WO2005069412A1 - Electrode en nanotubes de carbone ou en nanofibres de carbone comprenant des particules de soufre ou de metal utilisees en tant que liant et procede de fabrication correspondant - Google Patents

Electrode en nanotubes de carbone ou en nanofibres de carbone comprenant des particules de soufre ou de metal utilisees en tant que liant et procede de fabrication correspondant Download PDF

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WO2005069412A1
WO2005069412A1 PCT/KR2005/000064 KR2005000064W WO2005069412A1 WO 2005069412 A1 WO2005069412 A1 WO 2005069412A1 KR 2005000064 W KR2005000064 W KR 2005000064W WO 2005069412 A1 WO2005069412 A1 WO 2005069412A1
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carbon
electrode
sulfur
carbon nanotubes
metal
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PCT/KR2005/000064
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English (en)
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Young Nam Kim
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Kh Chemicals Co., Ltd.
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Priority to JP2006549121A priority Critical patent/JP2007527099A/ja
Priority to EP05721756A priority patent/EP1706911A4/fr
Publication of WO2005069412A1 publication Critical patent/WO2005069412A1/fr

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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896—Pressing, rolling, calendering
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
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    • H04M1/02—Constructional features of telephone sets
    • H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
    • H04M1/0206—Portable telephones comprising a plurality of mechanically joined movable body parts, e.g. hinged housings
    • H04M1/0208—Portable telephones comprising a plurality of mechanically joined movable body parts, e.g. hinged housings characterized by the relative motions of the body parts
    • H04M1/0214—Foldable telephones, i.e. with body parts pivoting to an open position around an axis parallel to the plane they define in closed position
    • H04M1/0216—Foldable in one direction, i.e. using a one degree of freedom hinge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/12—Supports; Mounting means
    • H01Q1/22—Supports; Mounting means by structural association with other equipment or articles
    • H01Q1/24—Supports; Mounting means by structural association with other equipment or articles with receiving set
    • H01Q1/241—Supports; Mounting means by structural association with other equipment or articles with receiving set used in mobile communications, e.g. GSM
    • H01Q1/242—Supports; Mounting means by structural association with other equipment or articles with receiving set used in mobile communications, e.g. GSM specially adapted for hand-held use
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/621—Binders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to carbon nanotube or carbon nanofiber electrodes comprising sulfur or metal nanoparticles as a binder and a process for preparing the same.
  • the present invention relates to carbon nanotube or carbon nanofiber electrodes in which the binding within the electrode material comprising carbon nanotubes or carbon nanofibers as well as between the electrode material and the current collector is achieved by using sulfur or metal nanoparticles as a binder and by heating and/or pressing the electrode system, and to a process for preparing the same.
  • This invention also relates to the use of the carbon nanotube or carbon nanofiber electrode in secondary batteries, supercapacitors or fuel cells.
  • electrochemical capacitors have a characteristic intermediate between electric capacitors and secondary batteries. They have not only a very short charging time but also a high power density, thus enabling to generate a high power. They also have a high energy density, and thus can discharge for a long time. Therefore, they are called supercapacitors or ultracapacitors (hereinafter, the electrochemical capacitors are referred to supercapacitors)
  • An electric double layer capacitor (EDLC) storing energy by means of an electric double layer is a type of supercapacitors and comprises electrodes to collect electricity, an electrolyte and a separating membrane.
  • the electrode constituting the most important part of the supercapacitor is required to have characteristics such as high electronic conductivity, large surface area, electrochemical inactivity, and ease of molding and processability. Therefore, highly porous carbonaceous materials are generally used as an electrode material due to their high electric conductivity (for example, the conductivities of copper, graphite and semiconductive germanium are 5.88 x 10 5 , 1.25 x 10 3 and 1.25 x 10 "2 S/cm, respectively), and good moldability and processability.
  • Porous carbonaceous materials include activated carbons, activated carbon fibers, amorphous carbons, carbon aerosols or carbon composites. Among these carbon materials, the most frequently used material at present is activated carbon- containing materials woven in a fibrous form.
  • activated carbons and activated carbon fibers have a large surface area of about 1000 to 3000 m 2 /g, most of the surface area resides in their micropores ( ⁇ 20 A) which do not contribute to the role as an electrode, and their effective pores occupy only from 20 to 30 % of the total surface area.
  • This feature of activated carbons and activated carbon fibers is a drawback for using them as an electrode material. Since the first synthesis of carbon nanotubes and carbon nanofibers in the early 1990's, there have been considerable attempts to use these carbon materials as an electrode material due to their superb characteristics.
  • Carbon nanofibers (GNF, Graphite Nano-Fiber) mentioned herein are similar to carbon nanotubes in shape and diameter, but mean carbon composites in a non-hollow, fibrous form having a diameter of up to a few hundred nanometers, whereas carbon nanotubes are in the form of a hollow tube as indicated in their name.
