WO2013067280A1 - Film de carbone et son procédé de production - Google Patents

Film de carbone et son procédé de production Download PDF

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Publication number
WO2013067280A1
WO2013067280A1 PCT/US2012/063204 US2012063204W WO2013067280A1 WO 2013067280 A1 WO2013067280 A1 WO 2013067280A1 US 2012063204 W US2012063204 W US 2012063204W WO 2013067280 A1 WO2013067280 A1 WO 2013067280A1
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Prior art keywords
graphene
graphite plates
carbon film
sheets
substrate
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PCT/US2012/063204
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English (en)
Inventor
Pavel Khokhlov
Pavel Lazarev
Evgeny MOROZOV
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Carben Semicon Ltd
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Carben Semicon Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 generally to a carbon film and particularly to the carbon film serving as an electrode in electrochemical devices.
  • Carbon films are widely used as electrodes with high specific surface area.
  • a number of different carbon forms such as graphite, amorphous carbon, activated carbon powders, activated carbon fabrics, carbon nanotubes and carbon aerogels (see, Patrice Simon and Andrew Burke, “Nanostructured Carbons: Double-Layer Capacitance and More", The Electrochemical Society Interface ⁇ Spring 2008, pp. 38 - 43; A.G. Pandolfo , A.F. Hollenkamp, “Carbon properties and their role in supercapacitors", Journal of Power Sources 157 (2006) 11-27) can be used as active materials in electrodes of the electrochemical devices such as double layer supercapacitors and secondary batteries.
  • Activated carbon powders are mostly used as active materials in supercapacitors, and graphite as an anode in Li-ion batteries (lithium secondary batteries).
  • Activated carbons are derived from carbon-rich organic precursors by heat treatment in inert atmosphere (a carbonization process).
  • Activated carbon powders can be obtained from natural sources such as wood, pitch, and coke, or from synthetic precursors such as selected polymers.
  • the activation process leads to the development of a porous network in the bulk of the carbon particles; micropores ( ⁇ 2 nm), mesopores (between 2 and 50 nm), and macropores (larger than 50 nm size) are randomly created.
  • the pore size distribution in the most activated carbon materials is not optimal for application as electrodes in supercapacitors because of a poor pore size control in the activation process, and as the result of it the surface area of the carbon material cannot be fully exploited to maximize charge density.
  • Activated carbon fabrics can be directly used as an active material in supercapacitor electrodes. These materials are produced from polymeric fibers such as rayon and polyacrylonitrile. However, the material cost is high which restricts their use. Carbon nanotubes (CNTs) are produced by the catalytic decomposition of hydrocarbons. Depending on the synthesis parameters, single wall (SWCNTs) as well as multi-wall carbon nanotubes (MWCNTs) can be prepared, combining both fully accessible external surface area and very high electrical conductivity.
  • SWCNTs single wall
  • MWCNTs multi-wall carbon nanotubes
  • Carbon aerogels are prepared with the sol-gel techniques, for example by the poly- condensation reaction of resorcinol and formaldehyde. Pyrolysis treatment in an inert atmosphere leads to the formation of a porous carbon aerogel with a controlled and uniform mesoporous structure (pore size between 2 and 50 nm), and high electrical conductivity (several S/cm). Published specific gravimetric capacitance for organic and aqueous electrolytes is in the range of 50 and 100 F/ g which limits application of these materials due to a low energy density (see, Patrice Simon and Andrew Burke, "Nanostructured Carbons: Double-Layer Capacitance and More", The Electrochemical Society Interface ⁇ Spring 2008, pp. 38 - 43).
  • a lithium secondary batteries as the ones having high energy density are widely employed as power sources of devices such as a notebook-sized personal computer and a cellular phone.
  • the NASA Glenn Research Center is evaluating the use of carbon nanotubes as anode materials for thin-film lithium secondary batteries. Directed structured nanotubes and nanofibers offer a superior intercalation media for the lithium secondary batteries (see http://www.grc.nasa.gov/WWW/RT/RT2001/5000/54 lOhepp 1.html).
