity of the electricity storage device by adopting a three-dimensional structure having a large porosity as a current collector of the electricity storage device.
  • a three-dimensional structure having a large porosity is used as a current collector for an electrode of an electricity storage device, the surface of the skeleton of the three-dimensional structure is generally uneven, and the active material is highly retained by the pores. Therefore, the surface of the skeleton of the three-dimensional structure has not been modified conventionally.
  • the present inventors paid attention to modifying the surface of the skeleton of the three-dimensional structure used as a current collector, and studied to form a carbon film on the surface of the skeleton using a carbon material dispersion.
  • the carbon material dispersion liquid is used, there has been found a problem that an unattached portion of the dispersion liquid is generated on the surface of the skeleton, or clogging occurs in the pore portions of the skeleton. That is, when the metal porous body is immersed in the carbon material dispersion, a portion where the dispersion does not come into contact with the surface of the skeleton due to surface tension or bubbles is generated, or the dispersion once entered into the pores of the metal porous body is removed. It was difficult to do so, and in many places, the pores of the metal porous body were filled and clogging occurred.
  • the metal porous body is immersed in the carbon material dispersion, it has been found that it is difficult to reduce the amount of carbon material applied.
  • the carbon film to be formed is thick, the porosity of the metal porous body is lowered, so that the energy density is lowered when an electrode is used. For this reason, if the amount of the carbon material in the carbon material dispersion is reduced in order to reduce the amount of the carbon material applied, uniform application becomes difficult, and a carbon film equivalent to the case of the aluminum foil cannot be obtained.
  • the present invention provides a carbon material-covered metal porous body suitable for a current collector capable of increasing the capacity and improving the output characteristics of an electricity storage device. Let it be an issue.
  • the carbon material-coated metal porous body of the present invention is a carbon material-coated metal porous body in which the surface of the skeleton of the metal porous body having communication holes is coated with a carbon material, and the apparent density of the carbon material is 5 mg.
  • a carbon material-coated metal porous body that is at least / cm 3 and at most 100 mg / cm 3 .
  • a carbon material-covered metal porous body suitable for a current collector capable of increasing the capacity and output of an electricity storage device can be provided.
  • a carbon material-coated porous metal body according to an embodiment of the present invention is a carbon material-coated metal porous body in which a surface of a skeleton of a metal porous body having communication holes is coated with a carbon material, A carbon material-coated porous metal body having an apparent density of 5 mg / cm 3 or more and 100 mg / cm 3 or less.
  • the carbon material-coated metal porous body described in (1) above has a pore portion when used as a current collector of an electricity storage device because the surface of the skeleton of the metal porous body is covered with a dense carbon film made of a carbon material. It is possible to improve the retention of the active material filled in and the contact with the active material.
  • the apparent density of the carbon material is determined by dividing the coating amount (mg) of the carbon material by the apparent volume (cm 3 ) of the metal porous body.
  • the porous metal body preferably has a three-dimensional network structure.
  • the porosity becomes very high, and therefore the active material filling amount when used as a current collector of an electricity storage device. This increases the capacity of the power storage device.
  • the metal porous body is preferably an aluminum porous body mainly composed of aluminum or a nickel porous body mainly composed of nickel. Since the metal porous body is an aluminum porous body as described in (3) above, for example, a lithium ion secondary battery, a sodium ion secondary battery, an electric double layer capacitor, a lithium ion capacitor, a sodium ion capacitor, etc.
  • a carbon material-coated porous metal body suitable for a current collector for an electricity storage device or the like can be provided.
  • the metal porous body is a nickel porous body
  • a carbon material-covered metal porous body suitable for a material for an electricity storage device such as a current collector of a nickel hydrogen battery or a gas diffusion layer of a fuel cell, a filter, etc.
  • the aluminum porous body mainly composed of aluminum means an aluminum porous body having an aluminum content of 55% by mass or more.
  • the nickel porous body mainly composed of nickel is nickel. This means a nickel porous body having a content of 55% by mass or more.
  • a current collector according to an embodiment of the present invention is a current collector including the carbon material-coated metal porous body according to any one of (1) to (3) above. Since the current collector described in (4) uses the carbon material-coated metal porous body according to the embodiment of the present invention as a current collector for an electricity storage device, the capacity of the electricity storage device is increased and the output is increased. Is a current collector capable of
  • the collector which concerns on embodiment of this invention is not coat
  • an external terminal and a carbon material covering metal porous body can join in the state of metals, and are preferred.
  • the electrode which concerns on embodiment of this invention is an electrode which used the carbon material covering metal porous body as described in any one of said (1) to (3) as a collector.
  • the electrode described in (6) above is obtained by filling the pores of the carbon material-coated porous metal according to the embodiment of the present invention with an active material or the like. It is an electrode that is excellent in contact with a substance and can increase the capacity and output of an electricity storage device.
  • the electrical storage device which concerns on embodiment of this invention is an electrical storage device using the electrode as described in said (6).
  • the electricity storage device according to the above (7) uses an electrode obtained by filling the pores of the carbon material-covered metal porous body according to the embodiment of the present invention with an active material or the like. It is an electricity storage device.
  • the carbon material-coated metal porous body according to the embodiment of the present invention is a carbon material-coated metal porous body in which the surface of the skeleton of the metal porous body having communication holes is coated with the carbon material,
  • the apparent density of the material is 5 mg / cm 3 or more and 100 mg / cm 3 or less. Since the carbon material-coated porous metal body according to the embodiment of the present invention has a skeleton whose surface is covered with a dense film made of a carbon material, when the active material or the like that is an electrode material of an electricity storage device is held, Holding property and contactability are good, and it is possible to increase the capacity and output of the electricity storage device.