  • Activated carbon fibers can be prepared by spinning to result in a few micrometers in diameter and a few hundred meters in length, whereas carbon nanofibers which are catalytically synthesized like carbon nanotubes have a diameter of up to a few hundred nanometers and a length of up to a few tens of micrometers.
  • Carbon nanofibers can be formed using a method similar to the synthetic methods for carbon nanotubes.
  • carbon nanotubes or carbon nanofibers Compared to other carbon materials, carbon nanotubes or carbon nanofibers have a definite pore size distribution in the order of nanometers, a large surface area accessible by the ions of the electrolyte and a highly stable chemical structure.
  • carbon nanotubes or carbon nanofibers are used as an electrode material, the resistance of the fabricated electrode itself is very low.
  • carbon nanotubes or carbon nanofibers have an electric conductivity of up to l.OxlO 4 S/cm, the effective use rate of their specific surface area reaches almost 100 %, and the highest value of their specific surface area known to the present is about 500m 2 /g.
  • carbon nanotubes or carbon nanofibers provide the perfect conditions that an electrode is required of in fabricating supercapacitors of high energy and long lifetime. Moreover, it has been studied that carbon nanotubes having a herring bone structure exhibit superior electric properties because they comprise many exposed edges having higher capacitance than the basal plane of graphite.
  • supercapacitors comprising activated carbon materials are incapable of storing a large amount of energy although activated carbon materials have a large surface area as mentioned above. Moreover, the stored energy can be withdrawn only at low frequencies not greater than 100 mHz and by DC voltage because activated carbon materials have a broad pore size distribution. Such properties of activated carbon materials explain the reason why supercapacitors comprising activated carbons are not easily generalized in spite of current considerable efforts in improvement. Accordingly, the use of carbon nanotubes or carbon nanofibers as an electrode material makes it possible to fabricate supercapacitors capable of dealing with energy of high frequencies.
  • the internal resistance of an electrode itself is an important factor determining the power density of supercapacitors comprising carbon electrodes.
  • the internal resistance of a carbon electrode itself consists of (i) the contact resistance between the carbon particles forming the electrode, (ii) the resistance between the electrolyte and the electrode material, and (iii) the contact resistance between the electrode and the current collector.
  • the contact resistance between carbon particles and the contact resistance between the electrode and the current collector can be improved during the process for fabricating an electrode.
  • various types of electrodes and preparation methods therefor in order to improve the contact resistance between carbon particles forming the electrode.
  • the electrode material is a traditional carbonaceous material such as activated carbon or activated carbon fiber
  • the electrode material has been a practice to fabricate the electrode as a compressed type, a binder type, a matrix type, a monolith type, a cloth type or a film type.
  • the compressed type is prepared by pressing an electrode material of carbon particles under pressure, thus improving the contact between the carbon particles, and is mostly used together with other types of carbon materials.
  • the binder type is made using a binder such as PTFE (polytetrafluoroethylene), thus improving the contact characteristic between the carbon particles.
  • the matrix type is formed by mixing activated carbon particles with a polymer matrix and then carbonizing this mixture.
  • the binder itself in the binder type is incapable of acting as an electrode
  • the polymer in the matrix type can act as an electrode as well as can achieve the binding between carbon particles.
  • the monolith type comprises carbon aerosols, carbon foams, and the like. Because these materials are porous whole units and have continuous carbon backbones, the contact within the carbon electrode materials needs not be considered.
  • the film type involves non-porous carbon materials, and an electrolyte is not included within the electrode but is contained only in the separating membrane. Amorphous carbons can be used for the film type.
  • the cloth type which is made of activated carbon fibers, is the most widely used type in making a carbon electrode.
  • Tatarchuk et al disclose a method of binding between an electrode and a current collector in the form of metal fiber by heating up to the melting point of the metal fiber.
  • a process for binding between the metal fiber used in the current collector and carbon fibers used in the electrode is carried out as follows.
  • Stainless steel fibers of about 2 ⁇ m in diameter and the carbon fibers of 1 ⁇ 5 ⁇ m in diameter are mixed uniformly with cellulose of 5 mm in length and water with agitation and then filtered, thus resulting in a mixed fiber composite for an electrode. This fiber composite is pressed in a mold into a thin sheet.
  • the aluminum foil is bonded to the aluminum/carbon composite elecfrode by a diffusion bonding technique which is carried out at a temperature below 600 °C corresponding to the meting point of aluminum in order to avoid the formation of aluminum carbide resulting from a reaction between carbon and aluminum, which significantly reduces the performance of the electrode.