  • Graphite particles represent a stack of graphene sheets and typically have plate-like shape with a dimension along their crystallographic c- axis much shorter than dimensions in perpendicular directions.
  • the electroconductive substrate e.g. a copper foil
  • planes of graphene sheets are located in parallel to the substrate surface (c-axis perpendicular to the substrate) due to anisotropic structure of the particles.
  • This orientation is not preferable for lithium ions transport inside the electrode material because in this case lithium ion intercalation occurs in the direction perpendicular to the direction of a current flow.
  • Graphite coating with a preferred orientation of graphene sheets parallel to the current flow and perpendicular to the substrate seems to be a preferable way to improve performance of Li-ion batteries.
  • Orientation in magnetic field has been suggested to produce graphite coatings with graphene sheets oriented perpendicularly to the substrate. See for example research that shows that graphite crystals can be oriented in magnetic field, Sung, M., Hattori, K., & Asai, S. (2009), "Crystal alignment of graphite as a negative electrode material of the lithium-ion secondary batteries", Materials & Design, 30(2), 387-390.
  • the present invention is intended to improve intercalation of ions in the carbon film electrode and overcome the drawbacks of the prior art carbon films such as low power performance.
  • the present invention provides a carbon film comprising a substrate, and a layer of graphite plates, each of which comprises a columnar stack of planar conjugated sp 2 carbon-based graphene-like sheets.
  • the number of the graphene-like sheets in the columnar stack is in the range from 1 to 20,000.
  • the graphite plates are directed in such a manner that planes of graphene-like sheets are located predominantly vertically in relation to the substrate surface. Distance between the graphene-like sheets is in the range from 3.35 A to 3.9 A in the columnar stacks, where the number of the graphene-like sheets is greater than 1.
  • the graphite plates possess ion conduction anisotropy.
  • the present invention provides an electrode of an electrochemical device comprising the carbon film on a substrate.
  • the carbon film comprises a layer of graphite plates, each of which comprises a columnar stack of planar conjugated sp 2 carbon-based graphene-like sheets.
  • the number of the graphene-like sheets in the columnar stack is in the range from 1 to 20000.
  • the graphite plates are directed in such a manner that planes of graphene-like sheets are located predominantly vertically in relation to the substrate surface, and a distance between the graphene-like sheets is in the range from 3.35 A to 3.9 A in the columnar stacks where the number of the graphene-like sheets is greater than 1.
  • the graphite plates possess ion conduction anisotropy.
  • the present invention provides a method of producing a carbon film comprising the following steps.
  • Step (a) is preparation of a coating material which comprises graphite plates each of which comprises a columnar stack of planar conjugated sp 2 carbon-based graphene-like sheets. Number of the graphene-like sheets in the columnar stack is in the range from 1 to 20000.
  • Step (b) is application of the coating material onto a substrate and formation of a coating layer.
  • Step (c) is application of alignment action upon the coating layer.
  • Step (d) is formation of the solid layer of the graphite plates on the substrate.
  • the graphite plates are directed in such a manner that planes of graphene-like sheets are located predominantly vertically in relation to the substrate surface.
  • the graphite plates possess ion conduction anisotropy.
  • Figure 1 schematically shows a film on the substrate according to the present invention.
  • Figure 2 shows scanning electron microscopy (SEM) images of carbon films (500 urn scale): (a) GNP 10, no magnetic field; (b) GNP10, magnetic field; (c) GNF09, no magnetic field, (d) GNF09, magnetic field.
  • SEM scanning electron microscopy
  • Figure 3 shows a cross-sectional SEM image of oriented carbon film.
  • Figure 4 shows performance of ordered vs. disordered electrodes (2 um plates): D and C curves are discharge (lithiation) and charge (delithiation) respectively
  • Figure 5 shows performance of ordered vs. disordered electrodes (5 um plates): D and C curves are discharge (lithiation) and charge (delithiation) respectively
  • Figure 6 shows SEM image of the film made of graphene-like sheets on a porous substrate.