  • the contact electrical resistance with the carbon film covering the surface of the skeleton can be reduced.
  • the carbon material-coated metal porous body has high adhesion between the surface of the skeleton of the metal porous body and the carbon film made of the carbon material. Therefore, when used as an electrode of an electricity storage device, the resistance in the electrode can be lowered. it can.
  • the carbon material preferably forms a carbon film substantially made of carbon. Further, other components may be intentionally contained for the purpose of modifying the film or as unavoidable impurities. As will be described later, a film made of such a carbon material is coated with a carbon paint while applying vibration to the metal porous body, or the metal porous body is an anode in a molten salt bath containing carbide ions (C 2 2 ⁇ ). It can be formed by acting to become.
  • the carbon material-coated metal porous body can be preferably used as a current collector for an electricity storage device when the apparent density of the carbon material is 5 mg / cm 3 or more and 100 mg / cm 3 or less. That is, when the apparent density is less than 5 mg / cm 3 , the carbon amount is insufficient and the effect of coating the carbon material cannot be sufficiently obtained. Further, the surface of the skeleton of the metal porous body cannot be sufficiently covered, and a portion where the surface of the skeleton of the metal porous body is exposed is generated.
  • the apparent density of the carbon material in the carbon material-coated porous metal body is preferably 6 mg / cm 3 or more and 60 mg / cm 3 or less, and is 6 mg / cm 3 or more and 35 mg / cm 3 or less. More preferably, it is 6 mg / cm 3 or more and 15 mg / cm 3 or less.
  • the density of the carbon film when the density of the carbon film is 1.5 g / cm 3 to 2.0 g / cm 3 , the apparent appearance of the carbon material in the carbon material-coated metal porous body If the density is about 6 mg / cm 3 , the thickness of the carbon film is about 1 ⁇ m, and if the apparent density is about 60 mg / cm 3 , the thickness is about 10 ⁇ m.
  • the metal porous body is an aluminum porous body having aluminum as a main component (aluminum content is 55% by mass or more) or a nickel porous body having nickel as a main component (nickel content is 55% by mass or more). It is preferable that it may contain other components for various purposes.
  • examples of the other components include Si, Mg, Mn, Co, Fe, Ni, and the like. Just choose.
  • examples of the other components include P, B, Fe, Sn, Cr, W, Cu, and Co. What is necessary is just to select suitably according to the use of.
  • the aluminum content in the aluminum porous body may be appropriately changed according to the use of the carbon material-covered metal porous body, but the carbon material-covered metal porous body is used as a current collector of an electricity storage device containing a non-aqueous electrolyte.
  • the aluminum content is high.
  • the content of the porous aluminum body is preferably 80% by mass or more, and more preferably 97% by mass or more. Since the carbon material-coated metal porous body has a carbon material coated on the surface of the skeleton of the metal porous body, for example, the purity of aluminum is higher than that when the aluminum porous body is used as a current collector for the electricity storage device as it is. Even if it is low, it can be used.
  • nickel porous bodies are excellent in heat resistance, corrosion resistance, current collection, pressure loss, and collection rate, and are suitably used for current collectors of nickel-metal hydride batteries, gas diffusion layers of fuel cells, filters, etc. Yes. What is necessary is just to change suitably the content rate of nickel in such a nickel porous body according to the use which uses a carbon material covering metal porous body.
  • the nickel content in the nickel porous body is 30% by mass or more and 100% by mass. It is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less.
  • the nickel porous body contains almost no inevitable impurities, in addition to a nickel porous body of almost 100% Ni, a NiP porous body, a NiB porous body, a NiCr porous body, a NiFe porous body, a NiSn porous body, A porous metal body exhibiting corrosion resistance similar to that of a nickel porous body, such as a porous body of NiSnCr, a porous body of NiW, a porous body of NiCu, or a porous body of NiCo, can be used. By coating the surface of the skeleton of the metal porous body with a carbon material to form a carbon film, the corrosion resistance and conductivity of the metal porous body can be further improved.
  • the structure of the carbon material-coated metal porous body is not particularly limited as long as it has a communication hole that can hold an active material or the like or can be used as a filter. It is preferable that it is 60% or more.
  • the capacity of the electricity storage device can be increased by increasing the filling amount of the active material, and therefore the porosity is 70% or more. Is more preferable, and it is still more preferable that it is 80% or more.
  • the carbon material-coated metal porous body preferably has a three-dimensional network structure with a porosity of 90% or more.
  • the thickness of the said carbon material covering metal porous body may be selected from a range of about 0.1 mm or more and 5 mm or less.
  • the metal porous body in the carbon material-covered metal porous body is not particularly limited as long as it has a porous structure having communication holes, but a nickel porous body having a three-dimensional network structure (manufactured by Sumitomo Electric Industries, Ltd.) And a porous aluminum body having a three-dimensional network structure obtained by a plating method described in JP 2011-225950 A.
  • the nickel porous body or aluminum porous body is a nickel porous body or aluminum porous body having a three-dimensional network structure produced by a plating method, so that the purity of nickel or aluminum of the carbon material-coated metal porous body is 99.9 masses. % Or more and the porosity can be 90% or more.