  • Zuckerbrod et al. in U.S. Pat. No. 4,448,856 discloses an electrode prepared by mixing powders of activated carbon and stainless steel with a binder. The density of the respective powders is limited to 25 ⁇ 450 ⁇ m, and these powders are coated onto a nickel wire or metal plate used as a current collector, thus fabricating the electrode.
  • the above-mentioned methods of fabricating activated carbon or activated carbon fiber electrodes represent various processes to reduce the resistance between the activated carbon electrode material and the current collector. It is possible to consider various methods of processing activated carbon into an electrode because activated carbon can be made into a fibrous form. However, it is impossible to make carbon nanotube or carbon nanofiber into a fibrous form, which imposes a limitation on fabricating a carbon nanotube or carbon nanofiber electrode.
  • the most generalized method is to fabricate a carbon nanotube or carbon nanofiber electrode in a disk shape by pressing a mixture of carbon nanotubes or carbon nanofibers with a binder. Niu et al.
  • Electrodes Journal of Power Sources, 84, pp.126-129 (1999)] prepared a carbon nanotube electrode using phenolic resin (PF) powder as a binder. Particularly, they suggested several processes for fabricating the carbon nanotube electrode as follows: a molded mixture of carbon nanotubes and PF powders (electrode (a)); the molded mixture was carbonized by heat-treatment (electrode (b)); electrode (b) was immersed in a hot mixture of concentrated sulfuric acid and nitric acid, then washed and dried (electrode (c)). From the result of comparative experiment, electrode (a) showed the highest internal resistance because the binder deteriorates the electrode performance. Thus, it is necessary to carry out a carbonization process.
  • PF phenolic resin
  • Electrodes prepared a carbon nanotube electrode via pressing a mixture of carbon nanotubes with poly(vinyldene chloride) (PNdC) as a binder, followed by carbonization.
  • PdC poly(vinyldene chloride)
  • they fabricated the electrodes using a plain Ni foil, a polished Ni foil and Ni foam as a current collector, respectively. From the ESR measurements for these electrodes, the ESRs for the polished Ni foil and the Ni foam were reduced to a half and a quarter of the ESR for the plain Ni, respectively.
  • the electrode prepared in this way has drawbacks such as that the carbon nanotubes are easily separated from the current collector because the binding force between them is weak; the elecfrode has a low density of carbon nanotubes compared to electrodes fabricated by pressing carbon nanotubes; and it is difficult to synthesize highly crystallized carbon nanotubes on the current collector.
  • a performance of a carbon nanotube electrode can be improved if the contact resistance between carbon nanotubes and a current collector is effectively reduced.
  • the use of organic binders can be considered as a generalized method for fabricating an electrode by processing carbon nanotubes using various methods.
  • the present invention provides a carbon nanotube or carbon nanofiber elecfrode which comprises a current collector, a binder such as sulfur or metal nanoparticles, and carbon nanotubes or carbon nanofibers as an electrode material, wherein the sulfur or metal nanoparticles are bonded, deposited, or fused on the surfaces of the carbon nanotubes or carbon nanofibers so that the carbon nanotubes or carbon nanofibers are bonded to each other and also bonded to the current collector.
  • electrodes made of carbon nanotubes or carbon nanofibers which can be used in secondary batteries, supercapacitors or fuel cells, can be prepared by a method in which the binding within the electrode material comprising carbon nanotubes or carbon nanofibers as well as between the electrode material and the current collector is achieved by using sulfur, metal or metal compound nanoparticles as a binder and by heating and/or pressing the electrode system so as to reduce the internal resistance of the electrode, impart strong durability to the electrode, minimize the contact resistance at the binding interfaces, and consequently lower ESR (Equivalent Series Resistance).
  • a carbon nanotube or carbon nanofiber electrode having strong durability, low contact resistance and very low ESR (Equivalent Series Resistance), in which the binding within the electrode material comprising carbon nanotubes or carbon nanofibers as well as between the electrode material and the current collector is achieved by using sulfur, metal or metal compound nanoparticles as a binder and by heating and/or pressing the elecfrode system.
  • ESR Equivalent Series Resistance
  • Figure 1 is a Ragon plot obtained in Test 1 using an elecfrode prepared by deposition of copper nanoparticles as a binder on carbon nanotubes followed by heat treatment according to the present invention.
  • the amount of the sulfur or metal nanoparticles used as the binder is in the range of from 0.01 to 3 times with respect to the amount by weight of the carbon nanotubes or carbon nanofibers.
  • the metal constituting the metal nanoparticles may be selected from the group consisting of alkali metals, alkaline earth metals, representative metals and transition metals, and the metal nanoparticles can also comprise a material selected from the group consisting of metal itself, metal sulfides, metal carbides, metal oxides and metal nitrides.