  • carbon-based graphene-like sheets refers to narrow one-atom-thick planar sheet of sp 2 carbon atoms that are packed in a honeycomb crystal lattice
  • the present invention provides the carbon film as disclosed hereinabove.
  • Figure 1 schematically shows the disclosed carbon film on a substrate 1 comprising a layer of graphite plates, each of which comprises a columnar stack 2 of planar conjugated sp 2 carbon-based graphene-like sheets 3.
  • the graphite plates are directed in such a manner that planes of graphene-like sheets are located predominantly vertically in relation to the substrate surface.
  • Distance between the graphene-like sheets (d) in the columnar stacks is in the range from 3.35 A to 3.9 A.
  • the graphite plates are anisometric and an aspect ratio of the graphite plates is greater than 5. In one embodiment of the carbon film, the graphite plates are anisometric and an aspect ratio of the graphite plates is greater than 10. In still another embodiment of the carbon film, the aspect ratio of the graphite plates is greater than 100. In one embodiment of the carbon film, at least one dimension of the graphene-like sheet is not less than 0.1 ⁇ . In another embodiment of the carbon film, at least one dimension of the graphene-like sheet is not less than 10 ⁇ . In still another embodiment of the carbon film, at least one dimension of the graphene-like sheet is not less than 100 ⁇ .
  • the film comprises additional particles of material characterized by a high specific capacity in relation to Li-ions, and content of the additional particles is less than 50 w.%.
  • the additional particles are anisometric with aspect ratio greater than 2.
  • the additional particles comprise titanium dioxide (T1O 2 ) and/or silicon (Si).
  • the substrate is made of electroconductive material.
  • the carbon film serves as an electrode in electrochemical devices.
  • the present invention provides the electrode of an electrochemical device as disclosed hereinabove.
  • the graphite plates are anisometric and an aspect ratio of the graphite plates is greater than 5.
  • the graphite plates are anisometric and an aspect ratio of the graphite plates is greater than 10.
  • the aspect ratio of the graphite plates is greater than 100.
  • At least one dimension of the graphene- like sheet is not less than 0.1 ⁇ . In another embodiment of the electrode, at least one dimension of the graphene-like sheet is not less than 10 ⁇ . In still another embodiment of the electrode, at least one dimension of the graphene-like sheet is not less than 100 ⁇ .
  • the carbon film further comprises additional particles of material characterized by a high specific capacity in relation to Li-ions, and content of the additional particles is less than 50 w.%.
  • the additional particles are anisometric with aspect ratio greater than 2.
  • the additional particles comprise titanium dioxide (T1O2) and/or silicon (Si).
  • the substrate is made of electroconductive material.
  • the present invention also provides the method of producing the carbon film as disclosed hereinabove.
  • the graphite plates are anisometric and an aspect ratio of the graphite plates is greater than 5. In another embodiment of the method, the graphite plates are anisometric and an aspect ratio of the graphite plates is greater than 10. In still another embodiment of the method, the aspect ratio of the graphite plates is greater than 100.
  • At least one dimension of the graphene- like sheet is not less than 0.1 ⁇ . In another embodiment of the method, at least one dimension of the graphene-like sheet is not less than 10 ⁇ . In still another embodiment of the method, at least one dimension of the graphene-like sheet is not less than 100 ⁇ .
  • the coating material comprises additional particles of material characterized by a high specific capacity in relation to Li-ions, and content of the additional particles is less than 50 w.%.
  • the additional particles are anisometric with aspect ratio greater than 2.
  • the additional particles comprise titanium dioxide (T1O 2 ) and/or silicon (Si).
  • the steps of the application of the coating material and application of alignment action are carried out simultaneously.
  • the steps of the formation of the solid layer and application of alignment action are carried out simultaneously.
  • the alignment action is selected from the list comprising action by an electric field, magnetic field, and any combination thereof.
  • the substrate is made of
  • the coating material is a dispersion which is prepared with dispersed graphite plates in a suitable solvent.