  • the carbon material-covered metal porous body according to the embodiment of the present invention is such that the metal porous body is coated with a carbon paint while applying vibration to the metal porous body or the metal porous body is an anode in a molten salt bath containing carbide ions (C 2 2- ). It can be formed by acting to become. (Method of applying carbon paint) As described above, the present inventors first studied to form a carbon film on the surface of the skeleton of the metal porous body by immersing the metal porous body in the carbon material dispersion.
  • the carbon material dispersion can be the same as the coating liquid used when forming the carbon film on the surface of the aluminum foil, but it is preferable to use a high-viscosity liquid with an increased amount of binder. . Specifically, carbon particles mixed with a binder or a dispersant and dispersed in a solvent may be used.
  • carbon blacks such as acetylene black and ketjen black, graphite powders and hard carbon powders can be used.
  • carbon blacks or graphites are preferable.
  • the solid content ratio of the carbon material dispersion is preferably 2% by mass or more and 30% by mass or less, although it depends on the type of binder and dispersant and the viscosity of the solvent.
  • a more preferable solid content ratio is 4% by mass or more and 25% by mass or less.
  • the ratio of the carbon particles in the solid content of the carbon material dispersion is preferably 20% by mass or more and 60% by mass or less, depending on the type of the binder.
  • a more preferable range of the ratio of carbon particles in the solid content is 30% by mass or more and 55% by mass or less.
  • the binder when used for an electricity storage device, the binder may be selected from those that are resistant to the slurry used in the electrode coating process of the electricity storage device.
  • carboxymethyl cellulose hereinafter referred to as CMC
  • acrylic styrene
  • PTFE polytetrafluoroethylene
  • PVA polyvinyl alcohol
  • an aqueous binder such as In the case where an aqueous slurry is used in the electrode coating process of the electricity storage device, an organic binder such as polyvinylidene fluoride (hereinafter referred to as PVDF) is preferable.
  • PVDF polyvinylidene fluoride
  • the carbon material dispersion By applying the carbon material dispersion while applying vibration to the metal porous body, it is possible to drop the excessively supplied carbon material dispersion from the metal porous body and apply an appropriate amount of carbon material dispersion. It becomes. Moreover, it can also suppress that the non-attached part of a carbon material dispersion liquid generate
  • the vibration applied to the metal porous body it is preferable to vibrate the sheet-like metal porous body in the thickness direction of the metal porous body rather than in the plane direction. At this time, the porous metal body may vibrate in the plane direction accompanying the vibration in the thickness direction.
  • the vibration frequency when vibrating the metal porous body is 0.1 Hz or more and 1000 Hz or less.
  • the frequency is more preferably 0.5 Hz or more and 800 Hz or less, and further preferably 1 Hz or more and 500 Hz or less.
  • the amplitude when the metal porous body is vibrated may be arbitrarily set within a range in which the metal porous body is not damaged. However, even when the metal porous body is thick, it is usually several millimeters in consideration of being 10 mm. It is preferable to suppress to the following extent. A more preferable amplitude is 0.2 mm or more and 8 mm or less, and a still more preferable amplitude is 0.5 mm or more and 6 mm or less. Moreover, what is necessary is just to change suitably the time which vibrates a metal porous body with the characteristic of the carbon material dispersion liquid to be used.
  • the carbon material dispersion when the carbon material dispersion has a low solid content ratio / low viscosity, the carbon material dispersion is set to a short time, and when the carbon material dispersion liquid has a high solid content ratio / high viscosity, it may be set to a long time. For example, it is preferable to vibrate in a time range of about 10 seconds to 5 minutes.
  • the carbon material dispersion liquid When vibrating the metal porous body, the carbon material dispersion liquid may be applied from the top of the metal porous body, or a necessary amount of the carbon material dispersion liquid is placed on the metal porous body. May be. A more uniform carbon film can be obtained when the timing at which the carbon material dispersion is applied to the porous metal body and the timing at which vibration is applied to the porous metal body overlap.
  • the thickness of the coating film made of the carbon material dispersion formed on the skeleton surface of the porous metal body is preferably about 0.1 ⁇ m or more and 15 ⁇ m or less.
  • the thickness of the coating film is more preferably 0.2 ⁇ m or more and 14 ⁇ m or less, and further preferably 0.5 ⁇ m or more and 13 ⁇ m or less.
  • the particle diameter of the carbon particles is preferably 0.03 ⁇ m or more and 12 ⁇ m or less.
  • the particle size of the carbon particles is more preferably 0.03 ⁇ m or more and 11 ⁇ m or less, and further preferably 0.03 ⁇ m or more and 8 ⁇ m or less.
  • the drying temperature is preferably a high temperature in order to shorten the drying time, but may be appropriately selected in consideration of the heat resistance temperature of the solvent and binder contained in the carbon material dispersion.
  • the drying temperature is preferably about 100 ° C.
  • NMP N-methylpyrrolidone
  • PVDF PVDF
  • Method of molten salt plating As a method of forming a carbon film made of a carbon material on the surface of the skeleton of the porous metal body, in addition to the above method, a method using carbon plating with a molten salt can be mentioned. That is, in a molten salt carbon plating bath containing at least carbide ions (C 2 2 ⁇ ), a step of electrodepositing a carbon material on the surface of the skeleton of the metal porous body by causing the metal porous body having communication holes to act as an anode The carbon material-covered metal porous body can be obtained by the method for producing a carbon material-covered metal porous body having the above.
  • the surface of the skeleton of the metal porous body can be covered with a dense carbon film made of a carbon material.