  • the binder When sulfur is used as the binder for the binding between the carbon nanotubes, it can be deposited on the surface of the carbon nanotubes by adding sulfur particles or by sulfurizing by various methods. In still another preferred embodiment of the present invention, the sulfur or metal nanoparticles have an average particle size of 1 ⁇ m or less.
  • the binder can comprise the sulfur or metal nanoparticles larger than 1 ⁇ m in size in the amount of 50 % or less, preferably 30 % or less, more preferably 10 % or less, even more preferably 5 % or less and still even more preferably 1 % or less with respect to the amount by weight of the carbon nanotubes or carbon nanofibers, without deteriorating the effects of the present invention.
  • the current collector for the carbon nanotube or carbon nanofiber electrode can comprise a metallic material as the main constituent and may have a shape that can be selected from a plate, a network and foam.
  • the sulfur or metal nanoparticles are chemically bonded, or physically deposited or fused on the carbon nanotubes or carbon nanofibers by pressing a mixture of the sulfur or metal nanoparticles with the carbon nanotubes or carbon nanofibers under a pressure of from 1 to 500 atm, preferably from 1 to 100 atm, or by heat-treating the mixture at a temperature which is in the range of the melting point (M.P.) of metals or metal compounds ⁇ 500 °C, preferably M.P.
  • M.P. melting point
  • a binder such as sulfur or metal nanoparticles or by depositing the sulfur or metal nanoparticles on the carbon nanotubes or carbon nanofibers
  • the above step (2) can be carried out by uniformly dispersing the electrode material on the current collector and then primarily pressing, or by simultaneously performing both dispersing and primarily pressing the electrode material under a pressure of from 1 to 500 atm.
  • the metal nanoparticles are pressed under a pressure of from 1 to 500 atm or by heat- treating at a temperature which is in the range of the melting point of the used metals or metal compounds ⁇ 50 ⁇ 500 °C in an inert gas atmosphere.
  • sulfur can be added into the carbon nanotubes or carbon nanofibers using a method similar to the rubber vulcanization process, thereby binding between the carbon nanotubes or carbon nanofibers.
  • mixing or applying the carbon nanotubes or carbon nanofibers with the sulfur or metal nanoparticles can be performed by a method chosen from the group consisting of physical mixing, microwave-mixing, solvent-mixing, and uniformly dispersing the sulfur or metal nanoparticles on the surfaces of the carbon nanotubes or carbon nanofibers.
  • the above-mentioned method of uniformly dispersing the sulfur or metal nanoparticles on the surfaces of the carbon nanotubes or carbon nanofibers can be carried out using a method selected from the group consisting of the impregnation method for catalysts followed by optional oxidation or reduction, precipitation, chemical vapor deposition (CND), electrodeposition, plasma spraying and sputtering.
  • this metal compound when nanoparticles formed of a metal compound are deposited on the surface of carbon nanotubes or carbon nanofibers, this metal compound can be partially or completely transformed into metal, metal sulfide, metal carbide or metal nitride before and after the primary pressing, or before and after the secondary pressing/heat-treatment.
  • the conductivity of the nanoparticles is increased and their processability is also enhanced due to ductility and malleability of metal, thereby increasing the effect of the metal nanoparticles as a binder.
  • metal compounds are reduced only if it is necessary because metals such as Li can have an increased reactivity in some cases.
  • Such transformation of metal compounds can be carried out using a conventional method used in the pertinent art, for example, reduction in the hydrogen gas, presulfiding using H 2 S, etc.
  • the primary pressing is carried out under a pressure with which the carbon nanotubes or carbon nanofibers can be made into the shape of a disk or thin film.
  • the pressure is generally in the range of from 1 to 100 atm.
  • the pressing and the heat-treatment in step (3) can be carried out simultaneously or consecutively.
  • the heat- treatment in step (3) can be performed using a heating method chosen from the group consisting of thermal heating, chemical vapor deposition, plasma heating, RF (radio frequency) heating, and microwave heating.
  • the present invention further provides electric double layer capacitors, secondary batteries or fuel cells comprising the carbon nanotube or carbon nanofiber electrode according to the embodiments described above.
  • the current collector comprises a metal plate, a metal network, or metal foam
  • the electrode material comprises carbon- containing materials, particularly carbon nanotubes or carbon nanofibers.
  • the carbon nanotubes or carbon nanofibers have a superior characteristic as an electrode material, but there still are problems to be solved for actually preparing the carbon nanotube or carbon nanofiber electrodes of high efficiency.
  • For activated carbon it is not difficult to be applied as an electrode material because activated carbon can be made into fibers.
  • activated carbon is woven into a fibrous form together with metal fibers, the problem in binding to a current collector can be solved to an extent.
  • carbon nanotubes which have a diameter of only a few hundred nanometers with a length of only from a few to tens of micrometers, are substantially impossible to be woven into a fibrous form. Accordingly, in order to fabricate an electrode, it is required to bind carbon nanotubes or carbon nanofibers to each other as well as to the current collector.