  • the method further comprises a pre-treatment of the dispersion for exfoliation of the graphite plates, wherein the treatment is selected from the list comprising treatment with ultrasound and mechanical treatment (shear milling), and wherein the treatment is carried out before the application of the coating material onto a substrate.
  • the suitable solvent is selected from the list comprising water, N-methyl-pyrrolidone (NMP) and dimethyl formamide (DMFA).
  • the formation step (d) comprises drying of the coating layer.
  • the coating material is a powder of crystalline graphite plates, comprising graphene-like sheets.
  • the formation step (d) is pressing (molding) of the coating layer.
  • the coating material further comprises a binding material selected from the list comprising enumerated polyanilines, polythiophenes, teflon. In the present invention, the binding material is used to bind crystalline graphite plates.
  • the method further comprises an additional step of coating a buffer layer on the substrate. The buffer layer is intended for decrease of an energy barrier between the substrate and the coating layer, wherein the additional step is carried out before the application step (a).
  • the method further comprises a pre-treatment step of coating a layer of adhesive on the substrate, wherein the pre-treatment step is carried out before the application step (a).
  • the formation step further comprises a drying step which is carried out after the pressing (molding).
  • the powder of crystalline graphite plates further comprises UV-polymerizable materials.
  • the method further comprises a step of UV-polymerization which is carried out after the formation step (d).
  • the example describes producing the carbon film and electrode on its base in accordance with the present invention.
  • Coating materials were prepared in the following composition, 2 wt%
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • Copper foil of 8-micron thickness was used as a substrate.
  • the foil was wiped with isopropyl alcohol and coated with the slurry.
  • the ordered carbon film were prepared with magnetic field by a blade coating with the applicator having a 100-um gap over the rare-earth magnet (14.8 kGauss).
  • the films deposited by the same method but without magnetic field were not specifically ordered and were prepared for comparison. Both coatings were dried on air at room temperature.
  • Comparative low resolution scanning electron microscopy (SEM) images (500 um scale) are presented in Figure 2, that shows images of the carbon films prepared with GNP 10 and GNF09 with and without applied magnetic field. Brighter image implies more particle edges exposed.
  • Oriented film cross-section SEM is presented in Figure 3. Films deposited under magnetic field have specific morphology, where graphite plates constituting the film are mainly vertical (with planes of graphene-like sheets located perpendicular to the substrate).
  • the example presents fabrication of a carbon film prepared with commercial graphite paste Asbury 592 A (2 um artificial graphite particles, aspect ratio 50, purity
  • the coating material is a paste prepared as a water suspension of graphite comprising 98% of graphite and 2% anti-sedimentation surfactants.
  • An aqueous suspension SBR was used as a binder with a 5% solid/solid ratio.
  • a 5-% carbon black was added to improve electric conductivity of the electrode.
  • Coating liquid was prepared by a thorough mixing of the components using Turrax homogenizer at 5000 rpm during 30 min. The resulting concentration of graphite in the coating liquid was 20%.
  • the ordered carbon film was prepared in a magnetic field by a blade coating with the applicator having 100 um gap over the rare-earth magnet (14.8 kGauss). After a complete drying on air at room temperature (for about 30 minutes) the coated foil was pulled on the glass plates and baked at 330°C for 30 minutes in nitrogen in order to eliminate surfactants out of the film.
  • Electrode testing was performed with the use of 8-channel battery analyzer (MTI) at currents of 0.2, 0.5, 1, 2, 5, 10 mA and 0.2 mA once again to estimate how much the electrodes have been affected. Cycling was done between 1 V and 10 mV. Testing protocol stipulated 15 minutes rest between charge-discharge cycles. Data in Figure 4 demonstrate difference between the ordered 4 and non-ordered 5 electrodes. The ordered graphitic plates show an improved performance of the electrode.
  • MMI battery analyzer
  • the coating materials were prepared in the following composition: 2 wt% CMC and 4 wt% SBR. Slurries were mixed using Turrax homogenizer at 8000 rpm during 40 minutes. The resulting carbon/water concentration was 50%. The prepared slurry was placed into a vacuum chamber for 1 minute for removal of bubbles.
