WO2018037910A1 - 電池用カーボンブラック、電極用導電性組成物、電池用電極、および電池 - Google Patents
電池用カーボンブラック、電極用導電性組成物、電池用電極、および電池 Download PDFInfo
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- WO2018037910A1 WO2018037910A1 PCT/JP2017/028762 JP2017028762W WO2018037910A1 WO 2018037910 A1 WO2018037910 A1 WO 2018037910A1 JP 2017028762 W JP2017028762 W JP 2017028762W WO 2018037910 A1 WO2018037910 A1 WO 2018037910A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/54—Acetylene black; thermal black ; Preparation thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a carbon black for a battery, an electrode conductive composition using the same, a battery electrode, and a battery.
- the content of the conductive agent in the electrode mixture is typically 2 mass percent or less, and more preferably 1 mass percent or less.
- carbon black which is a conductive agent, is required to exhibit sufficient electronic conductivity even when added in a small amount.
- carbon black has a structure in which primary particles close to a spherical shape are connected on a bead as a common structure, and such a structure is called a structure.
- a structure In general, the smaller the primary particle diameter, the more electrical contacts exist in the same mass of the conductive agent, and the electronic conductivity is improved. Also, the longer the structure is connected, the greater the distance that can be conducted without contact resistance, so that the electron conductivity is improved.
- carbon black with a small primary particle size and a long structure is excellent in conductivity, but has an aspect that it is difficult to disintegrate and easily aggregate because the interaction between particles is large. Therefore, a method of applying a conductive composition for an electrode in which an active material, a conductive agent, and a binder are dispersed in water or an organic solvent to a metal foil is generally used at the time of manufacturing an electrode, but carbon having a small primary particle size and a long structure.
- black is used as the conductive agent, aggregates of the conductive agent remain in the conductive composition for the electrode, resulting in unevenness on the electrode, or the viscosity in the conductive composition for the electrode is too high to be applied. Insufficient dispersion of the conductive agent is likely to occur.
- Patent Document 1 proposes to perform kneading in two stages of kneading and dilution / dispersion.
- the carbon black having a small primary particle diameter and a long structure as described above exhibits a sufficient effect.
- Patent Document 2 As a means for overcoming the poor dispersion of the conductive agent, there is a method of adding a polyvinyl pyrrolidone polymer and a nonionic surfactant as a dispersant (Patent Document 2).
- Patent Document 3 proposes that carbon black has a crystallite diameter (La) in the range of 22 to 50 mm to exhibit high conductivity, but the dispersibility of carbon black is sufficient. The effect cannot be demonstrated.
- An object of the present invention is to provide a carbon black for a battery that has good dispersibility, electronic conductivity, and oxidation resistance in view of the above problems and circumstances.
- the conductive composition for low-viscosity electrodes produced using this carbon black, the low-resistance battery electrode produced using them, and the battery having excellent cycle characteristics and excellent high output characteristics The purpose is to provide.
- this invention which solves the said subject is comprised from the following.
- a carbon black for a battery characterized in that the number of CO 2 desorption molecules per unit is 8.0 ⁇ 10 16 to 15 ⁇ 10 16 molecules / m 2 .
- the inventors of the present invention have a BET specific surface area of 50 to 220 m 2 / g, a crystallite diameter (La) of 30 to 42 mm, and a temperature-programmed desorption gas analysis method (measurement temperature 50 ° C.).
- the carbon black for a battery having a CO 2 desorption molecule number per unit surface area of 8.0 ⁇ 10 16 to 15 ⁇ 10 16 molecules / m 2 at a temperature of up to 1200 ° C. can achieve both high dispersibility and high conductivity. I found it.
- the conductive composition for an electrode manufactured using the carbon black for a battery has a high viscosity reducing effect, the battery electrode manufactured using these has a low electrode plate resistance, the battery has a high output characteristic and a good cycle. It has the characteristics of excellent characteristics.
- the carbon black for a battery of the present invention has a BET specific surface area of 50 to 220 m 2 / g, a crystallite diameter (La) of 30 to 42 mm, and a temperature programmed desorption gas analysis method (measurement temperature 50 ° C. to
- the carbon black for batteries is characterized in that the number of CO 2 desorption molecules per unit surface area at 1200 ° C. is 8.0 ⁇ 10 16 to 15 ⁇ 10 16 molecules / m 2 .
- the carbon black for batteries in the present invention is selected from acetylene black, furnace black, channel black and the like, as is carbon black as a general battery conductive agent. Among these, acetylene black having excellent crystallinity and purity is more preferable.
- the BET specific surface area of the battery carbon black in the present invention is 50 to 220 m 2 / g, more preferably 60 to 175 m 2 / g, and still more preferably 60 to 150 m 2 / g.
- the BET specific surface area is 50 to 220 m 2 / g, more preferably 60 to 175 m 2 / g, and still more preferably 60 to 150 m 2 / g.
- the crystallite diameter (La) of the battery carbon black in the present invention is a value measured in accordance with JIS R7651. Note that La means a value obtained by measuring the crystallite diameter in the a-axis direction of the carbon black crystal layer.
- the crystallite diameter (La) of the battery carbon black in the present invention is 30 to 42 mm, preferably 34 to 40 mm.
- the crystallite diameter (La) is 30 to 42 mm or less, the particle shape becomes more rounded, so that the interparticle interaction is suppressed and high dispersibility is easily obtained.
- the crystallite diameter (La) is 30 mm or more, electrons easily move through the crystal layer, and good electron conductivity is easily obtained.
- the number of CO 2 desorbed molecules per unit surface area (CO 2 M 2 [number / m 2 ]) of the carbon black for battery in the present invention is the number of CO 2 desorbed molecules per unit mass (CO 2 M 1 [number / g]. ]) Divided by the BET specific surface area (a BET [m 2 / g]).
