WO2022075387A1 - カーボンナノチューブ分散液およびその利用 - Google Patents

カーボンナノチューブ分散液およびその利用 Download PDF

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WO2022075387A1
WO2022075387A1 PCT/JP2021/037078 JP2021037078W WO2022075387A1 WO 2022075387 A1 WO2022075387 A1 WO 2022075387A1 JP 2021037078 W JP2021037078 W JP 2021037078W WO 2022075387 A1 WO2022075387 A1 WO 2022075387A1
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Prior art keywords
carbon nanotube
dispersion liquid
mass
carbon nanotubes
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English (en)
French (fr)
Japanese (ja)
Inventor
雄 森田
直人 岡
哲朗 泉谷
友明 枡岡
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Toyocolor Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyocolor Co Ltd
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Priority to EP21877686.2A priority Critical patent/EP4227368A4/en
Priority to CN202511744820.6A priority patent/CN121516855A/zh
Priority to US18/021,386 priority patent/US20230307653A1/en
Priority to KR1020237015460A priority patent/KR20230084248A/ko
Priority to CN202180058872.1A priority patent/CN116171307B/zh
Priority to CN202511744818.9A priority patent/CN121470477A/zh
Publication of WO2022075387A1 publication Critical patent/WO2022075387A1/ja
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Definitions

  • the present invention relates to a dispersion liquid of carbon nanotubes. More specifically, a carbon nanotube dispersion liquid, a resin composition containing a carbon nanotube dispersion liquid and a binder, a mixed material slurry containing a carbon nanotube dispersion liquid, a binder and an active material, and an electrode film formed by forming the mixture into a film shape. And related to non-aqueous electrolyte secondary batteries including electrode membranes and electrolytes.
  • non-aqueous electrolyte secondary batteries that use non-aqueous electrolytes, especially lithium-ion secondary batteries, have come to be used in many devices due to their characteristics of high energy density and high voltage.
  • the negative electrode material used for these lithium ion secondary batteries a carbon material typified by graphite having a low potential close to that of lithium (Li) and a large charge / discharge capacity per unit mass is used.
  • these electrode materials are used up to the point where the charge / discharge capacity per mass is close to the theoretical value, and the energy density per mass as a battery is approaching the limit. Therefore, in order to increase the utilization rate as an electrode, attempts are being made to reduce the amount of conductive auxiliary agents and binders that do not contribute to the discharge capacity.
  • carbon black, Ketjen black, fullerene, graphene, fine carbon material, etc. are used as the conductive auxiliary agent.
  • carbon nanotubes which are a type of fine carbon fiber, are often used.
  • adding carbon nanotubes to graphite or silicon negative electrodes improves electrode strength such as conductivity, adhesion and expansion / contraction of electrodes, rate characteristics and cycle characteristics of lithium ion secondary batteries.
  • Patent Document 1 For example, see Patent Document 1.
  • studies have been made to reduce the electrode resistance by adding carbon nanotubes to the positive electrode (see, for example, Patent Document 2 and Patent Document 3).
  • multi-walled carbon nanotubes having an outer diameter of 10 nm to several tens of nm are relatively inexpensive and are expected to be put into practical use.
  • Patent Document 5 the oxidized double-walled carbon nanotubes are dispersed in an aqueous solution of carboxymethyl cellulose using an ultrasonic homogenizer, but it is difficult to disperse the carbon nanotubes in a solvent at a high concentration.
  • Patent Document 6 the single-walled carbon nanotubes are dispersed in a polyvinylpyrrolidone-containing NMP solvent by using ultrasonic waves, but it is difficult to disperse the carbon nanotubes in the solvent at a high concentration.
  • Patent Document 7 proposes that the output characteristics of an electrode are improved by producing a multilayer carbon nanotube dispersion liquid having a specific complex elastic modulus.
  • the problem to be solved by the present invention is to provide a carbon nanotube dispersion liquid, a carbon nanotube resin composition and a mixed material slurry having high dispersibility and elastic modulus in order to obtain an electrode film having excellent electrode strength and conductivity. That is. More specifically, it is to provide a non-aqueous electrolyte secondary battery having excellent rate characteristics and cycle characteristics.
  • the present invention relates to a carbon nanotube dispersion liquid containing carbon nanotubes, a dispersant, and a solvent, which satisfies the following (1) to (4).
  • the maximum peak intensity in the range of 1560 to 1600 cm -1 is G and the maximum peak intensity in the range of 1310 to 1350 cm -1 is D in the Raman spectrum of carbon nanotubes, G / of carbon nanotubes.
  • the D ratio is 5 to 100.
  • the dispersant is contained in an amount of 30 parts by mass or more and less than 250 parts by mass with respect to 100 parts by mass of the carbon nanotubes.
  • the complex elastic modulus is 5 Pa or more and less than 650 Pa, and the phase angle is 5 ° or more and less than 50 °.
  • the BET specific surface area of the carbon nanotube is 550 to 1200 m 2 / g.
  • the carbon nanotube when the maximum peak intensity in the range of 1560 to 1600 cm -1 is G and the maximum peak intensity in the range of 1310 to 1350 cm -1 is D in the Raman spectrum of carbon nanotubes, the carbon nanotube is used.
  • the carbon nanotube dispersion liquid has a G / D ratio of 10 to 50.
  • the carbon nanotube dispersion liquid at 25 ° C. is 5 Pa ⁇ s or more and less than 40 Pa ⁇ s when measured at a shear rate of 1 (s -1 ) using a reometer. Regarding.
  • the present invention also relates to the carbon nanotube dispersion having a cumulative particle size D10 measured by a dynamic light scattering method of 200 nm or more and less than 500 nm.
  • the present invention also relates to the carbon nanotube dispersion liquid having a volume resistivity of carbon nanotubes of 1.0 ⁇ 10 -3 ⁇ ⁇ cm to 1.0 ⁇ 10 -2- ⁇ ⁇ cm.
  • the present invention also relates to the carbon nanotube dispersion having a cumulative particle size D50 measured by a dynamic light scattering method of 500 nm or more and less than 3000 nm.
  • the present invention also relates to the carbon nanotube dispersion liquid in which the weight average molecular weight of the dispersant is 10,000 to 100,000.
  • the present invention also relates to the carbon nanotube dispersion liquid containing water as a solvent.
  • the present invention also relates to a carbon nanotube resin composition containing the carbon nanotube dispersion liquid and a binder.
  • the present invention also relates to a mixture slurry containing the carbon nanotube resin composition and an active material.
  • the present invention relates to an electrode film which is a coating film of the mixture slurry.
  • the present invention also relates to a non-aqueous electrolyte secondary battery containing a positive electrode, a negative electrode, and an electrolyte, wherein at least one of the positive electrode and the negative electrode contains the electrode film.
  • the carbon nanotube dispersion liquid of the present invention By using the carbon nanotube dispersion liquid of the present invention, a resin composition, a mixed material slurry, and an electrode film having excellent electrode strength and adhesion can be obtained. Further, a non-aqueous electrolyte secondary battery having excellent rate characteristics and cycle characteristics can be obtained. Therefore, the carbon nanotube dispersion liquid of the present invention can be used in various application fields where high conductivity and durability are required.