  • the temperature of the molten salt carbon plating bath is 250 ° C. or more and 600 ° C. or less, and the molten salt electroplating is performed so that the apparent density of the carbon material is 5 mg / cm 3 or more and 100 mg / cm 3 or less.
  • a dense carbon film made of a carbon material on the surface of the skeleton of the porous metal body.
  • a method for forming a dense carbon film on the surface of a metal plate using the molten salt carbon plating bath is disclosed in Japanese Patent No. 51122010. That is, by making the aluminum porous body act as an anode in a molten salt carbon plating bath in which carbide ions as reactive species are dissolved, the surface of the skeleton of the aluminum porous body can be covered with a dense carbon film. .
  • the above document discloses that a carbon salt is melted in an alkali metal halide and an alkaline earth metal halide and carbon plating is performed at 250 ° C. to 800 ° C.
  • the temperature of the molten salt carbon plating bath is 250 ° C. or more and 600 ° C. or less.
  • the temperature of the molten salt carbon plating bath is 250 ° C. or higher, the viscosity of the molten salt is prevented from becoming too high, and the carbon film can be uniformly plated. Moreover, it can suppress that an aluminum softens because the temperature of the said molten salt carbon plating bath is 600 degrees C or less. From these viewpoints, the temperature of the molten salt carbon plating bath is more preferably 300 ° C. or more and 550 ° C. or less, and further preferably 400 ° C. or more and 500 ° C. or less.
  • molten salt carbon plating bath a solution obtained by adding CaC 2 to a molten salt obtained by mixing and melting an alkali metal halide or an alkaline earth metal halide can be used.
  • a molten salt that does not react with the molten salt component and does not react with the carbide ions (C 2 2 ⁇ ) in the molten salt may be selected.
  • the metal porous body as the base material is an aluminum porous body, if a molten salt of LiCl and KCl is used, Li and aluminum may be alloyed to cause embrittlement of the aluminum porous body.
  • the surface of the skeleton of the metal porous body is oxidized and a metal oxide film is formed, it is preferable to perform reverse electrolysis in order to perform carbon plating. That is, in the method for producing the carbon material-coated metal porous body, the skeleton of the metal porous body is obtained by causing the metal porous body to act as a cathode in the molten salt carbon plating bath before the step of electrodepositing the carbon material. It is preferable to have a step of dissolving the oxide film on the surface.
  • the reverse electrolysis potential becomes the alloying potential of Li and aluminum, and thus reverse electrolysis cannot be performed.
  • a carbon rod can be used as the counter electrode.
  • the film thickness When the film thickness is reduced, it becomes a dense carbon film reflecting the surface roughness of the skeleton of the porous metal body, so that the porous metal body has a rough skeleton surface. It is preferable to do. However, if the film thickness is too thin, the surface of the skeleton of the aluminum porous body cannot be sufficiently covered with the carbon material, and a part of the surface of the skeleton of the aluminum porous body may be exposed. For this reason, the apparent density of the carbon material formed on the surface of the skeleton of the aluminum porous body is set to 5 mg / cm 3 or more.
  • the film thickness is made too thick, a thick carbon layer is formed between the aluminum skeleton and the electricity storage device active material, which may increase the electrical resistance. Furthermore, since the porosity of a metal porous body will fall, when it uses as a collector of an electrical storage device, the fall of a capacity
  • molten salt electroplating is performed so that the apparent density of the carbon material in the carbon material-covered metal porous body is 6 mg / cm 3 or more and 60 mg / cm 3 or less. It is more preferable that the concentration be 6 mg / cm 3 or more and 35 mg / cm 3 or less, and it is more preferable that the concentration be 6 mg / cm 3 or more and 15 mg / cm 3 or less.
  • a carbon rod can be used as the counter electrode.
  • the aluminum porous body or nickel porous body described in the description of the carbon material-coated metal porous body according to the embodiment of the present invention can be preferably used. That is, as the aluminum porous body, one having an aluminum content of 55% by mass or more (preferably 80% by mass or more, more preferably 97% by mass or more) may be used. For various purposes, Si, Mg, Mn , Co, Fe, and Ni may be used.
  • the porosity of the aluminum porous body is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
  • the nickel content may be 55% by mass or more, and those containing other components may be used for various purposes.
  • the porosity of the nickel porous body is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
  • the aluminum porous body is not particularly limited as long as it has a porous structure having communication holes, but has a three-dimensional network structure obtained by a plating method described in JP2011-225950A. It is preferable to use an aluminum porous body. Thereby, the purity of aluminum of a carbon material covering metal porous body can be 99.9 mass% or more, and a porosity can be 90% or more.
  • the carbon material-coated metal porous body according to the embodiment of the present invention can be used as a current collector for an electricity storage device, and can be used as an electrode for an electricity storage device by filling an active material in a pore portion. . It is preferable that the current collector is not coated with the carbon material at a connection portion with an external terminal. As a result, the external terminal and the carbon material-covered metal porous body can be bonded together in a metal-to-metal state.
  • mechanical methods such as rivets and pressure welding, and welding such as resistance welding and ultrasonic welding are mainly used.
  • the electricity storage device using the electrode according to the embodiment of the present invention is not particularly limited, and examples thereof include a lithium ion secondary battery, a sodium ion secondary battery, an electric double layer capacitor, a lithium ion capacitor, a sodium ion capacitor, and a fuel cell. It is done. In the case of a fuel cell, it can be used as a gas diffusion layer. Other applications include filters.