- CO 2 M 2 CO 2 M 1 / a BET (1)
- the number of CO 2 desorbed molecules per unit surface area by the temperature-programmed desorption gas analysis method (measurement temperature 50 ° C. to 1200 ° C.) of the carbon black for batteries in the present invention is 8.0 ⁇ 10 16 to 15 ⁇ 10 16 / m 2 , more preferably 8.0 ⁇ 10 16 to 13 ⁇ 10 16 pieces / m 2 , and even more preferably 8.0 ⁇ 10 16 to 10 ⁇ 10 16 pieces / m 2 .
- the DBP oil absorption of the carbon black for batteries in the present invention is a value measured according to JIS K6217-4.
- the DBP oil absorption amount of the carbon black for batteries in the present invention is preferably 240 to 310 mL / 100 g, and more preferably 240 to 260 mL / 100 g.
- the DBP oil absorption amount of the carbon black for batteries in the present invention is preferably 240 to 310 mL / 100 g, and more preferably 240 to 260 mL / 100 g.
- the total number of electron spins (N) per unit mass of the carbon black for a battery is a value defined as in equation (3).
- N I / I REF ⁇ ⁇ s (s + 1) ⁇ / ⁇ S (S + 1) ⁇ ⁇ N REF / M (3)
- I is the electron spin resonance (hereinafter referred to as ESR) signal intensity of the carbon black for batteries
- I REF is the ESR signal intensity of the standard sample
- s is The spin quantum number of the standard sample
- N REF is the spin number of the standard sample
- M is the mass of the carbon black for batteries.
- the type of the standard sample is not particularly limited.
- a polyethylene film in which ions having a known spin quantum number are implanted by an electrochemical method can be used.
- the method for determining the spin number (N REF ) of the standard sample is not particularly limited.
- a method of measuring the concentration of ions having a known spin quantum number by titration can be used.
- the number of conduction electron spins (N c ) per unit mass of the carbon black for a battery is a value defined as in equation (4).
- N A / T + N c (4)
- the localized electron spin density per unit surface area at 23 ° C. of the battery carbon black in the present invention is preferably 8.0 ⁇ 10 16 atoms / m 2 or less, and usually 1.0 ⁇ 10 16 atoms / m 2 or more. is there.
- the localized electron spin density is smaller, the number of sites called lattice defects and edges that are liable to cause a side reaction such as a decomposition reaction of an electrolytic solution under a high voltage is reduced, and thus high oxidation resistance is easily obtained.
- a raw material gas such as hydrocarbon or natural gas is supplied from a nozzle installed at the top of a vertical reactor. Then, carbon black for a battery is manufactured by a thermal decomposition reaction and / or a combustion reaction, and collected from a bag filter directly connected to the lower part of the reaction furnace.
- the raw material gas to be used is not particularly limited, but it is preferable to use an acetylene gas having few impurities such as a sulfur content.
- a baking furnace such as a muffle furnace is used and heated at 1000 to 1500 ° C. for 1 hour or more in an inert atmosphere or in an inert air current. Thus, the sulfur content can be removed.
- hydrocarbon gas in addition to acetylene gas, oxygen gas, and water vapor, for example, hydrocarbon gas, hydrogen gas, carbon dioxide gas, or the like can be added to the raw material gas used in the production of battery carbon black in the present invention.
- hydrocarbon gas are gasified gases such as methane, ethane, propane, ethylene, propylene, butadiene, etc., and oily hydrocarbons such as benzene, toluene, xylene, gasoline, kerosene, light oil, heavy oil, etc. .
- the electrode conductive composition of the present invention comprises an active material, a polymer binder, and the above-described carbon black for a battery.
- the conductive composition for electrodes of the present invention may further contain a removable component such as a solvent. Since the conductive composition for electrodes of the present invention uses the above-described carbon black for batteries, the interparticle interaction is suppressed and the viscosity is low.
- the active material in the present invention is a composite oxide having a layered rock salt structure such as lithium cobaltate, lithium nickelate, nickel cobalt lithium manganate, nickel cobalt lithium aluminumate, etc. for positive electrode, lithium manganate, nickel manganate lithium, etc.
- Composite oxides having a spinel structure, composite oxides having an olivine structure such as lithium iron phosphate, lithium manganese phosphate, lithium manganese manganese phosphate, etc. are used as negative electrode for artificial graphite, natural graphite, soft carbon, Examples thereof include carbon-based materials such as hard carbon, metal-based materials alloyed with alkali metals such as silicon and tin, and metal composite oxides such as lithium titanate.
- the polymer binder in the present invention includes polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene copolymer, polyvinyl alcohol, acrylonitrile-butadiene copolymer, carboxylic acid-modified (meth) acrylic acid ester copolymer, etc.
- Examples include polymers.
- polyvinylidene fluoride is preferred from the viewpoint of oxidation resistance when used for the positive electrode
- polyvinylidene fluoride or styrene-butadiene copolymer is preferred from the viewpoint of adhesive strength when used for the negative electrode.
- a well-known method can be used for manufacture of the electroconductive composition for electrodes in this invention. For example, it is obtained by mixing a solvent dispersion solution of carbon black for battery, active material and polymer binder with a ball mill, sand mill, twin-screw kneader, rotation and revolution type stirrer, planetary mixer, disper mixer, etc. Specifically, it is used as a slurry.
- a solvent dispersion solution of carbon black for battery, active material and polymer binder with a ball mill, sand mill, twin-screw kneader, rotation and revolution type stirrer, planetary mixer, disper mixer, etc. Specifically, it is used as a slurry.
- carbon black for battery, active material, and polymer binder those described above may be used.
- Examples of the dispersion medium for the electrode conductive composition include water, N-methylpyrrolidone, cyclohexane, methyl ethyl ketone, and methyl isobutyl ketone.
- N-methylpyrrolidone is preferable from the viewpoint of solubility, and water is preferable when using a styrene-butadiene copolymer.
- the battery electrode of the present invention contains the above-described battery carbon black. Since the battery electrode of the present invention uses carbon black having good electron conductivity, it becomes a low resistance electrode.
- a well-known method can be used for manufacturing the battery electrode in the present invention.