  • FIG. 1 is a graph showing Raman spectra of carbon nanotubes used in Examples and Comparative Examples of the present invention.
  • Carbon Nanotube The carbon nanotube of the present embodiment is preferably a single-walled carbon nanotube.
  • Single-walled carbon nanotubes and multi-walled carbon nanotubes may be mixed.
  • Single-walled carbon nanotubes have a structure in which one layer of graphite is wound, and multi-walled carbon nanotubes have a structure in which two or three or more layers of graphite are wound.
  • the average outer diameter of the carbon nanotubes of the present embodiment is 0.5 nm to 5 nm, preferably 1 nm to 3 nm, and more preferably 1 nm to 2 nm.
  • the average outer diameter of carbon nanotubes can be calculated by observing the morphology of carbon nanotubes with a transmission electron microscope (manufactured by JEOL Ltd.), measuring the lengths of 100 short axes, and calculating the average value of the numbers. can.
  • the BET specific surface area of the carbon nanotubes of the present embodiment is 550 m 2 / g to 1200 m 2 / g, preferably 600 to 1200 m 2 / g, and more preferably 800 m 2 / g to 1200 m 2 / g. , 800 m 2 / g to 1000 m 2 / g is more preferable.
  • the carbon nanotube of the present embodiment is G / D when the maximum peak intensity in the range of 1560 to 1600 cm -1 is G and the maximum peak intensity in the range of 1310 to 1350 cm -1 is D in the Raman spectrum.
  • the ratio is 5 to 100, more preferably 10 to 50, and even more preferably 20 to 50.
  • the Raman spectrum can be measured using laser light having a wavelength of 532 nm according to Raman spectroscopy.
  • the volume resistivity of the carbon nanotubes of the present embodiment is preferably 1.0 ⁇ 10 -3 ⁇ ⁇ cm to 3.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, preferably 1.0 ⁇ 10 -3 ⁇ ⁇ cm to 1. It is more preferably 0.0 ⁇ 10 -2 ⁇ ⁇ cm.
  • the volume resistivity of carbon nanotubes can be measured using a powder resistivity measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: Lorester GP powder resistivity measuring system MCP-PD-51).
  • the carbon purity of the carbon nanotubes of this embodiment is represented by the content rate (%) of carbon atoms in the carbon nanotubes.
  • the carbon purity is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on 100% by mass of carbon nanotubes.
  • the amount of metal contained in the carbon nanotubes of the present embodiment is preferably less than 20% by mass, more preferably less than 10% by mass, still more preferably less than 5% by mass, based on 100% by mass of the carbon nanotubes.
  • the metal contained in the carbon nanotube include a metal used as a catalyst in synthesizing the carbon nanotube, a metal oxide, and the like. Specific examples thereof include metals such as cobalt, nickel, aluminum, magnesium, silica, manganese and molybdenum, alloys of these metals, metal oxides of these metals, and composite oxides of these metals.
  • the carbon nanotubes of the present embodiment may be carbon nanotubes that have been surface-treated. Further, the carbon nanotube may be a carbon nanotube derivative to which a functional group typified by a carboxyl group is imparted. Further, carbon nanotubes containing a substance typified by an organic compound, a metal atom, or fullerene can also be used.
  • the carbon nanotube of this embodiment may be a pulverized carbon nanotube.
  • the pulverization process uses a pulverizer having a built-in pulverizing medium such as beads or steel balls to pulverize carbon nanotubes without substantially interposing a liquid substance, and is also called dry pulverization.
  • the crushing is performed by utilizing the crushing force and the destructive force due to the collision between the crushing media. Crushing mainly has the effect of reducing the size of the secondary particles of the carbon nanotubes, and can improve the dispersibility of the carbon nanotubes.
  • As the dry crushing device a known method such as a dry attritor, a ball mill, a vibration mill, or a bead mill can be used, and the crushing time can be arbitrarily set by the device.
  • the carbon nanotube of this embodiment may be a carbon nanotube manufactured by any method.
  • Carbon nanotubes can generally be produced by a laser ablation method, an arc discharge method, a thermal CVD method, a plasma CVD method and a combustion method, but are not limited thereto.
  • Dispersant of the present embodiment is not particularly limited as long as the carbon nanotubes can be dispersed and stabilized, and a surfactant or a resin-type dispersant can be used.
  • Surfactants are mainly classified into anionic, cationic, nonionic and amphoteric. Appropriately suitable types of dispersants can be used in suitable blending amounts according to the characteristics required for dispersion of carbon nanotubes.
  • an anionic surfactant the type is not particularly limited. Specifically, fatty acid salt, polysulfonate, polycarboxylate, alkyl sulfate ester salt, alkylaryl sulfonate, alkylnaphthalene sulfonate, dialkyl sulfonate, dialkyl sulfosuccinate, alkyl phosphate, polyoxy.
  • Examples thereof include ethylene alkyl ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate sulfonate, glycerol volate fatty acid ester and polyoxyethylene glycerol fatty acid ester.
  • specific examples thereof include sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonylphenyl ether sulfate ester salt, and sodium salt of ⁇ -naphthalene sulfonate formalin condensate. , Not limited to these.
  • alkylamine salts and quaternary ammonium salts there are alkylamine salts and quaternary ammonium salts. Specifically, stearylamine acetate, trimethyl palmammonium chloride, trimethyl beef ammonium chloride, dimethyldiolyl ammonium chloride, methyloleyl diethanol chloride, tetramethylammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate, cetylpyridinium bromide.
  • amphoteric surfactant examples include, but are not limited to, aminocarboxylates.
  • nonionic surfactant examples include, but are not limited to, polyoxyethylene alkyl ether, polyoxyalkylene derivative, polyoxyethylene phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and alkyl allyl ether. Specific examples thereof include, but are not limited to, polyoxyethylene lauryl ether, sorbitan fatty acid ester and polyoxyethylene octylphenyl ether.
  • the selected surfactant is not limited to a single surfactant. Therefore, it is also possible to use two or more kinds of surfactants in combination. For example, a combination of anionic surfactant and nonionic surfactant, or a combination of cationic surfactant and nonionic surfactant can be used.
  • the blending amount at that time is preferably a blending amount suitable for each surfactant component.
  • a combination of an anionic surfactant and a nonionic surfactant is preferable.
  • the anionic surfactant is preferably a polycarboxylate.
  • the nonionic surfactant is preferably polyoxyethylene phenyl ether.
  • cellulose derivatives cellulose acetate, cellulose acetate butyrate, cellulose butyrate, cyanoethyl cellulose, ethyl hydroxyethyl cellulose, nitrocellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose) , Carboxymethyl cellulose, etc.
  • polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, polyacrylonitrile-based polymers and the like polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, and polyacrylonitrile-based polymers are preferable.
  • Carboxymethyl cellulose as a resin-type dispersant can be used in the form of a salt such as a sodium salt of carboxymethyl cellulose in which the hydroxy group of carboxymethyl cellulose is replaced with a sodium carboxymethyl group.