  • the aforementioned elecfrode of carbon nanotubes or carbon nanofibers has the following advantages as compared to the traditional elecfrode using an organic or carbonaceous binder.
  • sulfur or metal nanoparticles are used as the binder for the binding between the carbon nanotubes or carbon nanofibers, there is almost no internal resistance due to these binders, which is different from an organic or carbonaceous binder.
  • the sulfur or metal nanoparticles as a binder are physically mixed with the carbon nanotubes or carbon nanofibers or deposited on their surfaces, followed by heat-treatment, thereby achieving the binding between carbon nanotubes or carbon nanofibers without deteriorating the inherent advantages of the carbon nanotubes or carbon nanofibers, which is different from traditionally used binders resulting in such a deterioration by covering the whole surfaces of carbon nanotubes or carbon nanofibers.
  • the binding using the sulfur or metal nanoparticles as a binder is highly advantageous when these binders are chosen from sulfur or metals that are resistant to the corrosion by the electrolyte.
  • organic binders are susceptible to undergo a reaction with a corrosive electrolyte or to be dissolved into the electrolyte, but the sulfur or metal nanoparticles as a binder are not. Accordingly, the above advantages make it possible to effectively utilize a carbon nanotube or carbon nanofiber electrode in the present invention as the cathode in a secondary battery.
  • a secondary battery When a secondary battery is used for a long time, its life time or performance is decreased, which is mainly ascribed to the formation of solid materials precipitated at the time of charging which cause an internal short- circuit or a decrease in the accessible surface area by clogging an internal surface of an electrode.
  • cathode clogging This problem is referred to "cathode clogging" which can be solved by using a carbon nanotube or carbon nanofiber electrode having no micropores and constituted by a structure leading to easy mass transfer.
  • carbon nanotube or carbon nanofiber electrodes prepared according to the method in the present invention which have very low internal resistance and excellent durability, can exhibit superior performance as the cathode for a secondary battery.
  • a carbon nanotube or carbon nanofiber elecfrode according to the present invention has very low internal resistance and a favorable structure for reaction gas diffusion, thereby exhibiting superior performance as an electrode for a fuel cell as compared to traditional carbon electrodes.
  • nanoparticles of sulfur, metals or metal compounds are used as a binder with a sulfurizing process or with a pressing process at a temperature of the melting point of the metal nanoparticles or higher so that the carbon nanotubes are stably bonded to each other. Because the carbon nanotubes are bonded to each other using stable metal of substantially no resistance, the resulting carbon nanotube electrode has greatly improved internal resistance and excellent durability than an electrode fabricated using organic or carbonaceous binders. Furthermore, in the present invention, a current collector and an electrode material is not physically bonded but bonded using energy to induce a direct bonding between the current collector and the elecfrode material, thereby minimizing the ESR of an elecfrode and providing a highly-efficient electrode.
  • the present invention also provides a process for preparing a carbon nanotube or carbon nanofiber electrode having low internal resistance and specifically, the process comprises the steps of mixing sulfur or metal nanoparticles as a binder with the carbon nanotubes or carbon nanofibers or depositing the binder on the surfaces of the carbon nanotubes or carbon nanofibers using various deposition methods, and then pressing and /or heat-treating.
  • the above-mentioned pressing and heat-treatment can be carried out consecutively or simultaneously. Specifically, the mixture of the carbon nanotubes or carbon nanofibers with the nanoparticle binder can be pressed and then heat- treated, or the mixture can be heat-treated simultaneously with pressing.
  • a carbon nanotube or carbon nanofiber elecfrode can be fabricated by uniformly dispersing the carbon nanotubes or carbon nanofibers deposited or mixed with the sulfur or metal nanoparticles on the current collector followed by pressing simultaneously with heat-treating.
  • a method of mixing them is not specifically limited.
  • the term "metal” indicates, without being particularly limited literally, any material having electrical conductivity.
  • it means any of the elements excluding nonmetals (in the Periodic Table, the elements of Group NIII, F, Cl, Br and I of Group Nil, O of Group NI, ⁇ of Group V, and H of Group I) and semimetals (B of Group IIIB, C, Si and Ge of Group IN and Se, Te and Po of Group V).
  • metal in the present invention includes, with no particular limitation, representative metals such as alkali metal and alkaline earth metal, transition metals, and any other metals having electrical conductivity and ability to bind carbon nanotubes or carbon nanofibers to each other by being mixed with the carbon nanotubes or carbon nanofibers or by being deposited on these carbon nanomaterials followed by pressing and heat-treating.
  • metal nanoparticles can comprise not only metal itself but also other metal compounds such as metal oxides, metal sulfides, metal nitride, metal carbides and the like. Accordingly, in the embodiments of the invention, the term “metal nanoparticles" includes not only metal nanoparticles but also nanoparticles of metal compounds.
