WO2024142939A1 - カーボンナノチューブ及びその精製方法、カーボンナノチューブ分散液、バインダー組成物、電極用組成物、並びに二次電池 - Google Patents

カーボンナノチューブ及びその精製方法、カーボンナノチューブ分散液、バインダー組成物、電極用組成物、並びに二次電池 Download PDF

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WO2024142939A1
WO2024142939A1 PCT/JP2023/044636 JP2023044636W WO2024142939A1 WO 2024142939 A1 WO2024142939 A1 WO 2024142939A1 JP 2023044636 W JP2023044636 W JP 2023044636W WO 2024142939 A1 WO2024142939 A1 WO 2024142939A1
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cnt
carbon nanotube
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dispersion
cnts
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French (fr)
Japanese (ja)
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悠貴 松下
友明 枡岡
優真 野々山
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Toyocolor Co Ltd
Artience Co Ltd
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Toyocolor Co Ltd
Artience Co Ltd
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Priority to EP23911720.3A priority Critical patent/EP4644317A1/en
Priority to CN202380078289.6A priority patent/CN120693302A/zh
Publication of WO2024142939A1 publication Critical patent/WO2024142939A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/17—Purification
    • 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
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/28—Solid content in solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/30—Purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter
    • 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

  • One embodiment of the present invention relates to carbon nanotubes and a purification method thereof, a carbon nanotube dispersion, a binder composition, an electrode composition, and a secondary battery.
  • An electrode film is included, A carbon nanotube dispersion liquid comprising the carbon nanotubes according to any one of ⁇ 1> to ⁇ 4> above, a dispersant, and a dispersion medium; A secondary battery obtained by using a binder composition containing the carbon nanotube dispersion and a binder, or a composition for an electrode containing the carbon nanotube dispersion and an electrode active material.
  • the maximum peak intensity in the range of 1560 to 1600 cm ⁇ 1 is G
  • the maximum peak intensity in the range of 1310 to 1350 cm ⁇ 1 is D.
  • the G/D ratio of the CNT is 0.5 to 3.0, more preferably 0.5 to 2.5, even more preferably 0.5 to 2.0, particularly preferably 0.5 to 1.5, and even more preferably 0.5 to 1.3. If the G/D ratio of the CNT exceeds the above range, the CNT becomes hard, so that the CNT is easily damaged during dispersion, and the contact resistance may increase. On the other hand, if the G/D ratio of the CNT falls below the above range, the conductivity of the CNT itself is likely to be low. As a result, if the G/D ratio of the CNT is within the above range, the rate characteristics and cycle characteristics of a secondary battery using an electrode film using a CNT dispersion liquid are improved.
  • the total cobalt content in the CNT is 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 2500 ppm or less, and even more preferably 1000 ppm or less.
  • the total iron content is preferably 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 2500 ppm or less, and even more preferably 1000 ppm or less.
  • the total content of metals contained in the CNT can be reduced by calcining the CNT and dissolving the exposed metals with acid, as in the CNT purification method described below.
  • the heat generation peak temperature can be increased, and CNT with improved safety can be obtained.
  • a secondary battery containing such CNT can exhibit good performance.
  • the BET specific surface area of the CNT of this embodiment is preferably 150 m 2 /g or more, more preferably 180 m 2 /g or more.
  • the BET specific surface area of the CNT is preferably 800 m 2 /g or less, more preferably 600 m 2 /g or less, and even more preferably 400 m 2 /g or less.
  • the BET specific surface area of the CNT can be calculated by the BET method using nitrogen adsorption measurement. There is often a correlation between the specific surface area of the CNT and the average outer diameter of the CNT, and the smaller the specific surface area, the larger the outer diameter of the CNT and the smaller the number of CNTs per mass.
  • the larger the specific surface area of the CNT the smaller the outer diameter of the CNT and the larger the number of CNTs per mass.
  • the specific surface area of the CNT is 150 m2 /g or more, the number of carbon nanotubes per mass can be secured and a conductive network can be efficiently formed, resulting in excellent rate characteristics and cycle characteristics of the battery.
  • the specific surface area of the CNT is 800 m2 /g or less, the CNT is well dispersed and a good conductive network can be formed in the electrode film.