  • Carboxymethyl cellulose as a resin-type dispersant preferably has a degree of etherification of 0.5 to 1.5, more preferably 0.6 to 1.0. The degree of etherification of carboxymethyl cellulose can be measured according to a conventional method, and more specifically, it can be measured according to the method described in Examples.
  • the dispersant of the present embodiment has a pullulan-equivalent weight average molecular weight of 5,000 or more and 300,000 or less, more preferably 10,000 or more and 100,000 or less, and further preferably 10,000 or more and 50,000 or less. ..
  • a dispersant having an appropriate weight average molecular weight is used, the adsorptivity to carbon nanotubes is improved, and the stability of the carbon nanotube dispersion liquid is further improved.
  • a dispersant exceeding the above range is used, the viscosity of the carbon nanotube dispersion liquid becomes high, and when a disperser such as a nozzle-type high-pressure homogenizer in which the dispersant liquid passes through a narrow flow path is used, the dispersion efficiency becomes high. May decrease.
  • the resin-type dispersant may have a binding ability in addition to the dispersive ability, and the above-mentioned resin-type dispersant can also be used as a binder, and the same type of binder as the resin-type dispersant can be used.
  • a resin may be used.
  • the same type of resin as the resin type dispersant is used as the binder, it is preferable to use a resin having a weight average molecular weight larger than the weight average molecular weight of the resin type dispersant.
  • the weight average molecular weight (Mw) of the dispersant can be measured by gel permeation chromatography (GPC) equipped with a differential refractive index (RI) detector, and is a pullulan-equivalent value.
  • an inorganic base and / or an inorganic metal salt may be contained.
  • the inorganic base and the inorganic metal salt are preferably compounds having at least one of an alkali metal and an alkaline earth metal, and more particularly, chlorides, hydroxides and carbonates of the alkali metal and the alkaline earth metal. Examples thereof include salts, nitrates, sulfates, phosphates, tungstates, vanadium salts, molybdenates, niobates, borates and the like. Among these, alkali metals, chlorides, hydroxides and carbonates of alkaline earth metals are preferable in terms of easily supplying cations.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • Examples of the hydroxide of the alkaline earth metal include calcium hydroxide and magnesium hydroxide.
  • Examples of the carbonate of the alkali metal include lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like.
  • Examples of the carbonate of the alkaline earth metal include calcium carbonate and magnesium carbonate. Among these, lithium hydroxide, sodium hydroxide, lithium carbonate and sodium carbonate are more preferable.
  • an acid may be contained.
  • an acid By adding an acid, the charge state in the dispersion system and the balance between the hydrophilic part and the hydrophobic part may change, and the dispersibility may be improved.
  • the type of acid is not particularly limited, and one type or a plurality of types may be used in combination. For example, oxalic acid, lactic acid, citric acid, polyacrylic acid, polystyrene sulfonic acid, acetic acid, malonic acid, hydrochloric acid, nitric acid, sulfuric acid, boric acid, phosphoric acid and the like can be mentioned.
  • an antifoaming agent may be contained.
  • the defoaming agent can be arbitrarily used as long as it has a defoaming effect, such as a commercially available defoaming agent, a wetting agent, a hydrophilic organic solvent, and a water-soluble organic solvent. You may.
  • alcohol-based ethanol, propanol, isopropanol, butanol, octyl alcohol, hexadecyl alcohol, acetylene alcohol, ethylene glycol monobutyl ether, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetylene glycol, polyoxyalkylene glycol, propylene glycol, etc. Glycols, etc.
  • Fatty acid ester type diethylene glycol laurate, glycerin monolithinolate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, natural wax, etc.
  • Amide type polyoxyalkylene amide, acrylate polyamine, etc.
  • Phosphoric acid ester type tributyl phosphate, sodium octyl phosphate, etc.
  • Metal soap type aluminum stearate, calcium oleate, etc. Oils and fats; animal and vegetable oils, sesame oil, castor oil, etc.
  • Mineral oil system kerosene, paraffin, etc.
  • Silicone type dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane, fluorosilicone oil and the like can be mentioned.
  • the solvent of the present embodiment is not particularly limited as long as the carbon nanotubes can be dispersed, but is selected from any one selected from the group consisting of water and a water-soluble organic solvent, or selected from these groups. It is preferable that it is a mixed solvent containing two or more kinds of the above-mentioned substances, and it is more preferable that it contains water. When water is contained, it is preferably 95% by mass or more, more preferably 98% by mass or more, and may be a single solvent of water with respect to 100% by mass of the solvent.
  • Water-soluble organic solvents include alcohol-based (methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, benzyl alcohol, etc.) and polyhydric alcohol-based (ethylene glycol, diethylene glycol, triethylene glycol, polyethylene).
  • the carbon nanotube dispersion liquid of the present embodiment contains carbon nanotubes, a dispersant, and a solvent.
  • the complex elastic modulus of the carbon nanotube dispersion liquid of the present embodiment at 25 ° C. and a frequency of 1 Hz is preferably 5 Pa or more and less than 650 Pa, preferably 5 Pa or more and less than 400 Pa, and further preferably 10 Pa or more and less than 400 Pa.
  • the complex elastic modulus of the carbon nanotube dispersion shows the hardness of the carbon nanotube dispersion, the dispersibility of the carbon nanotubes is good, and the viscosity of the carbon nanotube dispersion tends to be smaller.
  • the complex elastic modulus may be a high value because of the structural viscosity of the carbon nanotube itself.
  • the phase angle of the carbon nanotube dispersion liquid of the present embodiment at 25 ° C. and a frequency of 1 Hz is 5 ° or more and less than 50 °, and more preferably 10 ° or more and less than 50 °.
  • the phase angle means the phase shift of the stress wave when the strain applied to the carbon nanotube dispersion is a sine wave. In the case of a pure elastic body, the phase angle is 0 ° because the sine wave has the same phase as the applied strain. On the other hand, if it is a purely viscous material, it will be a stress wave advanced by 90 °.
  • a carbon nanotube dispersion having a complex elastic modulus and a phase angle in the above range has a good dispersed particle size and dispersed state of carbon nanotubes, and is suitable as a carbon nanotube dispersion liquid for improving electrode strength and conductivity.
  • the complex elastic modulus and phase angle of the carbon nanotube dispersion are dynamically viscoelastic in the range of 0.01% to 5% strain rate at 25 ° C and 1 Hz frequency using a leometer with a cone having a diameter of 35 mm and 2 °. It can be requested to carry out an elastic measurement. If the measured value contains a decimal point, it is rounded to an integer according to Rule B of JISZ8401: 1999.
  • the complex elastic modulus of the carbon nanotube dispersion liquid at 25 ° C. and a frequency of 1 Hz is preferably 4.5 Pa or more and less than 650.4 Pa, and the carbon nanotube dispersion liquid has a frequency of 25 ° C.
  • the phase angle at 1 Hz is preferably 4.5 ° or more and less than 50.4 °.
  • a developed conductive network is formed by uniformly and satisfactorily dispersing the carbon nanotubes while maintaining a certain length so that the fiber length does not become short due to breakage. Therefore, it is not only necessary that the viscosity of the conductive material dispersion is low and the dispersibility (apparently) is good, but the complex elastic modulus and / or the phase angle is combined with a conventional index such as viscosity to obtain a dispersed state. Judgment is especially useful. By setting the complex elastic modulus and / or the phase angle in the above range, a conductive material dispersion having good conductivity and electrode strength can be obtained.