  • a battery grade copper foil was used as an anode current collector. Deposition was done by a blade coating with the gap of 100 um. The coatings were dried on air. The ordered electrodes were deposited in magnetic field with use of a powerful rare-earth magnet (magnetization 14.8 kGauss). The dried electrodes were pressed using a hydraulic press (MTI). As a result of pressing thickness was reduced for 25%.
  • MMI hydraulic press
  • the foils were cut to prepare 10-mm round electrodes.
  • Celgard2500 separators were 16 mm in diameter. Batteries were assembled in CR2032 coin cells (MTI) in a nitrogen filled glovebox. Copper/graphite electrode was placed into the positive half-cell and covered with the separator. Then 200 uL of electrolyte was introduced with a pipette. A Li-disc was scratched in order to expose metallic Li, stuck to the steel washer and put onto the soaked ion separator. After a spring was placed the cell was sealed. Cells were kept in rest for 5 hrs, and then tested. Testing was performed using a
  • MTI battery analyzer at currents of 0.1, 0.2, 0.3, 0.5, 1, 3, 5, 10 mA and again at 0.1 mA. Specific parameters like capacity, power and current densities are reported with respect to the structured anode as a weight of cathode is much higher.
  • the example describes producing of a carbon film made of graphene-like platelets deposited onto a porous substrate.
  • a beaker with 7 g of natural flake graphite (-325 mesh) was filled up with 140 ml of N-methyl pyrrolidone (NMP) and mixed to form a suspension.
  • the suspension was treated with ultrasound in an ultrasonic bath (Branson 1510, 70 W, 42 kHz) with a simultaneous heating (-50 °C) for 2 hours. Then, about 120 ml of the suspension was collected with a pipette. The collected suspension was centrifuged at 3,000 rpm for 1 hour. Supernatant fraction was collected with a pipette (-100 ml) and filtered through polyamide membrane (0.45 ⁇ ).
  • NMP N-methyl pyrrolidone
  • the example describes dispersing of the chemically modified graphite plates, and application of the coating material onto a porous substrate by filtration.
  • Graphite was mixed with 4-aminobenzoic acid, polyphosphoric acid and phosphorus penta-oxide, and thick slurry was heated at 130 °C with mechanical stirring for 3 days. Then the resulted mixture was cooled to room temperature and quenched by adding water which produced a thick precipitate. The precipitate was collected by filtration, was thoroughly washed with water and then rinsed with methanol. The precipitate was then transferred to Soxhlet thimble and extracted with hot water (1 day) and methanol (1 day). It was then dried in vacuum at 81 °C for 1 more day to produce a final product.
  • edge functionalized graphite with 4-ethylbenzoate substituents were stirred in 60 ml of N-methyl pyrrolidone by a magnetic stirrer at 300 rpm at room temperature for 1 hour. Then the prepared dispersion was centrifuged at 3000 rpm for 1 hour. Dark brown supernatant liquid comprises dispersed particles of chemically modified graphite.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne d'une manière générale un film de carbone et en particulier un film de carbone servant d'électrode dans des dispositifs électrochimiques. La présente invention concerne un film de carbone composé d'un substrat et d'une couche de plaques en graphite, chaque plaque comprenant un empilement en colonne de feuilles planaires conjuguées à base de carbone sp² de type graphène. Le nombre de feuilles de type graphène de l'empilement en colonne est dans la plage de 1 à 20 000. Les plaques de graphite sont dirigées de telle manière que les plans des feuilles de type graphène sont principalement situés verticalement par rapport à la surface des substrats. La distance entre les feuilles de type graphène est dans la plage de 3,35 Å à 3,9 Å dans les empilements en colonne où le nombre de feuilles de type graphène est supérieur à 1. Les plaques de graphite possèdent une anisotropie de conduction ionique.