- the above-described carbon black for a battery is made into a slurry-like conductive composition for an electrode by the above-described method, applied onto a current collector such as an aluminum foil or a copper foil, and then the solvent contained in the slurry is removed by heating. Then, an electrode mixture layer, which is a porous body in which the active material is bound to the surface of the current collector through a polymer binder, is formed.
- the target battery electrode can be obtained by pressurizing the current collector and the electrode mixture layer with a roll press or the like to bring them into close contact with each other.
- the battery of the present invention includes the above-described battery electrode.
- the battery of the present invention has excellent high output characteristics due to the small resistance of the electrodes, and also has good cycle characteristics due to good oxidation resistance.
- the battery manufacturing method used in the present invention is not particularly limited and may be performed using a conventionally known secondary battery manufacturing method.
- a conventionally known secondary battery manufacturing method for example, in the configuration schematically shown in FIG. Can also be produced. That is, after welding the aluminum tab 4 to the positive electrode 1 using the electrode and welding the nickel tab 5 to the negative electrode 2, the polyolefin microporous film 3 serving as an insulating layer is disposed between the electrodes, It can be prepared by injecting the positive electrode 1, the negative electrode 2, and the polyolefin microporous film 3 until the non-aqueous electrolyte is sufficiently infiltrated and sealing with the exterior 6.
- the use of the battery of the present invention is not particularly limited, for example, a digital AV camera, a video camera, a portable audio player, a portable AV device such as a portable liquid crystal television, a portable information terminal such as a notebook computer, a smartphone, a mobile PC, etc. It can be used in a wide range of fields such as portable game devices, electric tools, electric bicycles, hybrid cars, electric cars, and power storage systems.
- the raw material gas mixture ratio was 65% by volume of acetylene gas, 17.5% by volume of oxygen gas, 0% by volume of water vapor, and 17.5% by volume of toluene gas as hydrocarbon gas, and a carbon black production furnace (furnace length 5 m, furnace diameter) 0.5m) sprayed from a nozzle installed at the top of the furnace to produce carbon black for the battery using thermal decomposition and / or combustion reaction of acetylene gas, and carbon black for the battery from the bag filter directly connected to the lower part of the furnace Was collected.
- the jet speed of the raw material gas was set to 6.5 m / s by adjusting the nozzle diameter.
- the carbon black for batteries produced under the production conditions was referred to as carbon black A (CBA).
- K is a form factor constant of 0.9
- ⁇ is an X-ray wavelength of 1.54 mm
- ⁇ is an angle indicating a maximum value in the (110) plane diffraction line absorption band
- ⁇ is a half in the (110) plane diffraction line absorption band.
- the number of CO 2 desorption molecules per unit surface area measured by the temperature programmed desorption gas analysis method was measured by the following method. Using a temperature-programmed desorption gas analyzer (Electronic Science Co., Ltd., TDS1200II), 2 mg of battery carbon black was placed on a quartz sample pan, covered with a SiC lid (with a hole), then set in the chamber, The vacuum was drawn to a vacuum of 1 ⁇ 10 ⁇ 6 Pa or less. After the degree of vacuum was stabilized, the temperature was raised from a measurement temperature of 50 ° C. to 1200 ° C.
- DBP oil absorption The DBP oil absorption was measured according to JIS K6217-4. The evaluation results are shown in Table 1.
- the localized electron spin density per unit surface area at 23 ° C. was measured by the following method. Using an electron spin resonance measuring apparatus (ESP350E manufactured by Bruker) at a sample temperature of ⁇ 263, ⁇ 253, ⁇ 233, ⁇ 173, ⁇ 113, ⁇ 53, and 23 ° C. under conditions of a central magnetic field of 3383 Gauss and a magnetic field sweep width of 200 Gauss. The ESR signal of carbon black was measured. Since the ESR signal is output in a differential format, the ESR signal intensity was calculated by integrating the ESR signal twice in the entire region.
- ESR electron spin resonance measuring apparatus
- the ESR signal intensity of an ion-implanted polyethylene film having a known spin number was measured under the same conditions, and this was used as a standard sample for carbon at each temperature.
- the total electron spin number of black was calculated.
- a graph with the total electron spin number on the vertical axis and the reciprocal of the sample temperature expressed in absolute temperature on the horizontal axis was created, and the conduction electron spin number was calculated as an intercept of the regression line calculated using the method of least squares.
- the localized electron spin density was calculated by dividing the localized electron spin number obtained by subtracting the conduction electron spin number from the total electron spin number at 23 ° C. by the BET specific surface area of the carbon black for the battery. .
- the evaluation results are shown in Table 1.
- the oxidation resistance of the carbon black for batteries was measured by the following method. 100 mg of carbon black CBA for a battery, 100 mg of polyvinylidene fluoride (manufactured by Arkema, “HSV900”, hereinafter referred to as PVdF) as a polymer binder, and 300 mg of NMP as a solvent are weighed, and a rotating / revolving mixer (Sinky) After mixing until uniform using Awatori Nertaro ARV-310) manufactured by the company, it was coated on an aluminum foil so that the thickness after drying was 20 ⁇ m, and dried at 105 ° C. for 1 hour. A test piece was obtained.
- cyclic voltammetry hereinafter abbreviated as CV is performed at 2.5 ° C. at a scanning speed of 10 mV / sec at 25 ° C.
- the current value at 5.0 V was determined as the oxidative decomposition current value of the carbon black for batteries. It is judged that the lower the oxidative decomposition current value, the less oxidative decomposition is and the higher the oxidation resistance.
- the evaluation results are shown in Table 1.
- the prepared conductive composition for an electrode was formed into a film on an aluminum foil (manufactured by UACJ) having a thickness of 15 ⁇ m with an applicator, and was left to stand in a dryer and preliminarily dried at 105 ° C. for one hour. Next, the film was pressed at a linear pressure of 200 kg / cm with a roll press machine so that the thickness of the film containing an aluminum foil having a thickness of 15 ⁇ m was 60 ⁇ m. In order to remove a volatile component, it vacuum-dried at 170 degreeC for 3 hours, and obtained the electrode for batteries.