  • the viscosity of the carbon nanotube dispersion liquid of the present embodiment is preferably 5 Pa ⁇ s or more and less than 60 Pa ⁇ s when measured at a shear rate of 1 (s -1 ) at 25 ° C. using a leometer. It is more preferably s or more and less than 40 Pa ⁇ s, and further preferably 20 Pa ⁇ s or more and less than 40 Pa ⁇ s. Further, when measured at a shear rate of 10 (s -1 ) using a leometer at 25 ° C., it is preferably 1 Pa ⁇ s or more and less than 10 Pa ⁇ s.
  • the dispersibility of the carbon nanotube dispersion can be determined, and the carbon nanotube dispersion in the above range has good dispersion particle size and dispersion state of the carbon nanotubes. It is suitable as a carbon nanotube dispersion liquid for improving electrode strength and conductivity.
  • the viscosity of the carbon nanotube dispersion is determined by allowing the carbon nanotube dispersion to stand in a constant temperature bath at 25 ° C for 1 hour or more, stirring the carbon nanotube dispersion sufficiently, and then using a cone with a diameter of 35 mm and 2 ° to measure the viscosity. Can be obtained by measuring the shear viscosities at 25 ° C. and shear rates 1s -1 and 10s -1 . If the measured value contains a decimal point, it is rounded to an integer according to Rule B of JISZ8401: 1999.
  • the cumulative particle size D10 measured by the dynamic light scattering method of the carbon nanotube dispersion liquid of the present embodiment is preferably 200 nm or more and less than 500 nm, more preferably 200 nm or more and less than 400 nm, and more preferably 300 nm or more and less than 400 nm. Is even more preferable.
  • the cumulative particle size D50 measured by the dynamic light scattering method of the carbon nanotube dispersion is preferably 500 nm or more and less than 3000 nm, more preferably 500 nm or more and less than 2000 nm, and more preferably 500 nm or more and less than 1500 nm. More preferred.
  • the cumulative particle size D10 and D50 of the carbon nanotube dispersion can be measured using a particle size distribution meter (Nanotrac UPA, model UPA-EX manufactured by Microtrac Bell Co., Ltd.).
  • the particle size measured by the dynamic light scattering method correlates with the fiber length of the carbon nanotubes, and the carbon nanotube dispersion having the cumulative particle size D10 in the above range has a good dispersion state of the carbon nanotubes in the dispersion.
  • the carbon nanotube dispersion liquid of the present embodiment it is preferable to carry out a treatment of dispersing the carbon nanotubes in a solvent.
  • the dispersive device used to perform such processing is not particularly limited.
  • a disperser usually used for pigment dispersion or the like can be used.
  • mixers such as disposables, homomixers, planetary mixers, homogenizers (BRANSON Advanced Digital Sonifer (registered trademark), MODEL 450DA, M-Technique "Clearmix”, PRIMIX “Fillmix”, etc., silver.
  • the amount of carbon nanotubes in the carbon nanotube dispersion liquid of the present embodiment is preferably 0.2 parts by mass to 1.5 parts by mass, and 0.4 parts by mass to 1.2 parts by mass with respect to 100 parts by mass of the carbon nanotube dispersion liquid. Parts are preferable, and 0.4 parts by mass to 1.0 part by mass are more preferable.
  • the amount of the dispersant in the carbon nanotube dispersion liquid of the present embodiment is preferably 30 parts by mass to 250 parts by mass, and more preferably 50 parts by mass to 150 parts by mass with respect to 100 parts by mass of carbon nanotubes. It is preferable to use 50 parts by mass to 100 parts by mass, and it is more preferable to use it.
  • the pH of the carbon nanotube dispersion liquid of the present embodiment is preferably 6 to 11, more preferably 7 to 11, further preferably 8 to 11, and particularly preferably 9 to 11.
  • the pH of the carbon nanotube dispersion can be measured using a pH meter (pH METER F-52, manufactured by HORIBA, Ltd.).
  • Binder A binder is a resin for binding substances such as carbon nanotubes.
  • binder of the present embodiment examples include ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, and the like.
  • Carboxymethyl cellulose as a binder resin preferably has a high viscosity, for example, the viscosity when a 1% aqueous solution is prepared is preferably 500 to 6000 mPa ⁇ s, and more preferably 1000 to 3000 mPa ⁇ s. ..
  • the viscosity of the 1% aqueous solution of carboxymethyl cellulose can be measured under the condition of 25 ° C. at a rotor rotation speed of a B-type viscometer rotor of 60 rpm.
  • Carboxymethyl cellulose as a binder resin preferably has a high degree of etherification.
  • the degree of etherification is preferably 0.6 to 1.5, more preferably 0.6 to 1.2, and even more preferably 0.8 to 1.2.
  • the amount of the binder in the mixture slurry of the present embodiment is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, when the mass of the active material is 100% by mass. It is particularly preferably 2 to 20% by mass.
  • the type and amount ratio of the binder are appropriately selected according to the properties of coexisting substances such as carbon nanotubes and active substances.
  • the ratio of carboxymethyl cellulose is preferably 0.5 to 3.0% by mass, preferably 1.0, when the mass of the active material is 100% by mass. -2.0% by mass is more preferable.
  • the styrene-butadiene rubber if it is an oil droplet emulsion in water, one generally used as a binder for electrodes can be used.
  • the proportion of styrene-butadiene rubber is preferably 0.5 to 3.0% by mass, preferably 1.0. -2.0% by mass is more preferable.
  • the proportion of polyacrylic acid is preferably 1 to 25% by mass, and further 5 to 20% by mass. preferable.
  • the proportion of polyacrylic acid is preferably 1 to 10% by mass, and further 1 to 5% by mass. preferable.
  • the carbon nanotube resin composition of the present embodiment contains carbon nanotubes, a dispersant, a solvent, and a binder.
  • the carbon nanotube resin composition of the present embodiment it is preferable to mix and homogenize the carbon nanotube dispersion liquid and the binder.
  • the mixing method various conventionally known methods can be used.
  • the carbon nanotube resin composition can be produced by using the dispersant described in the above carbon nanotube dispersion liquid.
  • the mixture slurry of the present embodiment contains carbon nanotubes, a dispersant, a solvent, a binder, and an active material.
  • the active material of the present embodiment is a material that is the basis of a battery reaction.
  • the active material is divided into a positive electrode active material and a negative electrode active material according to the electromotive force.
  • the positive electrode active material is not particularly limited, but a metal oxide capable of doping or intercalating lithium ions, a metal compound such as a metal sulfide, a conductive polymer, or the like can be used.
  • a metal oxide capable of doping or intercalating lithium ions a metal compound such as a metal sulfide, a conductive polymer, or the like can be used.
  • examples thereof include oxides of transition metals such as Fe, Co, Ni and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides.
  • transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered lithium nickelate, lithium cobaltate, lithium manganate, lithium manganate having a spinel structure, etc.