  • the average outer diameter of the CNTs in this embodiment is preferably 3 nm or more, and more preferably 5 nm or more.
  • the average outer diameter of the CNTs is also preferably 15 nm or less, more preferably 13 nm or less, and even more preferably 11 nm or less.
  • the average outer diameter of the CNTs is 15 nm or less, the number of carbon nanotubes per mass can be ensured, and a conductive network can be formed efficiently.
  • the average outer diameter of the CNTs is 3 nm or more, the CNTs are well dispersed, and a good conductive network can be formed in the electrode film.
  • CNTs usually exist as aggregates. This shape may be, for example, a state in which a single CNT is intricately entangled (entangled). It may also be an aggregate of linear CNTs (bundle-like). A bundle-like CNT aggregate is easier to disentangle than an entangled CNT aggregate. Also, a bundle-like CNT aggregate has better dispersibility than an entangled CNT aggregate, and is therefore suitable for use as CNT.
  • the CNTs of this embodiment can be produced by, but are not limited to, laser ablation, arc discharge, thermal CVD, plasma CVD, and combustion.
  • CNTs can be produced by contacting a carbon source with a catalytic metal at 500 to 1000° C. in an atmosphere with an oxygen concentration of 1% by volume or less.
  • the carbon source may be at least one of a hydrocarbon and an alcohol.
  • carbon-containing raw gases that can be used include, but are not limited to, hydrocarbons such as methane, ethylene, propane, butane, and acetylene, carbon monoxide, and alcohols. From the standpoint of ease of use, it is preferable to use at least one of hydrocarbons and alcohols as the raw gas.
  • CNT Carbon Nanotubes
  • the raw material CNTs are heat-treated in an inert atmosphere, whereby the CNTs are sintered.
  • the inert atmosphere include a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, and a combination of these.
  • the heat treatment time may be appropriately set depending on the firing device and firing scale, but for example, 1 to 3 hours is preferable.
  • the above-mentioned heat treatment melts the metal contained in the CNT, and also removes the amorphous carbon on the CNT surface, exposing the metal on the CNT surface, facilitating contact between the metal and acid in the second step described below.
  • CNTs oxidize and burn at temperatures of 500°C or higher in the air, but the heat treatment in the first step is performed in an inert atmosphere and at a relatively low heat treatment temperature, so that the combustion of the CNT itself can be suppressed.
  • the CNTs are heat-treated in an inert atmosphere, oxidation of the CNT surface can be suppressed. It is also possible to shorten the heat treatment time, in which case the high crystallization of the CNTs can be further suppressed.
  • the CNT heat-treated in the first step is brought into contact with an acid.
  • an acid This allows the metal contained in the CNT to dissolve.
  • a strong acid to dissolve the metal contained in the CNT.
  • an acid dissociation constant (pKa) of 3 or less in an aqueous medium is more preferable.
  • the heat treatment is performed in an inert atmosphere to suppress the surface oxygen amount of the CNT, and it is preferable to use an acid with a relatively low oxidizing power.
  • an acid with low oxidizing power an acid with a standard electrode potential (E °) in an aqueous solution of 0.80 V vs.
  • E° refers to the potential versus the standard hydrogen electrode (SHE) at 25°C.
  • hot concentrated sulfuric acid fluoric acid
  • the CNTs that have been heat-treated in an inert atmosphere in the first step are brought into contact with an acid of low oxidizing power in the second step, which inhibits surface oxidation in the resulting CNTs and reduces the acidic groups on the surface, thereby further reducing the amount of oxygen on the surface of the resulting CNTs.
  • an acid of low oxidizing power in the second step which inhibits surface oxidation in the resulting CNTs and reduces the acidic groups on the surface, thereby further reducing the amount of oxygen on the surface of the resulting CNTs.
  • the heat-treated CNT may be brought into contact with an acid using either a gaseous acid or a liquid acid, but from the viewpoint of metal solubility, it is preferable to use a liquid acid.
  • a liquid acid For example, there is a method of bringing an aqueous acid solution into contact with the CNT.
  • the acid treatment conditions may be appropriately determined depending on the type of acid, the type of CNT, the type and amount of metal contained in the CNT, etc.
  • the acid treatment may be performed by heating.