  • Example 1 An aluminum porous body having a metal basis weight of 120 g / m 2 , a thickness of 1.0 mm, and a porosity of 95% was prepared as a base material. The purity of aluminum in the aluminum porous body was 99.9% by mass.
  • the aluminum porous body before coating with the carbon material is defined as an aluminum porous body ⁇ .
  • a carbon material dispersion 1 was prepared by mixing acetylene black, carboxymethylcellulose, and pure water at a weight ratio of 1: 1: 50. The solid content ratio was 4% by mass, and the ratio of carbon particles in the solid content was 50% by mass.
  • the carbon material dispersion 1 was applied from the top of the base material to apply the carbon material dispersion 1.
  • the vibration amplitude of the aluminum porous body was set to about 1 mm.
  • the carbon material dispersion 1 was turned to confirm that the exposed portion of the aluminum porous body was not visible, and the carbon material dispersion 1 was not applied. From that time point, vibration was continuously applied to the aluminum porous body for 15 seconds.
  • a porous aluminum body was placed on another mesh and dried with a hot air dryer at 100 ° C. for 1 hour. As a result, a carbon material-coated porous metal body 1 having a carbon film made of the carbon material dispersion 1 on the surface of the skeleton was obtained.
  • the apparent density of the carbon material was 39.6 mg / cm 3 .
  • Example 2 In Example 1, the carbon material-coated metal porous body 2 was produced in the same manner as in Example 1 except that the application of the carbon material dispersion liquid 1 was stopped and the time during which vibration was continued was 1 minute. As a result, a carbon material-covered metal porous body 2 having an apparent density of the carbon material of 21.4 mg / cm 3 was obtained.
  • Example 3 In Example 1, the carbon material-coated metal porous body 3 was produced in the same manner as in Example 1 except that the application of the carbon material dispersion liquid 1 was stopped and then the vibration was continued for 2 minutes. Thus, the apparent density of the carbon material to obtain a carbon material coated metal porous body 3 of 6.7 mg / cm 3.
  • Example 4 The same porous aluminum body as in Example 1 was prepared.
  • the solid content ratio was 25% by mass, and the ratio of carbon particles in the solid content was 55% by mass.
  • the carbon material dispersion 2 was applied by rotating the carbon material dispersion 2 from above the base material while applying vibration of 10 Hz in the thickness direction of the aluminum porous body on the mesh.
  • the vibration amplitude of the aluminum porous body was set to about 1 mm. In this state, the carbon material dispersion liquid 2 was turned to confirm that the exposed portion of the aluminum porous body was not visible, and the carbon material dispersion liquid 2 was not applied.
  • Example 5 the carbon material-coated metal porous body 5 was produced in the same manner as in Example 4 except that the application of the carbon material dispersion 2 was stopped and the time for which vibration was continued was changed to 3 minutes. As a result, a carbon material-covered metal porous body 5 having an apparent density of 31.1 mg / cm 3 of the carbon material was obtained.
  • Example 6 the carbon material-covered metal porous body 6 was produced in the same manner as in Example 4 except that the time for which the carbon material dispersion liquid 2 was stopped and the time during which vibration was continued was changed to 5 minutes. As a result, a carbon material-covered metal porous body 6 having an apparent density of 8.3 mg / cm 3 of the carbon material was obtained.
  • Example 7 The same porous aluminum body as in Example 1 was prepared.
  • molten salt carbon plating bath a mixture obtained by mixing LiCl and KCl at a molar ratio of 6: 4 was maintained at 600 ° C. to obtain a molten salt, and 3 mol% of CaC 2 was added.
  • the aluminum porous body was immersed in the molten salt carbon plating bath so as to become an anode, and molten salt electroplating was performed using a carbon rod as a counter electrode, and the surface of the aluminum porous body was subjected to carbon plating.
  • the plating conditions were maintained for 5 minutes so that the potential of the porous aluminum body was 1.5 Vvs Li / Li + .
  • the aluminum porous body coated with the carbon material was taken out from the molten salt carbon plating bath, cooled, and washed with water to obtain a carbon material-coated metal porous body 7.
  • the apparent density of the carbon material in the carbon material-coated metal porous body 7 was 5.7 mg / cm 3 .
  • Example 8 The aluminum porous body was held in the molten salt carbon plating bath for 10 minutes in the same manner as in Example 7 to obtain a carbon material-coated porous metal body 8 with an apparent density of the carbon material of 11.6 mg / cm 3 .
  • Example 9 The aluminum porous body was held in the molten salt carbon plating bath for 60 minutes in the same manner as in Example 7 to obtain a carbon material-coated porous metal body 9 with an apparent density of the carbon material of 69.8 mg / cm 3 .
  • Example 10 The same porous aluminum body as in Example 1 was prepared.
  • a molten salt carbon plating bath a mixture of NaCl, KCl, and CaCl 2 in a molar ratio of 6: 1: 4 was used as a molten salt by maintaining at 600 ° C., and 3 mol% of CaC 2 was added.
  • the aluminum porous body was immersed in the molten salt carbon plating bath to form a cathode, and reverse electrolysis was performed using a carbon rod as a counter electrode to remove the oxide film on the surface of the aluminum porous body skeleton.
  • the reverse electrolysis conditions were such that the potential of the porous aluminum body was 0.4 Vvs Na / Na + and held for 30 seconds.
  • the porous aluminum body was made an anode in the molten salt carbon plating bath, and molten salt electroplating was performed using a carbon rod as a counter electrode, and the surface of the porous aluminum body was subjected to carbon plating.