  • Examples thereof include a composite oxide powder of lithium and a transition metal, a lithium iron phosphate-based material which is a phosphoric acid compound having an olivine structure, and a transition metal sulfide powder such as TiS 2 and FeS.
  • conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Further, the above-mentioned inorganic compounds and organic compounds may be mixed and used.
  • the negative electrode active material is not particularly limited as long as it can be doped with or intercalated with lithium ions.
  • metal Li alloys such as tin alloys, silicon alloys, and lead alloys thereof, Li x Fe 2 O 3 , Li x Fe 3 O 4 , Li x WO 2 (x is a number of 0 ⁇ x ⁇ 1).
  • Metal oxides such as lithium titanate, lithium vanadium, lithium siliconate, conductive polymers such as polyacetylene and poly-p-phenylene, and amorphous carbonaceous materials such as soft carbon and hard carbon.
  • Examples thereof include artificial graphite such as a highly graphitized carbon material, carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, air layer growth carbon fiber, and carbon-based material such as carbon fiber.
  • artificial graphite such as a highly graphitized carbon material
  • carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, air layer growth carbon fiber, and carbon-based material such as carbon fiber.
  • These negative electrode active materials may be used alone or in combination of two or more.
  • a silicon-based negative electrode active material is preferable, and specifically, a negative electrode active material containing silicon such as a silicon alloy and lithium siliconate is preferable.
  • Examples of the silicon-based negative electrode active material include so-called metallurgical grade silicon produced by reducing silicon dioxide with carbon, industrial grade silicon obtained by reducing impurities by acid treatment or unidirectional solidification of metallurgical grade silicon, and silicon.
  • High-purity silicon produced from silane obtained by reaction and having different crystal states such as single crystal, polycrystal, and amorphous, and industrial grade silicon are highly purified by sputter method or EB vapor deposition (electron beam vapor deposition). At the same time, silicon whose crystal state and precipitation state are adjusted can be mentioned.
  • silicon oxide which is a compound of silicon and oxygen, silicon and various alloys, and a silicon compound whose crystal state is adjusted by a quenching method or the like can be mentioned.
  • silicon-based negative electrode active material having a structure in which silicon nanoparticles are dispersed in silicon oxide, the outside of which is coated with a carbon film, is preferable.
  • the negative electrode active material of the present embodiment includes amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as graphitized carbon material, and carbonaceous powder such as natural graphite. It is preferable to use. Among them, it is preferable to use carbonaceous powder such as artificial graphite or natural graphite.
  • the amount of the silicon-based negative electrode active material is preferably 3 to 50% by mass, more preferably 5 to 25% by mass, when the carbonaceous powder such as artificial graphite or natural graphite is 100% by mass.
  • the BET specific surface area of the active material of the present embodiment is preferably 0.1 to 10 m 2 / g, more preferably 0.2 to 5 m 2 / g, and further preferably 0.3 to 3 m 2 / g. preferable.
  • the average particle size of the active material of the present embodiment is preferably in the range of 0.5 to 50 ⁇ m, and more preferably 2 to 20 ⁇ m.
  • the average particle size of the active material as used herein is an average value of the particle size of the active material measured with an electron microscope.
  • the mixed material slurry of the present embodiment can be produced by various conventionally known methods. For example, a method of adding an active material to a carbon nanotube resin composition to prepare the carbon nanotube resin composition, and a method of adding the active material to the carbon nanotube dispersion liquid and then adding a binder to prepare the carbon nanotube resin composition can be mentioned.
  • the mixed material slurry of the present embodiment it is preferable to add an active material to the carbon nanotube resin composition and then disperse it.
  • the dispersive device used to perform such processing is not particularly limited.
  • the mixed material slurry the mixed material slurry can be obtained by using the dispersion device described in the above-mentioned carbon nanotube dispersion liquid.
  • the amount of the active material in the mixture slurry of the present embodiment is preferably 20 to 85 parts by mass, more preferably 30 to 75 parts by mass, and 40 to 70 parts by mass with respect to 100 parts by mass of the mixture slurry. It is more preferably by mass.
  • the amount of carbon nanotubes in the mixed material slurry of the present embodiment is preferably 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the active material. It is preferably 03 to 1 part by mass.
  • the solid content of the mixed material slurry of the present embodiment is preferably 30 to 90% by mass, more preferably 30 to 80% by mass, and 40 to 75% by mass with respect to 100% by mass of the mixed material slurry. It is preferably mass%.
  • Electrode film of the present embodiment is formed by forming a mixture slurry.
  • it is a coating film in which an electrode mixture layer is formed by applying and drying a mixture slurry on a current collector.
  • the material and shape of the current collector used for the electrode film of the present embodiment are not particularly limited, and those suitable for various secondary batteries can be appropriately selected.
  • examples of the material of the current collector include metals such as aluminum, copper, nickel, titanium, and stainless steel, and alloys of these metals.
  • a foil on a flat plate is generally used, but a roughened surface, a perforated foil, or a mesh-shaped current collector can also be used.
  • the method of applying the mixture slurry on the current collector is not particularly limited, and a known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a knife coating method, a spray coating method, a gravure coating method, a screen printing method, an electrostatic coating method, and the like, and drying. As the method, a stand-alone dryer, a blower dryer, a warm air dryer, an infrared heater, a far-infrared heater, and the like can be used, but the method is not particularly limited thereto.
  • the thickness of the electrode mixture layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less.
  • Non-aqueous electrolyte secondary battery of the present embodiment includes a positive electrode, a negative electrode, and an electrolyte. It is preferable that at least one of the positive electrode and the negative electrode contains the electrode film of the present embodiment.
  • a current collector obtained by applying and drying a mixture slurry containing a positive electrode active material to prepare an electrode film can be used.
  • a current collector obtained by applying and drying a mixture slurry containing a negative electrode active material to prepare an electrode film can be used.
  • electrolyte various conventionally known electrolytes in which ions can move can be used.
  • the electrolyte is preferably dissolved in a non-aqueous solvent and used as an electrolytic solution.
  • the non-aqueous solvent is not particularly limited, and is, for example, carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate; ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ .
  • -Lactones such as octanoic lactones; tetrahydrofuran, 2-methyltetrachloride, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1, Glymes such as 2-dibutoxyetane; esters such as methylformate, methylacetate, and methylpropionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile.
  • solvents may be used alone, or two or more kinds may be mixed and used.
  • the non-aqueous electrolyte secondary battery of the present embodiment preferably contains a separator.
  • the separator include polyethylene non-woven fabric, polypropylene non-woven fabric, polyamide non-woven fabric, and those obtained by subjecting them to a hydrophilic treatment, but the separator is not particularly limited thereto.
  • the structure of the non-aqueous electrolyte secondary battery of the present embodiment is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as needed, and includes a paper type, a cylindrical type, a button type, a laminated type, and the like. It can have various shapes according to the purpose of use.
  • CNT carbon nanotubes
  • a CNT was installed in a Raman microscope (XploRA, manufactured by HORIBA, Ltd.), and measurement was performed using a laser wavelength of 532 nm.
  • the measurement conditions were an capture time of 60 seconds, an integration frequency of 2 times, a dimming filter of 10%, an objective lens magnification of 20 times, a confocus hole of 500, a slit width of 100 ⁇ m, and a measurement wavelength of 100 to 3000 cm -1 .