- Electrode plate resistance of battery electrodes The produced battery electrode was cut into a disk shape with a diameter of 14 mm, and the front and back surfaces were sandwiched between flat electrodes made of SUS304, using an electrochemical measurement system (Solartron Corporation, function generator 1260 and potentiogalvanostat 1287). The AC impedance was measured at 10 mV and a frequency range of 1 Hz to 100 kHz. The resistance value obtained by multiplying the obtained resistance component value by the disk-shaped area cut out was defined as an electrode plate resistance. The evaluation results are shown in Table 1.
- Tori-Taro ARV-310) was mixed until uniform. Further, SBR is weighed so that the solid content is 2% by mass, added to the above mixture, and mixed until it becomes uniform using a rotating / revolving mixer (Shinky Corp., Awatori Kentaro ARV-310). As a result, a negative electrode slurry for a non-aqueous battery was obtained. Next, a negative electrode slurry for a non-aqueous battery was formed into a film on a copper foil having a thickness of 10 ⁇ m (manufactured by UACJ) with an applicator, and allowed to stand in a dryer and pre-dried at 60 ° C. for one hour.
- the film was pressed with a roll press at a linear pressure of 100 kg / cm so that the thickness of the film including the copper foil was 40 ⁇ m.
- vacuum drying was performed at 120 ° C. for 3 hours to obtain a negative electrode.
- the battery electrode is processed to 40 ⁇ 40 mm to be a positive electrode, and the negative electrode is processed to 44 ⁇ 44 mm so that the electrode mixture coating surfaces face each other at the center. Furthermore, a polyolefin microporous film processed to 45 ⁇ 45 mm was disposed between the electrodes.
- the aluminum laminate sheet cut and processed into a 70 ⁇ 140 mm square was folded in half at the center of the long side, and placed and sandwiched so that the current collecting tab of the electrode was exposed to the outside of the laminate sheet.
- the battery performance of the fabricated battery was evaluated by the following method.
- Example 2 Carbon black for batteries was obtained in the same manner as in Example 1 except that the hydrocarbon gas of Example 1 was changed to benzene (the carbon black for batteries produced under the production conditions was carbon black B (CBB)).
- CBB carbon black B
- a conductive composition for electrodes, a battery electrode and a battery were prepared and evaluated. The evaluation results are shown in Table 1.
- Example 3 The raw material gas mixture ratio of Example 1 was changed to 69% by volume of oxygen gas and 31% by volume of hydrocarbon gas, and the hydrocarbon gas was changed to benzene (the carbon black for a battery manufactured under the manufacturing conditions was changed to carbon black C Except for (CBC), a carbon black for a battery, a conductive composition for an electrode, a battery electrode and a battery were produced in the same manner as in Example 1, and each evaluation was performed. The evaluation results are shown in Table 1.
- Example 4 The raw material gas mixing ratio in Example 1 was changed to acetylene gas 60% by volume, oxygen gas 2% by volume, water vapor 19% by volume and hydrocarbon gas 19% by volume, and the hydrocarbon gas was changed to benzene (in the production conditions) Except for the produced carbon black for battery was carbon black D (CBD)), carbon black for battery, conductive composition for electrode, battery electrode and battery were prepared in the same manner as in Example 1. Each evaluation was performed. The evaluation results are shown in Table 1.
- Example 5 The raw material gas mixing ratio in Example 1 was changed to 55% by volume of acetylene gas, 10% by volume of oxygen gas, 10% by volume of water vapor, and 25% by volume of toluene gas as a hydrocarbon gas (carbon for battery manufactured under the manufacturing conditions)
- a carbon black for a battery, a conductive composition for an electrode, a battery electrode and a battery were prepared in the same manner as in Example 1 except that the black was carbon black E (CBE).
- CBE carbon black E
- Example 6> The raw material gas mixing ratio of Example 1 was changed to 62% by volume of acetylene gas, 18% by volume of oxygen gas, 2% by volume of water vapor and 18% by volume of hydrocarbon gas, and the hydrocarbon gas was changed to benzene (in the production conditions) Except for the produced carbon black for battery was carbon black F (CBF).), Carbon black for battery, conductive composition for electrode, battery electrode and battery were prepared in the same manner as in Example 1. Each evaluation was performed. The evaluation results are shown in Table 1.
- Example 7 The raw material gas mixing ratio in Example 1 was changed to 25% by volume of acetylene gas, 40% by volume of oxygen gas, 17.5% by volume of water vapor, and 17.5% by volume of toluene gas as a hydrocarbon gas (manufactured under the production conditions).
- the battery carbon black, the electrode conductive composition, the battery electrode, and the battery were prepared in the same manner as in Example 1 except that the carbon black for the battery was carbon black G (CBG). Carried out.
- CBG carbon black G
- Example 1 The raw material gas mixing ratio in Example 1 was changed to 82% by volume of acetylene gas and 18% by volume of hydrocarbon gas, and the hydrocarbon gas was changed to benzene (the carbon black for batteries manufactured under the manufacturing conditions was changed to carbon black H Except for (CBH), a carbon black for a battery, a conductive composition for an electrode, a battery electrode and a battery were prepared in the same manner as in Example 1, and each evaluation was performed. The evaluation results are shown in Table 1. In the case of the carbon black for battery used in Comparative Example 1, the dispersibility and oxidation resistance were good, but the electron conductivity was poor and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 2 The raw material gas mixing ratio of Example 1 was changed to 67% by volume of acetylene gas, 15% by volume of oxygen gas, 15% by volume of water vapor, and 3% by volume of toluene gas as a hydrocarbon gas (carbon for battery manufactured under the manufacturing conditions)
- a carbon black for a battery, a conductive composition for an electrode, a battery electrode and a battery were prepared in the same manner as in Example 1 except that the black was carbon black I (CBI).