  • the plating conditions were such that the potential of the porous aluminum body was 1.4 Vvs Na / Na + and held for 5 minutes.
  • the aluminum porous body coated with the carbon material was taken out from the molten salt carbon plating bath, cooled, and washed with water to obtain a carbon material-coated metal porous body 10.
  • the apparent density of the carbon material in the carbon material-coated metal porous body 10 was 6.1 mg / cm 3 .
  • Example 11 The porous aluminum body after reverse electrolysis was held in a molten salt carbon plating bath for 10 minutes in the same manner as in Example 10, and the carbon material-coated porous metal body 11 with an apparent density of the carbon material of 12.4 mg / cm 3 was obtained. Obtained.
  • Example 12 The porous aluminum body after reverse electrolysis was held in a molten salt carbon plating bath for 60 minutes in the same manner as in Example 10, and the carbon material-coated porous metal body 12 with an apparent density of the carbon material of 71.8 mg / cm 3 was obtained. Obtained.
  • Example 1 The same porous aluminum body as in Example 1 was prepared.
  • a carbon material dispersion A was prepared by dispersing a mixture of acetylene black and carboxymethylcellulose in a mass ratio of 1: 1 in water.
  • the aluminum porous body was immersed in the carbon material dispersion A for 1 minute, taken out, placed on a net, and blown from above to remove excess carbon material dispersion A. Thereafter, it was dried for 1 hour in a hot air dryer at 100 ° C. to obtain a carbon material-coated metal porous body A (aluminum porous body A) in which the surface of the skeleton was coated with a carbon film made of carbon material dispersion A.
  • the apparent density of the carbon material in the carbon material-coated metal porous body A was 114.0 mg / cm 3 .
  • a nickel porous body having a metal basis weight of 400 g / m 2 , a thickness of 1.2 mm, and a porosity of 95% was prepared as a base material.
  • the purity of nickel in the nickel porous body was 99.9% by mass.
  • a carbon material dispersion 3 was prepared by mixing acetylene black, carboxymethylcellulose, and pure water at a weight ratio of 1: 1: 50.
  • the solid content ratio was 4% by mass, and the ratio of carbon particles in the solid content was 50% by mass. While applying a vibration of 1 Hz in the thickness direction of the nickel porous body on the mesh, the carbon material dispersion 3 was rotated from the upper part of the base material to apply the carbon material dispersion 3.
  • the vibration amplitude of the nickel porous body was set to about 1 mm.
  • the carbon material dispersion 3 was rotated to confirm that the exposed portion of the nickel porous body was not visible, and application of the carbon material dispersion 3 was stopped. From that point, vibration was continuously applied to the nickel porous body for 15 seconds.
  • a nickel porous body was placed on another mesh and dried with a hot air dryer at 100 ° C. for 1 hour. As a result, a carbon material-coated metal porous body 13 having a carbon film made of the carbon material dispersion 3 on the surface of the skeleton was obtained.
  • the apparent density of the carbon material was 48.1 mg / cm 3 .
  • Example 14 In Example 13, the carbon material-coated metal porous body 14 was produced in the same manner as in Example 13 except that the application of the carbon material dispersion liquid 3 was stopped and the time during which vibration was continued was 1 minute. As a result, a carbon material-coated porous metal body 14 having an apparent density of the carbon material of 24.5 mg / cm 3 was obtained.
  • Example 15 In Example 13, the carbon material-covered metal porous body 15 was produced in the same manner as in Example 13 except that the period of time during which vibration was continued after the application of the carbon material dispersion 3 was stopped was 2 minutes. As a result, a carbon material-covered metal porous body 15 having an apparent density of the carbon material of 7.9 mg / cm 3 was obtained.
  • Example 16 The same nickel porous body as in Example 13 was prepared. A carbon material dispersion 4 in which acetylene black, PVDF, and NMP were mixed at a weight ratio of 16:13:88 was prepared. The solid content ratio was 25% by mass, and the ratio of carbon particles in the solid content was 55% by mass. While applying a vibration of 10 Hz in the thickness direction of the nickel porous body on the mesh, the carbon material dispersion 4 was rotated from the upper part of the substrate to apply the carbon material dispersion 4. The vibration amplitude of the nickel porous body was set to about 1 mm. In this state, the carbon material dispersion 4 was turned to confirm that the exposed portion of the nickel porous body was not visible, and the carbon material dispersion 4 was not applied.
  • Example 17 the carbon material-coated porous metal body 17 was produced in the same manner as in Example 16 except that the time for which the carbon material dispersion liquid 4 was stopped and the time during which vibration was continued was changed to 3 minutes. As a result, a carbon material-coated metal porous body 17 having an apparent density of 35.6 mg / cm 3 of the carbon material was obtained.
  • Example 18 In Example 16, the carbon material-coated metal porous body 18 was produced in the same manner as in Example 16 except that the period of time during which vibration was continued after the application of the carbon material dispersion 4 was stopped was 5 minutes. As a result, a carbon material-coated porous metal body 18 having an apparent density of 10.2 mg / cm 3 of the carbon material was obtained.
  • Example 19 The same nickel porous body as in Example 13 was prepared.
  • molten salt carbon plating bath a mixture prepared by mixing LiCl and KCl in a molar ratio of 6: 4 at 600 ° C. was used as a molten salt, and 3 mol% of CaC 2 was added.