  • the acid treatment temperature is preferably 80°C or less, and more preferably 50°C or less. If the acid treatment temperature is 80°C or less, a higher metal dissolving ability can be obtained.
  • each of the first step and the second step may be performed two or more times.
  • other processing steps may be performed on the CNT between the first step and the second step, as long as the crystallinity and degree of surface oxidation of the CNT treated in the first step can be maintained.
  • the first and second steps increase the temperature at which the CNTs begin to burn, resulting in CNTs capable of forming an electrode film with good electrical conductivity, allowing secondary batteries containing CNTs to exhibit good performance.
  • the CNT of this embodiment may be CNT that has been dry-pulverized in order to crush the particles and increase the dispersibility.
  • Dry pulverization refers to a process of pulverizing CNT without the intervention of a liquid substance.
  • the dry pulverization may be media pulverization, pulverization without media, or a combination of two or more dry pulverizations.
  • a pulverizer containing pulverization media such as beads or steel balls is used to pulverize particles by utilizing the pulverization force or destructive force caused by the collision between the pulverization media.
  • the dry pulverization device a known method such as a dry attritor, ball mill, vibration mill, or bead mill can be used, and the pulverization time can be set arbitrarily depending on the device or the pulverization state of the particles.
  • the CNT dispersion according to the present embodiment includes the above-mentioned CNT, a dispersant, and a dispersion medium.
  • the CNT dispersion in this specification does not include an electrode active material.
  • a method for producing a CNT dispersion including the above-mentioned CNT, a dispersant, and a dispersion medium can be provided.
  • the dispersant is not particularly limited as long as it can disperse and stabilize the CNTs, and for example, a surfactant or a resin-type dispersant can be used.
  • Surfactants are mainly classified into anionic, cationic, nonionic, and amphoteric.
  • a suitable type of dispersant can be used in a suitable amount.
  • resin-type dispersants include cellulose derivatives (cellulose acetate, cellulose acetate butyrate, cellulose butyrate, cyanoethyl cellulose, ethylhydroxyethyl cellulose, nitrocellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, etc.), polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, polyacrylonitrile polymers, etc.
  • cellulose derivatives cellulose acetate, cellulose acetate butyrate, cellulose butyrate, cyanoethyl cellulose, ethylhydroxyethyl cellulose, nitrocellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, etc.
  • methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, and polyacrylonitrile polymers are preferred.
  • the molecular weight of the resin-type dispersant is preferably 10,000 to 300,000, and more preferably 10,000 to 150,000.
  • an amine compound or an inorganic base As the amine compound, primary amines (primary amines), secondary amines (secondary amines), and tertiary amines (tertiary amines) are used, and ammonia and quaternary ammonium compounds are not included.
  • As the amine compound in addition to monoamines, amine compounds such as diamines, triamines, and tetramines having multiple amino groups in the molecule can be used.
  • the inorganic base include, but are not limited to, primary aliphatic amines such as methylamine, ethylamine, butylamine, and octylamine; secondary aliphatic amines such as dimethylamine, diethylamine, and dibutylamine; tertiary aliphatic amines such as trimethylamine, triethylamine, and dimethyloctylamine; amino acids such as alanine, methionine, proline, serine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid, and cysteine; alkanolamines such as dimethylaminoethanol, monoethanolamine, diethanolamine, methylethanolamine, and triethanolamine; and alicyclic nitrogen-containing heterocyclic compounds such as hexamethylenetetramine, morpholine, and piperidine.
  • primary aliphatic amines such as methylamine, ethy
  • inorganic bases include hydroxides of alkali metals, hydroxides of alkaline earth metals, carbonates of alkali metals, carbonates of alkaline earth metals, phosphates of alkali metals, and phosphates of alkaline earth metals.
  • the dispersion medium is not particularly limited as long as it is capable of dispersing CNTs, but is preferably composed of one or more of water and water-soluble organic solvents.
  • the water content in the dispersion medium is preferably 500 ppm or less, more preferably 300 ppm or less, and particularly preferably 100 ppm or less.
  • circulation dispersion the dispersion liquid that has passed through the dispersion device itself is returned to the tank that supplies the dispersion liquid, and dispersion is performed while circulating.