- CBI carbon black I
- Table 1 The evaluation results are shown in Table 1. In the case of the carbon black for battery used in Comparative Example 2, the dispersibility was poor, the viscosity was high, the oxidation resistance was poor, and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 3 The carbon black for battery of Example 1 is shown in Table 1. BET specific surface area, crystallite diameter (La), CO 2 desorption molecules per unit surface area by temperature programmed desorption gas analysis method (measurement temperature 50 ° C. to 1200 ° C.) The carbon black for the battery and the conductive composition for the electrode were prepared in the same manner as in Example 1 except that the number was changed to SuperPLi (made by Imeris) with the DBP oil absorption and the localized electron spin density per unit surface area at 23 ° C. Products, battery electrodes and batteries were prepared and evaluated. The evaluation results are shown in Table 1. In the case of the carbon black for battery used in Comparative Example 3, the dispersibility and oxidation resistance were good, but the electron conductivity was poor and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 4 The carbon black for battery of Example 1 is shown in Table 1. BET specific surface area, crystallite diameter (La), CO 2 desorption molecules per unit surface area by temperature programmed desorption gas analysis method (measurement temperature 50 ° C. to 1200 ° C.) The carbon black for the battery and the electrode in the same manner as in Example 1 except that the number was changed to ECP (manufactured by Lion Specialty Chemicals) having DBP oil absorption and localized electron spin density per unit surface area at 23 ° C. Conductive compositions, battery electrodes and batteries were prepared and evaluated. The evaluation results are shown in Table 1.
- ECP manufactured by Lion Specialty Chemicals
- Example 5 The raw material gas mixing ratio in Example 1 was changed to acetylene gas 60 volume%, oxygen gas 2 volume%, water vapor 25 volume%, and hydrocarbon gas 13 volume%, and the hydrocarbon gas was changed to benzene (in the production conditions)
- a battery carbon black, an electrode conductive composition, a battery electrode and a battery were produced in the same manner as in Example 1 except that the produced carbon black for a battery was carbon black J (CBJ).
- CBJ carbon black J
- Table 1 The evaluation results are shown in Table 1. In the case of the carbon black for battery used in Comparative Example 5, the dispersibility was poor, the viscosity was high, the oxidation resistance was poor, and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 6 The raw material gas mixing ratio in Example 1 was changed to 57% by volume of acetylene gas, 3% by volume of oxygen gas, 20% by volume of water vapor and 20% by volume of hydrocarbon gas, and the hydrocarbon gas was changed to benzene (in the production conditions)
- a battery carbon black, an electrode conductive composition, a battery electrode and a battery were produced in the same manner as in Example 1 except that the produced carbon black for a battery was carbon black K (CBK).
- CBK carbon black K
- Table 1 The evaluation results are shown in Table 1. In the case of the battery carbon black used in Comparative Example 6, the oxidation resistance was good, but the dispersibility was poor, the viscosity was high, and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 7 The raw material gas mixing ratio of Example 1 was changed to 80% by volume of acetylene gas, 5% by volume of oxygen gas, 7.5% by volume of water vapor, and 7.5% by volume of hydrocarbon gas, and the hydrocarbon gas was changed to benzene (
- the battery carbon black, the electrode conductive composition, the battery electrode, and the battery were produced in the same manner as in Example 1 except that the battery carbon black produced under the production conditions was carbon black L (CBL).
- CBL carbon black L
- Table 1 The evaluation results are shown in Table 1. In the case of the carbon black for battery used in Comparative Example 7, the dispersibility and oxidation resistance were good, but the electron conductivity was poor and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 8 The raw material gas mixing ratio in Example 1 was changed to 65% by volume of acetylene gas, 16% by volume of oxygen gas, 3% by volume of water vapor, and 16% by volume of toluene gas as a hydrocarbon gas (carbon for battery manufactured under the manufacturing conditions)
- a carbon black for a battery, a conductive composition for an electrode, a battery electrode and a battery were prepared in the same manner as in Example 1 except that the black was carbon black M (CBM).
- CBM carbon black M
- Table 1 The evaluation results are shown in Table 1. In the case of the carbon black for battery used in Comparative Example 8, the dispersibility and oxidation resistance were good, but the electron conductivity was poor and the electrode plate resistance was also high. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- Example 9 The raw material gas mixing ratio of Example 1 was changed to acetylene gas 40% by volume, oxygen gas 10% by volume, water vapor 25% by volume and hydrocarbon gas 25% by volume, and the hydrocarbon gas was changed to benzene (in the production conditions)
- a battery carbon black, an electrode conductive composition, a battery electrode and a battery were produced in the same manner as in Example 1 except that the produced carbon black for the battery was carbon black N (CBN).
- CBN carbon black N
- Each evaluation was performed.
- the evaluation results are shown in Table 1.
- the battery carbon black used in Comparative Example 9 had poor dispersibility, high viscosity, poor oxidation resistance, and high electrode plate resistance. Also in the battery evaluation, the discharge capacity maintenance rate during 3C discharge was low.
- the carbon black for batteries of Examples 1 to 7 can achieve both dispersibility, electronic conductivity and oxidation resistance as compared with the carbon blacks for batteries of Comparative Examples 1 to 9.
- the conductive composition for electrodes of the examples of the present invention had a low viscosity, and the battery electrode using the conductive composition for electrodes had a low electrode plate resistance, so that a voltage drop during discharge could be suppressed. .
- the batteries of Examples 1 to 7 were found to have higher discharge rate characteristics and higher cycle characteristics than the batteries of Comparative Examples 1 to 9. As a result, it was found that a battery using the carbon black for a battery of the present invention can suppress a decrease in output accompanying an increase in discharge current and has a long life.