  • the nickel porous body was immersed in the molten salt carbon plating bath so as to be an anode, and molten salt electroplating was performed using a carbon rod as a counter electrode, and the surface of the nickel porous body was subjected to carbon plating.
  • the plating conditions were such that the potential of the nickel porous body was 1.5 Vvs Li / Li + and held for 5 minutes.
  • the nickel porous body coated with the carbon material was taken out from the molten salt carbon plating bath, cooled and washed with water to obtain a carbon material-coated metal porous body 19.
  • the apparent density of the carbon material in the carbon material-coated porous metal body 19 was 6.9 mg / cm 3 .
  • Example 21 The nickel porous body was held in the molten salt carbon plating bath for 60 minutes in the same manner as in Example 19 to obtain a carbon material-coated porous metal body 21 with an apparent density of the carbon material of 84.9 mg / cm 3 .
  • Example 22 The same nickel porous body as in Example 13 was prepared.
  • a molten salt carbon plating bath a mixture of NaCl, KCl, and CaCl 2 in a molar ratio of 6: 1: 4 was used as a molten salt by maintaining at 600 ° C., and 3 mol% of CaC 2 was added.
  • the nickel porous body was immersed in the molten salt carbon plating bath to become a cathode, and reverse electrolysis was performed using a carbon rod as a counter electrode to remove the oxide film on the surface of the nickel porous body.
  • the reverse electrolysis conditions were such that the potential of the nickel porous body was 0.4 Vvs Na / Na + and held for 30 seconds.
  • the nickel porous body was made an anode in the molten salt carbon plating bath, and molten salt electroplating was performed using a carbon rod as a counter electrode, and the surface of the nickel porous body was subjected to carbon plating.
  • the plating conditions were such that the potential of the nickel porous body was 1.4 Vvs Na / Na + and held for 5 minutes.
  • the nickel porous body coated with the carbon material was taken out of the molten salt carbon plating bath, cooled, and washed with water to obtain a carbon material-coated metal porous body 22.
  • the apparent density of the carbon material in the carbon material-coated porous metal body 22 was 7.1 mg / cm 3 .
  • Example 23 In the same manner as in Example 22, the nickel porous body was held in the molten salt carbon plating bath for 10 minutes to obtain a carbon material-coated metal porous body 23 having an apparent density of the carbon material of 13.8 mg / cm 3 .
  • Example 24 The nickel porous body was held in the molten salt carbon plating bath for 60 minutes in the same manner as in Example 22 to obtain a carbon material-coated porous metal body 24 with an apparent density of the carbon material of 85.6 mg / cm 3 .
  • Example 2 The same nickel porous body as in Example 13 was prepared.
  • a carbon material-coated metal porous body B (nickel porous body B) was produced in the same manner as in Comparative Example 1 except that the nickel porous body was used instead of the aluminum porous body in Comparative Example 1.
  • the apparent density of the carbon material in the carbon material-coated metal porous body B was 131.0 mg / cm 3 .
  • LiCoO 2 powder as an active material, acetylene black as a conductive assistant, and PVDF as a binder were mixed at a mass ratio of 88: 6: 6, and NMP was added as a solvent to form a slurry. After the lead was attached to the carbon material-coated porous metal 1, 3, 4, 6, 7, 9, 10, 12 and the aluminum porous body ⁇ , the slurry was filled.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the composition ratio after drying and removing NMP was 92% by mass for activated carbon powder, 3% by mass for Ketjen Black, and 5% by mass for PVDF powder.
  • This activated carbon slurry was filled in each of the current collectors so that the activated carbon content was 30 mg / cm 2 .
  • the actual filling amount was 30 mg / cm 2 .
  • pressure was applied with a roller press having a diameter of 500 mm (slit: 300 ⁇ m) to obtain an electrode for each electric double layer capacitor.
  • the thickness of each electrode after pressurization was 470 ⁇ m.
  • Electrodes obtained above were punched into a diameter of 14 mm (2 sheets), and a cellulose fiber separator (thickness 60 ⁇ m, density 450 mg / cm 3 , porosity 70%) was sandwiched between the same electrodes. In this state, it was dried under reduced pressure at 180 ° C. for 12 hours. Thereafter, the electrode and the separator were impregnated with a propylene carbonate solution in which tetraethylammonium borofluoride was dissolved in a non-aqueous electrolyte so as to have a concentration of 1 mol / L using a stainless steel spacer in a coin cell case of R2032. Further, the case lid was tightened and sealed through an insulating gasket made of propylene to produce coin-shaped test electric double layer capacitors 1, 3, 4, 6, 7, 9, 10, 12, and ⁇ . The rated voltage was 2.5V.
  • each positive electrode current collector having a thickness of 0.72 mm prepared above so that the content of activated carbon was 30 mg / cm 2 .
  • the actual filling amount was 31 mg / cm 2 .
  • each positive electrode was obtained by pressing with a roller press machine (slit: 300 ⁇ m) having a diameter of 500 mm.
  • the thickness of each positive electrode after pressurization was 480 ⁇ m, and the capacity was 0.67 mAh / cm 2 .
  • a copper foil having a thickness of 20 ⁇ m was used as the negative electrode current collector.
  • 100 parts by mass of natural graphite powder capable of inserting and extracting lithium 2 parts by mass of ketjen black (KB) as a conductive additive, 4 parts by mass of PVDF powder as a binder, and 15 parts by mass of N-methylpyrrolidone (NMP) as a solvent
  • the graphite-based negative electrode slurry was prepared by adding and stirring with a mixer. This graphite-based negative electrode slurry was applied onto the above copper foil using a doctor blade (gap 400 ⁇ m). The actual coating amount was 10 mg / cm 2 . Next, after drying with a dryer at 100 ° C.