  • the longer the processing time the more the dispersion progresses, so it is sufficient to repeat the pass or circulation until the desired dispersion state is achieved, and the processing volume can be increased by changing the size of the tank or the processing time.
  • Pass dispersion is preferable in that it is easier to homogenize the dispersion state than circulation dispersion.
  • Circulation dispersion is preferable in that the work and manufacturing equipment are simpler than pass dispersion.
  • the disintegration of aggregated particles, the loosening, wetting, and stabilization of the conductive material proceed sequentially or simultaneously, and the final dispersion state differs depending on how the steps proceed. Therefore, it is preferable to control the dispersion state in each dispersion process by using various evaluation methods. For example, it can be controlled by the method described in the examples.
  • the solid content of the CNT dispersion liquid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, relative to 100% by mass of the CNT dispersion liquid. Furthermore, the solid content of the CNT dispersion liquid is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less, relative to 100% by mass of the CNT dispersion liquid.
  • the content of the dispersant in the CNT dispersion liquid is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to 100% by mass of CNT, from the viewpoint of CNT loading, dispersibility, and dispersion stability. Also, the content of the dispersant in the CNT dispersion liquid is preferably 300% by mass or less, more preferably 100% by mass or less, and even more preferably 50% by mass or less, relative to 100% by mass of CNT, from the viewpoint of electrical conductivity.
  • the CNT dispersion may contain particulate foreign metal matter and dissolved metal ions as metals.
  • the foreign metal matter is a metal present in the CNT dispersion in the form of particles, and specifically includes the metals contained in the CNTs described above.
  • the CNTs, dispersants, and other materials may contain foreign metal matter derived from their respective manufacturing processes, and foreign metal matter may also be mixed in during the manufacturing process of the CNT dispersion. If foreign metal matter exists inside the battery, the battery is more likely to short-circuit, so removing the foreign metal matter is very important from the viewpoint of safety. It is preferable to include a step of removing contaminants such as metallic foreign matter at any timing during the process of producing the CNT dispersion liquid (metallic foreign matter removal step). From the viewpoint of efficiency, the metallic foreign matter removal step is preferably performed during the dispersion step of the CNT dispersion liquid and/or at the end of the dispersion step. The metallic foreign matter removal step may be performed multiple times.
  • the magnetic flux density is preferably 5,000 Gauss or more, more preferably 10,000 Gauss or more when considering removing stainless steel, which has a low magnetic property, and most preferably 12,000 Gauss or more.
  • coarse metal particles may pass through the magnetic filter, so when arranging the magnetic filter in the production line, it is preferable to include a process of removing coarse foreign matter or metal particles using a filter such as a cartridge filter upstream of the magnetic filter.
  • the magnetic filter is effective even if it only filters once, it is more preferable that the magnetic filter is of a circulating type. By adopting a circulating type, the efficiency of removing metal particles is improved.
  • the weight average molecular weight of the binder is preferably 10,000 or more, more preferably 100,000 or more, and particularly preferably 200,000 or more.
  • the weight average molecular weight of the binder is preferably 2,000,000 or less, more preferably 1,500,000 or less, and particularly preferably 1,000,000 or less.
  • the weight average molecular weight is 10,000 or more, it is possible to suppress a decrease in the resistance and adhesion of the binder.
  • the weight average molecular weight is 2,000,000 or less, it is possible to improve the resistance and adhesion of the binder while suppressing a decrease in workability due to an increase in the viscosity of the binder itself, and to suppress significant aggregation of the dispersed particles.
  • the electrode composition according to this embodiment includes the above-mentioned CNT dispersion liquid and an electrode active material.
  • the electrode composition can be further mixed with a binder to produce a composite slurry.
  • a method for producing a binder composition including the above-mentioned CNT, a dispersant, a dispersion medium, and an electrode active material and a method for producing a binder composition including the above-mentioned CNT, a dispersant, a dispersion medium, an electrode active material, and a composite slurry can be provided.
  • transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , or TiO 2 ; composite oxide powders of lithium and transition metals such as lithium nickel oxide, lithium cobalt oxide, lithium manganate, or lithium manganate having a layered structure; or a lithium iron phosphate-based material that is a phosphoric acid compound having an olivine structure.
  • positive electrode active materials may be used alone or in combination.
  • the above inorganic compounds and organic compounds may also be used in a mixture.