  • nanoparticles means particles constituting the corresponding substance having an average diameter of 1 ⁇ m or less, preferably from 10 to 500 nm, and more preferably from 10 to 100 nm.
  • the particle size distribution of the metal nanoparticles is such that 50% or more, preferably 70% or more, more preferably 90% or more of the particles having a diameter of 1 ⁇ m or less.
  • nanoparticles also means that the size distribution of the particles constituting the corresponding material includes particles of nanometer scale in size and may substantially include particles having an average diameter of from a few to tens of micrometers if they could provide microscopic binding between carbon nanotubes or carbon nanofibers as an electrode material.
  • the methods for preparing the nanoparticles used as a binder comprise, without particular limitation, any conventional method that can provide nanoparticles, such as mechanical grinding, co-precipitation, spraying, the sol-gel method, electrolysis, the emulsion method, the reversed-phase emulsion method, or the like.
  • the methods for depositing nanoparticles on the surface of the carbon nanotubes or carbon nanofibers comprise, without particular limitation, any method that can deposit the nanoparticles as a binder on these carbon nanomaterials, such as impregnation which is generally used for catalyst deposition, precipitation, the sol-gel method, the CND method which is generally used for metal deposition on a substrate, sputtering, evaporation method, or the like.
  • a process for pressing an electrode material comprising a mixture of carbon nanotubes or carbon nanofibers with sulfur or metal nanoparticles can be performed using traditionally used processes, and this mixture as an electrode material can be first pressed under a pressure of any value, for example, a pressure of from 1 to 500 atm, thus fabricating the elecfrode material into any desired shape, for example, into a disk shape.
  • prepared electrode material is then pressed under a pressure of from 1 to 500 atm and/or heat-treated at a temperature where the nanoparticles of sulfur, metal or metal compounds can be made into a melted or similar state, and thus the sulfur or metal nanoparticles deposited on the carbon nanotubes or carbon nanofibers achieve three-dimensional junction or fusion between these carbon nanomaterials and also smooth binding between the electrode material and a current collector.
  • the methods for heat-treating the sulfur or metal nanoparticles deposited on the carbon nanotubes or carbon nanofibers may include, without particular limitation, any heating method that can heat sulfur, metal elements or metal compounds, such as thermal heating, the CND method, plasma heating, radio-frequency heating, or microwave heating.
  • the temperature and time of the above-mentioned heat-treatment are varied with the kind of metal used as a binder, and they are not limited specifically as long as the conditions of the heat-treatment can achieve the junction or fusion between the carbon nanotubes or carbon nanofibers via, for example, physical and/or chemical changes such as melting or softening.
  • the treatment temperature is particularly in the range of the melting point of the sulfur or metal nanoparticles ⁇ 500 °C, preferably the melting point of the sulfur or metal nanoparticles ⁇ 200 °C, more preferably the melting point of the sulfur or metal nanoparticles ⁇ 100 °C, still more preferably the melting point of the sulfur or metal nanoparticles ⁇ 50 °C.
  • the treatment temperature can be controlled according to the pressure for the pressing, and this temperature, for example, may be lowered as the pressure increases. Furthermore, through the heat-treatment, the surface of a current collector can be melted or made into a similar state, thus binding the current collector to an elecfrode.
  • This example represents the preparation of a carbon nanotube or carbon nanofiber elecfrode using Cu nanoparticles as a binder, wherein the Cu nanoparticles are prepared by depositing copper compound nanoparticles on the carbon nanotubes and then reducing these nanoparticles.
  • the carbon nanotubes (CNTs) used as the elecfrode material is single wall nanotubes (SWCNTs) (KH Chemicals Co., Ltd.) having an average diameter of 1 nm and a surface area of 210 m 2 /g which is synthesized by catalytic evaporation.
  • a copper compound, Cu(NO 3 ) 2 was deposited on the carbon nanotubes in a weight ratio of 8 : 2 (CNT : Cu) using an impregnation method.
  • the carbon nanotubes deposited with copper compound nanoparticle were dried at 110 °C for 1 day, and then reduced in a hydrogen atmosphere at 400 °C for 2 h.
  • the as-prepared Cu nanoparticle deposited-carbon nanotubes were made into a disc shape by pressing at a pressure of 10 atm
  • the disc of the Cu nanoparticle-deposited carbon nanotubes was placed on a Ni foil as a current collector having a thickness of 75 ⁇ m, and then was maintained at 900 °C for 10 min while pressed under a pressure of 10 atm in a nitrogen atmosphere.
  • the electrode thus prepared in this example had a thickness of 150 ⁇ 300 ⁇ m.