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Abstract
Description
これらの技術に共通して必要となるキーデバイスの一つが電池であり、このような電池に対しては、システムを小型化するための高いエネルギー密度が求められる。また、使用環境温度に左右されずに安定した電力の供給を可能にするための高い出力特性が求められる。さらに、長期間の使用に耐えうる良好なサイクル特性等も求められている。そのため、従来の鉛蓄電池、ニッケル-カドミウム電池、ニッケル-水素電池から、より高いエネルギー密度、出力特性およびサイクル特性を有するリチウムイオン二次電池への置き換えが急速に進んでいる。
(1)BET比表面積が50~220m2/gであり、かつ結晶子径(La)が30~42Åであり、かつ昇温脱離ガス分析法(測定温度50℃~1200℃)による単位表面積あたりのCO2脱離分子数が8.0×1016~15×1016個/m2であることを特徴とする電池用カーボンブラック。
(2)DBP吸油量が240~310mL/100gであることを特徴とする(1)に記載の電池用カーボンブラック。
(3)23℃における単位表面積あたりの局在電子スピン密度が8.0×1016個/m2以下であることを特徴とする(1)または(2)に記載の電池用カーボンブラック。
(4)前記電池用カーボンブラックがアセチレンブラックであることを特徴とする(1)~(3)の何れか一項に記載の電池用カーボンブラック。
(5)活物質、高分子結着材および(1)~(4)の何れか一項に記載の電池用カーボンブラックを含むことを特徴とする電極用導電性組成物。
(6)(5)に記載の電極用導電性組成物を金属箔上に塗布してなる電池用電極。
(7)(6)に記載の電池用電極を正極または負極の少なくとも一方として用いた電池。
なお、本願明細書において、特にことわりがない限り、「~」という記号は両端の値「以上」および「以下」の範囲を意味する。例えば、「A~B」というのは、A以上、B以下であるという意味である。
本発明の電池用カーボンブラックは、BET比表面積が50~220m2/gであり、かつ結晶子径(La)が30~42Åであり、かつ昇温脱離ガス分析法(測定温度50℃~1200℃)による単位表面積あたりのCO2脱離分子数が8.0×1016~15×1016個/m2であることを特徴とする電池用カーボンブラックである。
本発明における電池用カーボンブラックの単位表面積あたりのCO2脱離分子数(CO2M2[個/m2])は単位質量あたりのCO2脱離分子数(CO2M1[個/g])をBET比表面積(aBET[m2/g])で割った式(1)のように定義される値である。
CO2M2=CO2M1/aBET (1)
なお、本発明における電池用カーボンブラックの昇温脱離ガス分析法(測定温度50℃~1200℃)による単位質量あたりのCO2脱離分子数(CO2M1[個/g])は、電池用カーボンブラックを真空下で50℃~1200℃まで昇温した際に脱離したCO2ガスを質量分析計で測定した値である。
本発明における電池用カーボンブラックの単位表面積あたりの局在電子スピン密度(Dl[個/m2])は単位質量あたりの局在電子スピン数(Nl[個/g])をBET比表面積(aBET[m2/g])で割った式(2)のように定義される値である。
Dl=Nl/aBET=(N-Nc)/aBET (2)
但し、Nは電池用カーボンブラックの単位質量あたりの総電子スピン数、Ncは電池用カーボンブラックの単位質量あたりの伝導電子スピン数である。
電池用カーボンブラックの単位質量あたりの総電子スピン数(N)は、式(3)のように定義される値である。
N=I/IREF×{s(s+1)}/{S(S+1)}×NREF/M (3)
但し、Iは電池用カーボンブラックの電子スピン共鳴(以下ESR)信号強度、IREFは標準試料のESR信号強度、Sは電池用カーボンブラックのスピン量子数(すなわちS=1/2)、sは標準試料のスピン量子数、NREFは標準試料のスピン数、Mは電池用カーボンブラックの質量である。
標準試料の種類は特に限定されるものではないが、例えば電気化学的な方法によりスピン量子数が既知のイオンを注入されたポリエチレンフィルムなどを用いることができる。また、標準試料のスピン数(NREF)を決定する方法は特に限定されるものではないが、例えば滴定法によりスピン量子数が既知のイオンの濃度を測定する方法を用いることができる。
電池用カーボンブラックの単位質量あたりの伝導電子スピン数(Nc)は式(4)のように定義される値である。
N=A/T+Nc (4)
但し、Aは定数、Tは電池用カーボンブラックの絶対温度[K]である。
すなわち、電池用カーボンブラックの伝導電子スピン数(Nc)は、例えば下記のようにして決定することができる。まず、2点以上の異なる温度で電池用カーボンブラックの総電子スピン数(N)を測定する。Nを縦軸に、絶対温度単位で表した測定温度の逆数(1/T)を横軸にとったグラフを作成する。次いでそのグラフの回帰直線を最小自乗法により求め、その切片の値(すなわち1/T=0に外挿した値)をNcとする方法である。
本発明の電極用導電性組成物は、活物質、高分子結着材、及び上記の電池用カーボンブラックを含むものである。なお、本発明の電極用導電性組成物は、溶媒などの除去可能な成分をさらに含んでいても良い。
本発明の電極用導電性組成物は、上述した電池用カーボンブラックを用いているため、粒子間相互作用が抑制されており、粘度が低いという特徴を有する。
本発明における活物質は、正極用としてコバルト酸リチウム、ニッケル酸リチウム、ニッケルコバルトマンガン酸リチウム、ニッケルコバルトアルミニウム酸リチウムなどの層状岩塩型構造を持つ複合酸化物、マンガン酸リチウム、ニッケルマンガン酸リチウムなどのスピネル型構造を持つ複合酸化物、リン酸鉄リチウム、リン酸マンガンリチウム、リン酸鉄マンガンリチウムなどのオリビン型構造を持つ複合酸化物などが、負極用として人造黒鉛、天然黒鉛、ソフトカーボン、ハードカーボンなどの炭素系材料、ケイ素、スズなどのアルカリ金属と合金化する金属系材料、チタン酸リチウムなどの金属複合酸化物などが挙げられる。