  • the negative electrode active material is not particularly limited, but may be one capable of doping or intercalating lithium ions.
  • the BET specific surface area of the electrode active material is preferably from 0.1 to 10 m 2 /g, more preferably from 0.2 to 5 m 2 /g, and even more preferably from 0.3 to 3 m 2 /g.
  • the average particle size of the electrode active material is preferably 0.05 to 100 ⁇ m, and more preferably 0.1 to 50 ⁇ m.
  • the average particle size of the electrode active material in this specification is the average value of particle sizes measured by an electron microscope.
  • the electrode composition is preferably produced by mixing and homogenizing the CNT dispersion liquid and the electrode active material, and the binder may be dissolved in the CNT dispersion liquid beforehand.
  • the electrode active material may be added at any timing in the process of producing the CNT dispersion liquid.
  • the dispersing device used for carrying out the process of dispersing the electrode active material and the dispersing devices exemplified in the production of the CNT dispersion liquid may be used.
  • the content of the electrode active material contained in the composite slurry is preferably 20% by mass or more, more preferably 40% by mass or more, based on 100% by mass of the composite slurry.
  • the content of the electrode active material contained in the composite slurry is preferably 99% by mass or less, more preferably 97% by mass or less, based on 100% by mass of the composite slurry. If it is within the above range, it is suitable from the viewpoint of coatability or productivity, and from the viewpoint of uniformity of the electrode film.
  • the content of CNT contained in the composite slurry is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the electrode active material.
  • the content of CNT contained in the composite slurry is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on 100% by mass of the electrode active material.
  • the content of the binder contained in the composite slurry is preferably 0.3% by mass or more, more preferably 0.7% by mass or more, based on 100% by mass of the electrode active material.
  • the content of the binder contained in the composite slurry is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the electrode active material.
  • the secondary battery according to this embodiment includes the above-mentioned electrode film.
  • the electrode film can be used as an electrode of the secondary battery, and is preferably used as an electrode of a non-aqueous electrolyte secondary battery using an organic electrolyte.
  • the non-aqueous electrolyte secondary battery is a battery including a positive electrode, a negative electrode, and an electrolyte containing an organic electrolyte.
  • the electrode film can be used for either the positive electrode or the negative electrode, or for both.
  • an electrode film obtained by coating a current collector with a composition for an electrode containing a positive electrode active material and drying the same can be used as a positive electrode.
  • the volume resistivity of the electrode was evaluated by preparing a composite composition for the positive electrode using the prepared CNT dispersion liquid and the positive electrode active material, applying the composite composition for the positive electrode onto a PET (polyethylene terephthalate) foil, drying the composite coating film, measuring the surface resistivity of the composite layer, and converting it into a volume resistivity.
  • the CNT dispersion liquid used was prepared in the examples and comparative examples described below.
  • the surface resistivity ( ⁇ / ⁇ ) of the composite layer of the prepared composite coating film was measured using Mitsubishi Chemical Analytec's Loresta GP, MCP-T610. After the measurement, the thickness of the composite layer was multiplied to obtain the volume resistivity ( ⁇ cm) of the electrode. The thickness of the composite layer was determined by subtracting the film thickness of the PET foil from the average value measured at three points in the electrode using a film thickness meter (NIKON, DIGIMICRO MH-15M).
  • ⁇ 10B Multi-walled carbon nanotube (JEIO, JENOTUBE10B)
  • BT1001M Multi-walled carbon nanotubes (LG Chem, BT1001M)
  • 6A Multi-walled carbon nanotube (JEIO, JENOTUBE6A)

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PCT/JP2023/044636 2022-12-28 2023-12-13 カーボンナノチューブ及びその精製方法、カーボンナノチューブ分散液、バインダー組成物、電極用組成物、並びに二次電池 Ceased WO2024142939A1 (ja)

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EP23911720.3A EP4644317A1 (en) 2022-12-28 2023-12-13 Carbon nanotubes and method for purifying same, carbon nanotube dispersion, binder composition, electrode composition, and secondary cell
CN202380078289.6A CN120693302A (zh) 2022-12-28 2023-12-13 碳纳米管及其精制方法、碳纳米管分散液、粘合剂组合物、电极用组合物、以及二次电池

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