  • the CNTs for measurement were separated on a slide glass and flattened using a spatula.
  • the maximum peak intensity is G in the range of 1560 to 1600 cm -1 in the spectrum
  • the maximum peak intensity is D in the range of 1310 to 1350 cm -1
  • the G / D ratio is G / of CNT. It was set to D ratio.
  • ⁇ BET specific surface area of CNT> After weighing 0.03 g of CNTs using an electronic balance (MSA225S100DI manufactured by Sartorius), the CNTs were dried at 110 ° C. for 15 minutes while degassing. Then, the BET specific surface area of CNT was measured using a fully automatic specific surface area measuring device (HM-model 1208 manufactured by MOUNTECH).
  • ⁇ Average outer diameter of CNT> Weigh 0.2 g of CNT into a 450 mL SM sample bottle (manufactured by Sansho Co., Ltd.) using an electronic balance (MSA225S100DI manufactured by Sartorius), add 200 mL of toluene, and add an ultrasonic homogenizer (Advanced Digital Sonifer) (registered).
  • a CNT dispersion liquid was prepared by performing a dispersion treatment under ice-cooling for 5 minutes at an amplitude of 50% using (trademark), MODEL 450DA, manufactured by BRANSON.
  • the CNT dispersion was appropriately diluted, dropped in the form of a collodion film in the form of several ⁇ L, dried at room temperature, and then observed using a direct transmission electron microscope (H-7650, manufactured by Hitachi, Ltd.). Observation is performed at a magnification of 50,000 times, multiple photographs containing 10 or more CNTs in the field of view are taken, the outer diameters of 300 arbitrarily extracted CNTs are measured, and the average value is the average outer diameter of the CNTs (the average outer diameter of the CNTs. nm).
  • ⁇ Particle size distribution of CNT dispersion liquid> After allowing the CNT dispersion to stand in a constant temperature bath at 25 ° C. for 1 hour or more, the CNT dispersion is sufficiently stirred and diluted, and then a particle size distribution meter (Nanotrac UPA, model UPA-EX manufactured by Microtrac Bell Co., Ltd.) ) was used to measure the cumulative particle sizes D10 and D50 of the CNT dispersion.
  • the permeability was absorbed, the density of CNT was 1.8, and the shape was non-spherical.
  • the refractive index of the solvent was 1.333.
  • the concentration of the CNT dispersion was diluted so that the value of the loading index was in the range of 0.8 to 1.2.
  • the complex elastic modulus and phase angle of the CNT dispersion liquid are a strain rate of 0 at 25 ° C. and a frequency of 1 Hz using a leometer (RheoStress 1 rotary leometer manufactured by Thermo Fisher Scientific Co., Ltd.) with a cone having a diameter of 35 mm and a diameter of 2 °. It was evaluated by performing dynamic viscoelasticity measurements in the range of 0.01% to 5%.
  • ⁇ Peeling strength of electrode film for negative electrode> The negative electrode mixture slurry was applied onto a copper foil using an applicator so that the basis weight per unit of the electrode was 8 mg / cm 2 , and then in an electric oven at 120 ° C. ⁇ 5 ° C. for 25 minutes. The coating film was dried. Then, two pieces were cut into a rectangle of 90 mm ⁇ 20 mm with the coating direction as the major axis.
  • a desktop tensile tester (Strograph E3, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure the peel strength, and the peel strength was evaluated by a 180-degree peel test method. Specifically, a 100 mm ⁇ 30 mm size double-sided tape (No.
  • ⁇ Peeling strength of electrode film for positive electrode> The positive electrode mixture slurry is applied onto an aluminum foil using an applicator so that the basis weight per unit of the electrode is 20 mg / cm 2 , and then in an electric oven at 120 ° C. ⁇ 5 ° C. for 25 minutes. The coating film was dried. Then, two pieces were cut into a rectangle of 90 mm ⁇ 20 mm with the coating direction as the major axis. A desktop tensile tester (Strograph E3, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure the peel strength, and the peel strength was evaluated by a 180-degree peel test method. Specifically, a 100 mm ⁇ 30 mm size double-sided tape (No.
  • the mixture slurry for the positive electrode is applied on an aluminum foil having a thickness of 20 ⁇ m as a current collector using an applicator, and then dried in an electric oven at 120 ° C. ⁇ 5 ° C. for 25 minutes per unit area of the electrode.
  • the basis weight was adjusted to 20 mg / cm 2 .
  • a rolling process was performed by a roll press (3t hydraulic roll press manufactured by Thunk Metal Co., Ltd.) to prepare a standard positive electrode having a density of the mixture layer of 3.1 g / cm 3 .
  • a laminated lithium-ion secondary battery was installed in a constant temperature room at 25 ° C., and charge / discharge measurement was performed using a charge / discharge device (SM-8 manufactured by Hokuto Denko Co., Ltd.). After performing constant current constant voltage charging (cutoff current 1.1mA (0.02C)) at a charging end voltage of 4.2V at a charging current of 11mA (0.2C), a discharge current of 11mA (0.2C). A constant current discharge was performed at a discharge end voltage of 2.5 V.
  • a laminated lithium-ion secondary battery was installed in a constant temperature room at 25 ° C., and charge / discharge measurement was performed using a charge / discharge device (SM-8 manufactured by Hokuto Denko Co., Ltd.). After performing constant current constant voltage charging (cutoff current 1.38mA (0.025C)) at a charging end voltage of 4.2V at a charging current of 55mA (1C), the discharge end voltage is applied at a discharge current of 55mA (1C). Constant current discharge was performed at 2.5 V. This operation was repeated 200 times. 1C is a current value that discharges the theoretical capacity of the positive electrode in 1 hour.
  • the weight average molecular weight (Mw) of the dispersant (A) was 38,000.
  • the weight average molecular weight (Mw) of the produced dispersant (A) was measured by gel permeation chromatography (GPC) equipped with an RI detector under the following conditions. The molecular weight is a pullulan equivalent.
  • Measurement sample 0.1% by mass aqueous solution
  • Device HLC-8320GPC (manufactured by Tosoh)
  • Eluent 0.1M NaCl aqueous solution
  • Temperature 25 ° C
  • Injection volume 100 ⁇ l
  • Table 1 shows the CNTs used in Examples and Comparative Examples, the outer diameters of CNTs, the specific surface area of CNTs, the G / D ratio, and the volume resistivity.
  • Table 2 shows the dispersants used in Examples, Comparative Examples and Reference Examples.
  • Example 1 98.25 parts of ion-exchanged water was added to the stainless steel container, and 0.75 parts of the dispersant (A) was added while stirring with a disper, and the mixture was stirred with a disper until uniform. After that, one part of CNT (A) was weighed, added while stirring with a dispersion, and a square hole high shear screen was attached to a high shear mixer (L5MA, manufactured by SILVERSON), and the whole was added at a speed of 8,600 rpm. Batch dispersion was performed until uniform.
  • the dispersion liquid was supplied from a stainless steel container to a high-pressure homogenizer (Starburst Lab HJP-17007, manufactured by Sugino Machine Limited) via a pipe, and a pass-type dispersion treatment was performed 5 times to obtain a CNT dispersion liquid (WA1). rice field.