  • Each of the positive electrode and the negative electrode obtained above was cut into a size of 5 cm ⁇ 5 cm, a part of the active material was removed, and aluminum tab leads were welded to the positive electrode and nickel tab leads were welded to the negative electrode. These were transferred to a dry room and first dried at 140 ° C. for 12 hours in a reduced pressure environment.
  • a single-cell element was formed by facing a separator made of polypropylene between both electrodes and placed in a cell made of aluminum laminate. Further, a lithium electrode for a plate in which a lithium metal foil pressure-bonded to a nickel mesh was wrapped with the separator was also arranged in the cell so as not to contact the single cell element.
  • an electrolytic solution in which LiPF 6 having a concentration of 1 mol / L was dissolved and mixed with ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1 was injected to impregnate the electrodes and the separator. Finally, the aluminum laminate was sealed while reducing the pressure with a vacuum sealer to produce lithium ion capacitors 1, 3, 4, 6, 7, 9, 10, 12, and ⁇ .
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • rate characteristics were improved when a carbon material-coated metal porous body of 15 mg / cm 3 or less was used rather than an apparent density of the carbon material exceeding 60 mg / cm 3 . This is considered to be because when the carbon material coating amount is relatively large and the carbon film thickness is increased, the current collection distance is increased and the electrical resistance in the electrode is relatively increased. Furthermore, those using a carbon material-covered metal porous body in which an oxide film on the surface of the skeleton is removed by performing a reverse electrolysis treatment before carbon plating on the surface of the skeleton of the aluminum porous body is not subjected to the reverse electrolysis treatment. The rate characteristics were improved compared to the one. This is presumably because the adhesion between the aluminum porous body and the carbon film made of the carbon material is further improved by removing the oxide film.
  • the corrosion resistance was evaluated according to ASTM G5-94, which is a corrosion resistance evaluation standard for a current collector for a fuel cell (PEFC).
  • PEFC fuel cell
  • As the current collector carbon material-coated metal porous bodies of Examples 13 to 24 and Comparative Example 2 in which a carbon film was formed on a nickel porous body were used.
  • the potential scanning range was 0.1 V to 1.0 V vs SHE, and the pH of the test solution was adjusted to 4 using 10% sulfuric acid.
  • the sample was cut to a size of 5 mm ⁇ 5 mm and welded to the Pt line, and a Pt mesh was used as the counter electrode. The distance between the electrodes was set to 20 mm.
  • a silver / silver chloride electrode was used as the reference electrode.
  • the current value increased rapidly after 0 V, and the liquid turned green. It is thought that Ni was eluted.
  • the carbon material-coated metal porous body B (nickel porous body B) of Comparative Example 2 the absolute value of the current value was only about 10 mA / cm 2 , but the liquid was slightly discolored to green and it was thought that nickel had eluted. It is done.
  • the maximum value of the current was suppressed to 0.3 mA / cm 2 or less, no discoloration of the liquid was observed, and it was considered that the corrosion resistance was improved.

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Abstract

　La présente invention a pour objet de réaliser un corps poreux en métal revêtu de matériau carboné, etc., adéquat pour un collecteur capable d'améliorer les caractéristiques de capacité et de sortie d'un dispositif d'accumulation d'énergie. Un corps poreux en métal revêtu de matériau carboné selon l'invention est caractérisé en ce que la surface d'un squelette de corps poreux en métal présentant un trou de communication est recouverte d'un matériau carboné, le matériau carboné présentant une masse volumique apparente de 5 mg/cm3 à 100 mg/cm3.
PCT/JP2014/082776 2013-12-12 2014-12-11 Corps poreux en métal revêtu de matériau carboné, collecteur, électrode et dispositif d'accumulation d'énergie WO2015087948A1 (fr)

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CN109509877A (zh) * 2018-11-30 2019-03-22 清华大学深圳研究生院 碳包覆多孔金属涂层集流体、制备方法及锂电池
CN111101172A (zh) * 2019-12-31 2020-05-05 新疆烯金石墨烯科技有限公司 石墨烯铝复合材料及其制备方法
CN113564524A (zh) * 2021-07-13 2021-10-29 南京邮电大学 一种制备碳包覆三维多孔铜集流体的方法
JPWO2020262464A1 (ja) * 2019-06-24 2021-11-18 Ｔｐｒ株式会社 ハイブリッドキャパシタ

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CN109155395B (zh) * 2016-05-12 2023-01-06 艾利电力能源有限公司 非水电解质二次电池用正极和非水电解质二次电池
CN109509877A (zh) * 2018-11-30 2019-03-22 清华大学深圳研究生院 碳包覆多孔金属涂层集流体、制备方法及锂电池
JPWO2020262464A1 (ja) * 2019-06-24 2021-11-18 Ｔｐｒ株式会社 ハイブリッドキャパシタ
CN111101172A (zh) * 2019-12-31 2020-05-05 新疆烯金石墨烯科技有限公司 石墨烯铝复合材料及其制备方法
CN111101172B (zh) * 2019-12-31 2021-02-09 新疆烯金石墨烯科技有限公司 石墨烯铝复合材料及其制备方法
CN113564524A (zh) * 2021-07-13 2021-10-29 南京邮电大学 一种制备碳包覆三维多孔铜集流体的方法

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