本発明における高分子結着材は、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、スチレン-ブタジエン共重合体、ポリビニルアルコール、アクリロニトリル-ブタジエン共重合体、カルボン酸変性(メタ)アクリル酸エステル共重合体等の高分子が挙げられる。これらの中では、正極に用いる場合は耐酸化性の点でポリフッ化ビニリデンが好ましく、負極に用いる場合は接着力の点でポリフッ化ビニリデンまたはスチレン-ブタジエン共重合体が好ましい。
本発明における電極用導電性組成物の製造には公知の方法を用いることができる。例えば、電池用カーボンブラック、活物質および高分子結着材の溶媒分散溶液をボールミル、サンドミル、二軸混練機、自転公転式攪拌機、プラネタリーミキサー、ディスパーミキサー等により混合することで得られ、一般的には、スラリーにして用いられる。前記の電池用カーボンブラック、活物質および高分子結着材としては、既述したものを用いれば良い。電極用導電性組成物の分散媒としては、水、N-メチルピロリドン、シクロヘキサン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。高分子結着材としてポリフッ化ビニリデンを使用する際は、溶解性の点でN-メチルピロリドンが好ましく、スチレン-ブタジエン共重合体を使用する際は水が好ましい。また、製造した電極用導電性組成物スラリーは、塗膜に欠陥が生じないようにして平滑性を確保するため、塗工前の段階で真空脱泡を行うことが好ましい。電極用導電性組成物スラリー中に気泡が存在すると、電池用電極に塗布した際に、塗膜に欠陥が生じ、平滑性を損なう原因となる。
本発明の電池用電極は、上記の電池用カーボンブラックを含むものである。本発明の電池用電極は、電子伝導性が良好なカーボンブラックを用いていることから、低抵抗な電極となる。
本発明の電池は、上記の電池用電極を備えるものである。本発明の電池は、電極の抵抗が小さいために高出力特性に優れ、耐酸化性が良好なためにサイクル特性も良好である。
原料ガス混合比をアセチレンガス65体積%、酸素ガス17.5体積%、水蒸気0体積%および炭化水素ガスとしてトルエンガス17.5体積%で混合し、カーボンブラック製造炉(炉全長5m、炉直径0.5m)の炉頂に設置されたノズルから噴霧し、アセチレンガスの熱分解および又は燃焼反応を利用して電池用カーボンブラックを製造し、炉下部に直結されたバグフィルターから電池用カーボンブラックを捕集した。なお、ノズル径の調整により原料ガスの噴出速度を6.5m/sとした。以降、該製造条件で製造された電池用カーボンブラックをカーボンブラックA(CBA)とした。
BET比表面積は、吸着ガスとして窒素を用い、相対圧p/p0=0.30±0.04の条件でBET一点法にて測定した。評価結果を表1に示す。
結晶子径(La)は、JIS R7651に準拠して測定した値である。X線回折装置(Brucker社製「D8ADVANCE」)により、CuKα線を用いて測定範囲2θ=10~40゜、スリット幅0.5゜の条件でX線回折を行い、測定した。測定角度の校正にはX線標準用シリコン(三津和化学薬品社製金属シリコン)を用いた。得られた(110)面の回折線を用いて、Scherrerの式:
La(Å)=(K×λ)/(β×cosθ) (4)
式(4)により結晶子サイズLaを求めた。但し、Kは形状因子定数0.9、λはX線の波長1.54Å、θは(110)面回折線吸収バンドにおける極大値を示す角度、βは(110)面回折線吸収バンドにおける半価幅(ラジアン)である。評価結果を表1に示す。
昇温脱離ガス分析法による単位表面積あたりのCO2脱離分子数は、以下の方法で測定した。昇温脱離ガス分析装置(電子科学社製、TDS1200II)を用いて、石英試料皿に電池用カーボンブラックを2mg載せ、SiC製の蓋(穴付き)を被せた後、チャンバー内にセットし、真空度1×10-6Pa以下まで真空に引いた。真空度が安定した後、測定温度50℃から1200℃まで昇温速度60℃/分で昇温させ、その際に脱離するCO2分子数を昇温脱離ガス分析装置にて測定した。得られたCO2分子数を電池用カーボンブラックのBET比表面積で割ることによって、単位表面積あたりのCO2脱離分子数を算出した。評価結果を表1に示す。
DBP吸油量は、JIS K6217-4に準拠して測定した。評価結果を表1に示す。
23℃における単位表面積あたりの局在電子スピン密度は、以下の方法で測定した。電子スピン共鳴測定装置(Bruker社製 ESP350E)を用いて、中心磁場3383Gauss、磁場掃引幅200Gaussの条件で、試料温度-263、-253、-233、-173、-113、-53、23℃におけるカーボンブラックのESR信号を測定した。ESR信号は微分形式で出力されるため、これを全領域で2回積分することにより、ESR信号強度を算出した。次いで、既知のスピン数をもつイオン注入されたポリエチレンフィルム(厚み300μm、スピン数5.5×1013個/g)のESR信号強度を同一条件で測定し、これを標準試料として各温度におけるカーボンブラックの総電子スピン数を算出した。次いで縦軸に総電子スピン数、横軸に絶対温度で表した試料温度の逆数を取ったグラフを作成し、最小自乗法を用いて算出した回帰直線の切片として、伝導電子スピン数を算出した。次いで23℃における総電子スピン数の値から伝導電子スピン数の値を減じることで得られる局在電子スピン数を電池用カーボンブラックのBET比表面積で割ることによって、局在電子スピン密度を算出した。評価結果を表1に示す。
電池用カーボンブラックの分散性をJIS K5600-2-5に記載される粒ゲージを用いた方法で粗粒を評価した。具体的には、電池用カーボンブラックCBAを100mgおよび溶媒としてN-メチルピロリドン(関東化学株式会社製、以下、NMPと記載)を300mg秤量して、自転公転式混合機(シンキー社製、あわとり練太郎ARV-310)を用いて、均一になるまで混合した後、スクレパーを用い、CBAとNMPの混合溶液を10mg塗布し、試料面に10mm以上連続した線状痕が、一つの溝について3本以上並んだ箇所の目盛りを測定した。粒ゲージの数値が低い程、良好な分散性を意味する。評価結果を表1に示す。