  • EXAMPLE 2 The powder of the Cu nanoparticle-deposited carbon nanotubes prepared as in Example 1 was dispersed on a Ni foil as a current collector and then was maintained at 1100 °C while pressed in a nitrogen atmosphere, thus yielding an electrode. The exerted pressure was 10 atm and the pressing time was 5 min.
  • EXAMPLE 3 This example represents the preparation of a carbon nanotube electrode using Cu nanoparticles as a binder, wherein the Cu nanoparticles are prepared by the reverse-phase emulsion method.
  • the Cu nanoparticle-deposited carbon nanotubes disc prepared above was placed on a Ni foil as a current collector having a thickness of 75 ⁇ m and then maintained at 1000 °C for 10 min while pressed under a pressure of 20 atm in a nitrogen atmosphere, thus yielding an electrode.
  • EXAMPLE 4 This example represents the preparation of a carbon nanotube electrode using Co nanoparticles as a binder that is prepared by depositing a cobalt compound on the carbon nanotubes and then reducing these nanoparticles.
  • a cobalt compound, Co(NO 3 ) 2 was deposited on the same SWCNTs (KH Chemicals Co., Ltd.) as used in Example 1 in a weight ratio of 8 : 2 (CNT : Co) by an impregnation method.
  • the cobalt compound nanoparticle-deposited carbon nanotubes were dried at 110 °C for 1 day and then reduced in a hydrogen atmosphere at 400 °C for 2 h.
  • the as-prepared, Co nanoparticle deposited-carbon nanotubes were made into a disc shape by pressing under a pressure of 10 atm
  • the Co nanoparticle deposited-carbon nanotube disc was placed on a Ni foil as a current collector having a thickness of 75 ⁇ m and then maintained at 1200 °C for 10 min while pressed under a pressure of 10 atm in a nitrogen atmosphere, thus yielding an electrode.
  • EXAMPLE 5 This example represents the preparation of a carbon nanotube electrode using CoS 2 nanoparticles as a binder that is prepared by depositing a cobalt compound on the carbon nanotubes followed by pre-sulfiding the cobalt compound nanoparticles by H 2 S.
  • a cobalt compound, Co(NO 3 ) 2 was deposited on the same SWCNTs (KH Chemicals Co., Ltd.) as used in Example 1 in a weight ratio of 8 : 2 (CNT : Co) by the impregnation method.
  • the cobalt compound nanoparticle-deposited carbon nanotubes were dried at 110 °C for 1 day and then pre-sulfided by H 2 + H 2 S mixed gas at 400 °C for 2 h.
  • the as-prepared, CoS 2 nanoparticle deposited-carbon nanotubes were made into a disc shape by pressing under a pressure of 10 atm
  • the Co nanoparticle deposited-carbon nanotube disc was placed on a Ni foil as a current collector having a thickness of 75 ⁇ m and then maintained at 700 °C for 10 min while pressed under a pressure of 10 atm in a nifrogen atmosphere, thus yielding an electrode.
  • EXAMPLE 6 This example represents the preparation of a carbon nanotube elecfrode using Cu nanoparticles as a binder deposited on carbon nanotubes by sputtering.
  • Example 2 The same SWCNTs (KH Chemicals Co., Ltd.) as used in Example 1 were made into a disc shape having a thickness of from 100 to 300 ⁇ m by pressing under a pressure of 5 atm.
  • the as-prepared carbon nanotube disc was placed into a sputter (a thin-film maker) and the sputter was then evacuated to a vacuum of about 10 "6 Torr. Then, the pressure in the sputter was controlled to about 2 x 10 "2 Torr by flowing the Ar gas.
  • the Ar plasma was formed by exerting DC voltage and then a metallic copper target was sputtered for 5 min. After the copper was sputter-deposited on the carbon nanotubes disc, the disc was removed from the sputter and then grounded into powder.
  • the obtained powder was mixed uniformly and pressed again under a pressure of 5 atm into a disc shape.
  • the as-prepared disc was placed into the sputter again, and the copper was sputtered as described above.
  • a cycle of sputtering-grinding-pressing was repeated 20 times to result in a powder of Cu nanoparticle-deposited carbon nanotubes, and finally the powder was pressed into a disc under a pressure of 10 atm.
  • the Cu particle-deposited carbon nanotube disc prepared above was placed on a Ni foil as a current collector having a thickness of 75 ⁇ m and then maintained at 1000 °C for 10 min while pressed under a pressure of 10 atm in a nitrogen atmosphere, thus yielding an elecfrode.
  • EXAMPLE 7 This is an example of preparing a carbon nanotube electrode for a fuel cell by depositing Pt on the carbon nanotubes disc prepared in Example 1.
  • the disc of carbon nanotubes prepared in Example 1 was impregnated with a H 2 PtCl 6 aqueous solution and then the disc was dried at 110 °C.