PCT/US2012/063204 2011-11-04 2012-11-02 Film de carbone et son procédé de production Ceased WO2013067280A1 (fr)

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Cited By (8)

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US9640333B2 (en) 2012-10-03 2017-05-02 Georgia Tech Research Corporation High surface area carbon materials and methods for making same
WO2018047054A1 (fr) * 2016-09-06 2018-03-15 Battrion Ag Procédé et dispositif pour appliquer des champs magnétiques sur un objet
JP2018190575A (ja) * 2017-05-01 2018-11-29 トヨタ自動車株式会社 非水系電池およびその製造方法
US11189824B2 (en) 2016-09-06 2021-11-30 Battrion Ag Method and apparatus for applying magnetic fields to an article
US11312631B2 (en) 2017-09-28 2022-04-26 Murata Manufacturing Co., Ltd. Aligned film and method for producing the same
CN115871285A (zh) * 2021-09-29 2023-03-31 斯马特高科技有限公司 层压石墨烯基导热膜和垫以及制造该膜和垫的方法
WO2024080618A1 (fr) * 2022-10-13 2024-04-18 주식회사 엘지에너지솔루션 Dispositif d'alignement magnétique pour anode, et procédé de fabrication d'anode l'utilisant
EP4246614A4 (fr) * 2020-11-13 2025-09-10 Zeon Corp Feuille de matériau d'électrode négative pour accumulateur non aqueux, son procédé de fabrication, électrode négative pour accumulateur non aqueux et accumulateur non aqueux

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US20110042649A1 (en) * 2008-02-15 2011-02-24 Carben Semicon Limited Thin-Film Transistor, Carbon-Based Layer and Method of Producing Thereof
US20110111303A1 (en) * 2009-11-06 2011-05-12 Northwestern University Electrode material comprising graphene composite materials in a graphite network formed from reconstituted graphene sheets
US20110254432A1 (en) * 2010-03-30 2011-10-20 Heinrich Zeininger Substrate for a field emitter, and method to produce the substrate

Patent Citations (3)

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US20110042649A1 (en) * 2008-02-15 2011-02-24 Carben Semicon Limited Thin-Film Transistor, Carbon-Based Layer and Method of Producing Thereof
US20110111303A1 (en) * 2009-11-06 2011-05-12 Northwestern University Electrode material comprising graphene composite materials in a graphite network formed from reconstituted graphene sheets
US20110254432A1 (en) * 2010-03-30 2011-10-20 Heinrich Zeininger Substrate for a field emitter, and method to produce the substrate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9640333B2 (en) 2012-10-03 2017-05-02 Georgia Tech Research Corporation High surface area carbon materials and methods for making same
WO2018047054A1 (fr) * 2016-09-06 2018-03-15 Battrion Ag Procédé et dispositif pour appliquer des champs magnétiques sur un objet
US11189824B2 (en) 2016-09-06 2021-11-30 Battrion Ag Method and apparatus for applying magnetic fields to an article
JP2018190575A (ja) * 2017-05-01 2018-11-29 トヨタ自動車株式会社 非水系電池およびその製造方法
US11312631B2 (en) 2017-09-28 2022-04-26 Murata Manufacturing Co., Ltd. Aligned film and method for producing the same
EP4246614A4 (fr) * 2020-11-13 2025-09-10 Zeon Corp Feuille de matériau d'électrode négative pour accumulateur non aqueux, son procédé de fabrication, électrode négative pour accumulateur non aqueux et accumulateur non aqueux
CN115871285A (zh) * 2021-09-29 2023-03-31 斯马特高科技有限公司 层压石墨烯基导热膜和垫以及制造该膜和垫的方法
WO2024080618A1 (fr) * 2022-10-13 2024-04-18 주식회사 엘지에너지솔루션 Dispositif d'alignement magnétique pour anode, et procédé de fabrication d'anode l'utilisant
US12322543B2 (en) 2022-10-13 2025-06-03 Lg Energy Solution, Ltd. Magnetic alignment device for anode, and anode manufacturing method using same

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