  • the dispersion treatment was performed using a single nozzle chamber with a nozzle diameter of 0.25 mm and a pressure of 100 MPa.
  • Examples 2 to 15 (Examples 19 to 20), (Comparative Examples 1 to 2)
  • the CNT dispersion liquid (WA2 to WF4) was prepared by the same method as in Example 1 except that the CNT type, CNT addition amount, dispersant type, dispersant addition amount, ion-exchanged water addition amount, and number of passes shown in Table 3 were changed. ) was obtained.
  • Example 16 In a plastic container having a capacity of 150 cm3 , 4 parts by mass of the CNT dispersion liquid (WA1) prepared in Example 1 and 6 parts by mass of ion-exchanged water were weighed. Then, using a rotation / revolution mixer (Awatori Rentaro manufactured by Shinky Co., Ltd., ARE-310), the mixture was stirred at 2000 rpm for 30 seconds to obtain a CNT dispersion liquid (WA13).
  • Example 17 A CNT dispersion liquid (WA14) was obtained by the same method as in Example 16 except that the CNT dispersion liquid (WA3) prepared in Example 3 was used.
  • Example 18 A CNT dispersion liquid (WA15) was obtained by the same method as in Example 16 except that the CNT dispersion liquid (WA11) prepared in Example 11 was used.
  • Example 21 In a polypropylene bottle container, 20 parts of CNT (C) and 480 parts of zirconia beads having a diameter of 8 mm were charged as crushing media, and crushed for 40 minutes with a paint conditioner manufactured by Red Devil. Then, the zirconia beads were separated and CNT (C) was recovered. Next, 98.38 parts of ion-exchanged water was added to the stainless steel container, and 1.13 parts of the dispersant (C) was added while stirring with a disper, and the mixture was stirred with a disper until uniform.
  • Example 22 Add 98.40 parts of ion-exchanged water to a stainless steel container, and while stirring with a disper, add 0.50 parts of dispersant (C) and 0.10 parts of polyacrylic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 25000). In addition, the mixture was stirred with a disper until uniform. After that, 1.0 part of CNT (A) was weighed, added while stirring with a dispersion, and a square hole high shear screen was attached to a high shear mixer (L5MA, manufactured by SILVERSON) at a speed of 8,600 rpm. Batch dispersion was performed until the whole was uniform.
  • C dispersant
  • polyacrylic acid manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 25000
  • the dispersion liquid was supplied from a stainless steel container to a high-pressure homogenizer (Starburst Lab HJP-17007, manufactured by Sugino Machine Limited) via a pipe, and a pass-type dispersion treatment was performed 20 times to obtain a CNT dispersion liquid (WA28). rice field.
  • the dispersion treatment was performed using a single nozzle chamber with a nozzle diameter of 0.25 mm and a pressure of 100 MPa.
  • Example 23 99.3 parts of NMP was added to the stainless steel container, 0.3 part of the dispersant (E) was added while stirring with a disperser, and the mixture was stirred with the disperser until the dispersant (E) was dissolved. After that, 0.4 part of CNT (A) was weighed, added while stirring with a dispersion, and a square hole high shear screen was attached to a high shear mixer (L5MA, manufactured by SILVERSON) at a speed of 8,600 rpm. Batch dispersion was performed until the whole was uniform.
  • L5MA high shear mixer
  • the dispersion liquid was supplied from a stainless steel container to a high-pressure homogenizer (Starburst Lab HJP-17007, manufactured by Sugino Machine Limited) via a pipe, and a pass-type dispersion treatment was performed 20 times to obtain a CNT dispersion liquid (A20). rice field.
  • the dispersion treatment was performed using a single nozzle chamber with a nozzle diameter of 0.25 mm and a pressure of 100 MPa.
  • Example 24 to 26 CNT dispersions (A21 to A23) were obtained by the same method as in Example 23 except that the number of passes shown in Table 4 was changed.
  • Table 5 shows the evaluation results of the CNT dispersions prepared in Examples 1 to 26 and Comparative Examples 1 to 7.
  • 10 or more and less than 50 was evaluated as ⁇ (good)
  • 5 or more and less than 10 was evaluated as ⁇ (possible)
  • less than 5 or 50 or more was evaluated as ⁇ (impossible).
  • the evaluation of the complex elastic modulus of the CNT dispersion liquid at 25 ° C. and a frequency of 1 Hz was evaluated as ⁇ (good) for 5 or more and less than 400, ⁇ (possible) for 400 or more and less than 650, and ⁇ (impossible) for less than 5.
  • the shear viscosity at a shear rate of 1 is 20 or more and less than 40 ⁇ (excellent), 10 or more and less than 20, or 40 or more and less than 60 is ⁇ (good), and 5 or more and less than 10 is ⁇ . (Yes) Less than 5 was set as x (No).
  • the particle size evaluation of the CNT dispersion liquid when the particle size distribution was D10, the particle size distribution was 200 or more and less than 300 as ⁇ (excellent), 300 or more and less than 500 as ⁇ (good), and less than 200 as ⁇ (impossible).
  • Example 28 12.5 parts by mass of an aqueous solution prepared by dissolving 0.63 parts by mass of CNT dispersion liquid (WA1) and 2% by mass of CMC (manufactured by Daicel FineChem Co., Ltd., # 1190) in a plastic container having a capacity of 150 cm 3 , and 13.8 parts by mass of ion-exchanged water. Weighed by mass. Then, using a rotation / revolution mixer (Awatori Rentaro manufactured by Shinky Co., Ltd., ARE-310), the mixture was stirred at 2000 rpm for 30 seconds to obtain a CNT resin composition (WA1).
  • a rotation / revolution mixer Alwatori Rentaro manufactured by Shinky Co., Ltd., ARE-310
  • Example 28 except that the CNT dispersion liquid shown in Table 6 was changed and the addition amount of the CNT dispersion liquid and the ion-exchanged water was adjusted so that the CNT in 100 parts by mass of the mixed material slurry was 0.025 parts by mass.
  • CNT resin compositions (WA2-WA19) and negative electrode mixture slurries (WA2-WA19) were obtained.
  • the non-volatile content of the mixture slurry for the negative electrode was 48% by mass.
  • Example 50 7.0 parts by mass of NMP in which 8% by mass of PVDF (Solvey's Solef # 5130) was dissolved in a plastic container having a capacity of 150 cm 3 was weighed. Then, 0.19 parts by mass of the CNT dispersion liquid (A20) was added, and the mixture was stirred at 2000 rpm for 30 seconds using a rotation / revolution mixer (Awatori Rentaro, ARE-310) to obtain the CNT resin composition (A20).
  • a rotation / revolution mixer Awatori Rentaro, ARE-310
  • Example 51 to 53 (Comparative Example 13)
  • the CNT resin composition (A21 to A24) and the positive electrode mixture slurry (A21 to A24) were obtained by the same method as in Example 50 except that the CNT dispersion liquid was changed to the CNT dispersion liquid shown in Table 6.