  • the disc was reduced by flowing a hydrogen gas at 400 °C for 2 h, thus resulting in a carbon nanotube elecfrode for a fuel cell.
  • EXAMPLE 8 This is an example of preparing a carbon nanotube electrode for a fuel cell using Pt nanoparticles as a binder, in which nanoparticles of platinum compound were deposited on carbon nanotubes and then reduced.
  • EXAMPLE 9 This example represents the preparation of a carbon nanotube electrode using atomic sulfur as a binder.
  • the carbon nanotubes as used in Example 1 were mixed with atomic sulfur in a weight ratio of 95 : 5 (CNT : S).
  • CNT carbon nanotube
  • S sulfur
  • a process such as this is called vulcanization.
  • the above- prepared material of the carbon nanotubes physically mixed with sulfur was pressed under 10 atm and then subjected to vulcanization at 200 °C for 30 min, thus yielding an electrode. Test of Elecfrode Performance Performance tests of all the above-prepared electrodes were carried out as described below. A 7 M KOH aqueous solution was used as the electrolyte for the electrodes.
  • the above-prepared elecfrodes were each fabricated to have a diameter of 1.5 cm.
  • the separator for the electrodes was a polymer separating membrane (Celgard Inc.).
  • the gap between two electrodes was maintained at 300 ⁇ m.
  • the resistivity of the electrodes was measured by the Nan der Pauw method.
  • TEST 1 The resistivity of the electrode prepared in Example 1 was measured to be 9.1 m ⁇ -cm using the Nan der Pauw method.
  • the equivalent series resistance (ESR) of the unit cell was obtained to be 35 m ⁇ by extrapolation from a complex plane impedance plot.
  • the capacitance was measured to be 175 F/g in a manner of supplying a constant current with DC voltage. After charging to 1 N, the energy density and power density were measured with varying the current from 1 to 50 mA.
  • the power density was 15 kW/kg and the energy density 5.8 Wh/kg, as calculated by weight of the whole electrode.
  • a Ragon plot of the electrode in the unit cell is shown in Figure 1.
  • TEST 2 The resistivity of the elecfrode prepared in Example 2 was measured to be
  • the resistivity of the electrode prepared in Example 4 was measured to be 15 m ⁇ -cm.
  • the ESR of the unit cell was obtained to be 91 m ⁇ by extrapolation from a complex plane impedance plot.
  • TEST 5 The resistivity of the electrode prepared in Example 5 was measured to be
  • the ESR of the unit cell was obtained to be 95 m ⁇ by extrapolation from a complex plane impedance plot.
  • the ESR of the unit cell was obtained to be 102 m ⁇ by exfrapolation from a complex plane impedance plot.
  • the capacitance of the electrode was measured to be 155 F/g in a manner of supplying a constant current with DC voltage. After charging to 1 V, the energy density and power density of the elecfrode were measured with varying the current from 1 to 50 mA. The power density was 12.5 kW/kg and the energy density 4 Wh/kg, as calculated by weight of the whole elecfrode.
  • an electrode prepared according to the present invention has internal resistance lower than the values of internal resistance reported previously, and this proves that the use of sulfur or metal nanoparticles as a binder is a better process for binding carbon nanotubes to each other as compared to traditional processes such as binding using organic binders or binding after surface treatments. Moreover, an electrode prepared according to the present invention has an electrostatic capacity of 175 F/g.

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Abstract

La présente invention concerne une électrode fabriquée à partir de nanotubes de carbone ou de nanofibres de carbone et un procédé de fabrication correspondant. L'électrode comprend un collecteur de courant, et des particules de soufre ou de métal utilisées en tant que liant, les nanotubes de carbone ou les nanofibres de carbone étant caractérisées en ce que les particules de soufre ou de métal sont liées, déposées ou fusionnées sur les surfaces de nanotubes de carbone ou des nanofibres de carbone, de manière à ce que les nanotubes ou les nanofibres de carbone soient liées entre elles et au collecteur de courant. L'électrode fabriquée selon cette invention présente une faible résistance interne, une bonne durabilité et une faible résistance série équivalente. De cette manière, l'électrode peut s'utiliser efficacement dans des batteries secondaires, des super-condensateurs ou des piles à combustible.
PCT/KR2005/000064 2004-01-14 2005-01-10 Electrode en nanotubes de carbone ou en nanofibres de carbone comprenant des particules de soufre ou de metal utilisees en tant que liant et procede de fabrication correspondant WO2005069412A1 (fr)

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EP05721756A EP1706911A4 (fr) 2004-01-14 2005-01-10 Electrode en nanotubes de carbone ou en nanofibres de carbone comprenant des particules de soufre ou de metal utilisees en tant que liant et procede de fabrication correspondant

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EP1706911A1 (fr) 2006-10-04
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