  • Example 54 The negative electrode mixture slurry (WA1) is applied onto a copper foil using an applicator so that the basis weight per unit of the electrode is 8 mg / cm 2 , and then in an electric oven at 120 ° C. ⁇ 5 ° C. The coating film was dried for 25 minutes to obtain an electrode film (WA1).
  • Electrode films (WA2) to (WA19) were obtained by the same method as in Example 54 except that the slurry was changed to the negative electrode mixture slurry shown in Table 7.
  • Example 76 The positive electrode mixture slurry (A20) is applied onto a copper foil using an applicator so that the basis weight per unit of the electrode is 20 mg / cm 2 , and then in an electric oven at 120 ° C. ⁇ 5 ° C. The coating film was dried for 25 minutes to obtain an electrode film (A20).
  • Electrode films (A21) to (A24) were obtained by the same method as in Example 76 except that the slurry was changed to the positive electrode mixture slurry shown in Table 7.
  • Table 7 shows the evaluation results of the electrode films prepared in Examples 54 to 79 and Comparative Examples 14 to 19.
  • peel strength ( ⁇ ⁇ cm) of 0.5 or more is ⁇ (excellent), 0.3 or more and less than 0.5 is ⁇ (good), and 0.1 or more and less than 0.3 is ⁇ (possible).
  • Less than 0.1 was defined as x (impossible).
  • Example 80 to 101 (Comparative Examples 20 to 24)
  • the electrode films (WA1 to WA19) were rolled by a roll press (3t hydraulic roll press manufactured by Thunk Metal Co., Ltd.) to prepare a negative electrode having a mixture layer density of 1.7 g / cm 3 .
  • Example 102 to 105 (Examples 102 to 105), (Comparative Example 25)
  • the electrode films (A20 to A24) were rolled by a roll press (3t hydraulic roll press manufactured by Thunk Metal Co., Ltd.) to prepare a positive electrode having a mixture layer density of 3.2 g / cm 3 .
  • Table 8 shows the negative electrodes and positive electrodes manufactured in Examples 80 to 105 and Comparative Examples 20 to 25.
  • Example 106 The negative electrode (WA1) and the standard positive electrode are punched into 50 mm ⁇ 45 mm and 45 mm ⁇ 40 mm, respectively, and the separator (porous polyproprene film) inserted between them is inserted into an aluminum laminated bag at 60 ° C. in an electric oven. It was dried for 1 hour. Then, in a glove box filled with argon gas, an electrolytic solution (a mixed solvent in which ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate were mixed at a ratio of 3: 5: 2 (volume ratio) was prepared, and further used as an additive.
  • an electrolytic solution a mixed solvent in which ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate were mixed at a ratio of 3: 5: 2 (volume ratio
  • VC vinyl carbonate
  • FEC fluoroethylene carbonate
  • Laminated lithium ion secondary batteries (WA2-WA19) were produced by the same method except that the negative electrode was changed to the negative electrode shown in Table 9.
  • Example 1278 The standard negative electrode and the positive electrode (A20) are punched into 50 mm ⁇ 45 mm and 45 mm ⁇ 40 mm, respectively, and the separator (porous polyproprene film) inserted between them is inserted into an aluminum laminated bag at 60 ° C. in an electric oven. It was dried for 1 hour. Then, in a glove box filled with argon gas, an electrolytic solution (a mixed solvent in which ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate were mixed at a ratio of 3: 5: 2 (volume ratio) was prepared, and further used as an additive.
  • an electrolytic solution a mixed solvent in which ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate were mixed at a ratio of 3: 5: 2 (volume ratio
  • VC vinyl carbonate
  • FEC fluoroethylene carbonate
  • Table 10 shows the evaluation results of the laminated lithium ion secondary batteries produced in Examples 106 to 131 and Comparative Examples 26 to 31.
  • rate characteristics those with a rate characteristic of 80% or more are ⁇ (excellent), those with a rate characteristic of 70% or more and less than 80% are ⁇ (good), those with a rate characteristic of 60% or more and less than 70% are ⁇ (possible), and less than 60%.
  • the thing was set as x (impossible).
  • the cycle characteristics are as follows: ⁇ (excellent) for cycle characteristics of 90% or more, ⁇ (good) for 85% or more and less than 90%, ⁇ (possible) for 80% or more and less than 85%, and-(impossible) for less than 80%. ..
  • it is a carbon nanotube dispersion liquid containing a carbon nanotube, a dispersant, and a solvent, and the G / D ratio of the carbon nanotube is 5 to 100, and the dispersant is based on 100 parts by mass of the carbon nanotube.
  • a carbon nanotube dispersion liquid containing 30 parts by mass or more and less than 250 parts by mass the complex elastic modulus of the carbon nanotube dispersion liquid at 25 ° C. and a frequency of 1 Hz is 5 Pa or more and less than 650 Pa, and the phase angle is 5 ° or more and less than 50 °.
  • a certain carbon nanotube dispersion liquid was used.
  • the adhesion of the electrodes tended to be improved as compared with the comparative examples.
  • a lithium ion secondary battery with excellent rate characteristics and cycle characteristics was obtained. Therefore, it has been clarified that the present invention can provide a lithium ion secondary battery having high capacity, high output and high durability, which cannot be realized by a conventional carbon nanotube dispersion liquid.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Conductive Materials (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Secondary Cells (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
PCT/JP2021/037078 2020-10-09 2021-10-07 カーボンナノチューブ分散液およびその利用 Ceased WO2022075387A1 (ja)

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EP21877686.2A EP4227368A4 (en) 2020-10-09 2021-10-07 CARBON NANOTUBE DISPERSION AND USE THEREOF
CN202511744820.6A CN121516855A (zh) 2020-10-09 2021-10-07 碳纳米管分散液及其利用
US18/021,386 US20230307653A1 (en) 2020-10-09 2021-10-07 Carbon nanotube dispersion and use thereof
KR1020237015460A KR20230084248A (ko) 2020-10-09 2021-10-07 카본나노튜브 분산액 및 그의 이용
CN202180058872.1A CN116171307B (zh) 2020-10-09 2021-10-07 碳纳米管分散液及其利用
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EP4545480A4 (en) * 2022-06-21 2026-04-01 Artience Co Ltd DISPERSED LIQUID OF CARBON NANOTUBE, ELECTRODE MIXTURE SUSPENSION, ELECTRODE FILM AND SECONDARY BATTERY

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WO2024112175A1 (ko) * 2022-11-25 2024-05-30 주식회사 베터리얼 카본블랙 분산액, 이의 제조방법, 이를 포함하는 전극 슬러리 조성물, 이를 포함하는 전극 및 이를 포함하는 이차전지
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JP7669897B2 (ja) 2020-10-09 2025-04-30 ａｒｔｉｅｎｃｅ株式会社 カーボンナノチューブ分散液およびその利用
JP2025109720A (ja) * 2020-10-09 2025-07-25 ａｒｔｉｅｎｃｅ株式会社 カーボンナノチューブ分散液およびその利用
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JP7617341B1 (ja) 2023-09-01 2025-01-17 ａｒｔｉｅｎｃｅ株式会社 カーボンナノチューブ分散組成物、合材スラリー、電極膜、および二次電池
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