電池用カーボンブラックの耐酸化性は、以下の方法で測定した。電池用カーボンブラックCBAを100mg、高分子結着材としてポリフッ化ビニリデン(アルケマ社製、「HSV900」、以下、PVdFと記載)100mgおよび溶媒としてNMPを300mg秤量して、自転公転式混合機(シンキー社製、あわとり練太郎ARV-310)を用いて、均一になるまで混合した後、アルミ箔上に乾燥後の厚さが20μmとなるように塗工し、105℃で1時間乾燥させて試験片とした。作用極に得られた試験片、対極及び参照極にリチウム金属(本城金属社製)、電解液にエチレンカーボネート/ジエチルカーボネート=1/2(体積比)+1M LiPF6溶液(キシダ化学製、以下、電解液と記載)を用いて3極セル(東洋システム株式会社製)を組み立てた。電気化学測定システム(ソーラトロン社製、ファンクションジェネレーター1260およびポテンショガルバノスタット1287)を用いてサイクリックボルタンメトリー(以下CVと略す)を25℃で10mV/secの走査速度にて2.5V~5.0Vの範囲で行った。5.0V時の電流値を電池用カーボンブラックの酸化分解電流値と定めた。酸化分解電流値が低い程、酸化分解しにくく耐酸化性が高いと判断される。評価結果を表1に示す。
製造した電池用カーボンブラックCBA、活物質としてLiCoO2(ユミコア社製、「KD20」平均一次粒子径15μm)、溶媒としてNMP、高分子結着材としてPVdFをそれぞれ用意した。電池用カーボンブラックCBAが固形分で0.5質量%、LiCoO2が固形分で98.5質量%およびPVdFが固形分で1.0質量%になるように秤量して混合し、この混合物に固形分含有量が78質量%になるようにNMPを添加し、自転公転式混合機(シンキー社製、あわとり練太郎ARV-310)を用いて、均一になるまで混合し電極用導電性組成物を得た。
電極用導電性組成物の分散性をJIS K7244-10に記載される回転型レオメータを用いた方法で粘度を評価した。具体的には、回転型レオメータ(アントンパール社製、MCR300)を用いて、固形分含有量が78質量%の電極組成物1gをディスク上に塗布し、せん断速度を100s-1~0.01s-1まで変化させて測定を行い、せん断速度1s-1の粘度を評価した。粘度の数値が低い程、良好な分散性を意味する。評価結果を表1に示す。
調製した電極用導電性組成物を、厚さ15μmのアルミニウム箔(UACJ社製)上に、アプリケータにて成膜し、乾燥機内に静置して105℃、一時間で予備乾燥させた。次に、ロールプレス機にて200kg/cmの線圧でプレスし、厚さ15μmのアルミニウム箔を含んだ膜の厚さが60μmになるように調製した。揮発成分を除去するため、170℃で3時間真空乾燥して電池用電極を得た。
作製した電池用電極を直径14mmの円盤状に切り抜き、表裏をSUS304製平板電極によって挟んだ状態で、電気化学測定システム(ソーラトロン社製、ファンクションジェネレーター1260およびポテンショガルバノスタット1287)を用いて、振幅電圧10mV、周波数範囲1Hz~100kHzにて交流インピーダンスを測定した。得られた抵抗成分値に切り抜いた円盤状の面積を掛けた抵抗値を極板抵抗とした。評価結果を表1に示す。
溶媒として純水(関東化学社製)、負極活物質として人造黒鉛(日立化成社製、「MAG-D」)、結着材としてスチレンブタジエンゴム(日本ゼオン社製、「BM-400B」、以下、SBRと記載)、分散剤としてカルボキシメチルセルロース(ダイセル社製、「D2200」、以下、CMCと記載)をそれぞれ用意した。次いで、CMCが固形分で1質量%、人造黒鉛が固形分で97質量%となるように秤量して混合し、この混合物に純水を添加し、自転公転式混合機(シンキー社製、あわとり練太郎ARV-310)を用いて、均一になるまで混合した。さらに、SBRが固形分で2質量%となるように秤量し、上記混合物に添加し、自転公転式混合機(シンキー社製、あわとり練太郎ARV-310)を用いて、均一になるまで混合し、非水系電池用負極スラリーを得た。次いで、非水系電池用負極スラリーを、厚さ10μmの銅箔(UACJ社製)上にアプリケータにて成膜し、乾燥機内に静置して60℃、一時間で予備乾燥させた。次に、ロールプレス機にて100kg/cmの線圧でプレスし、銅箔を含んだ膜の厚さが40μmになるように調製した。残留水分を完全に除去するため、120℃で3時間真空乾燥して負極を得た。
露点-50℃以下に制御したドライルーム内で、上記電池用電極を40×40mmに加工して正極とし、上記負極を44×44mmに加工した後、電極合材塗工面が中央で対向するようにし、さらに電極間に45×45mmに加工したポリオレフィン微多孔質膜を配置した。次に70×140mm角に切断・加工したアルミラミネートシートを、長辺の中央部で二つ折りにし、電極の集電用タブがラミネートシートの外部に露出するように配置して挟み込んだ。次にヒートシーラーを用いて、アルミラミネートシートの集電用タブが露出した辺を含む2辺を加熱融着した後、加熱融着していない一辺から、2gの電解液を注液し、上記電池用電極を用いた正極、負極およびポリオレフィン微多孔膜に十分に染み込ませてから、真空ヒートシーラーにより、電池の内部を減圧しながら、アルミラミネートシートの残り1辺を加熱融着して電池を得た。
[放電レート特性(3C放電時の容量維持率)]
作製した電池を、25℃において4.35V、0.2C制限の定電流定電圧充電をした後、0.2Cの定電流で3.0Vまで放電した。次いで、放電電流を0.2C、0.5C、1C、2C、3Cと変化させ、各放電電流に対する放電容量を測定した。各測定における回復充電は4.35V、0.2C制限の定電流定電圧充電を行った。そして、0.2C放電時に対する3C放電時の容量維持率を計算した。評価結果を表1に示す。
作製した電池を、25℃において4.35V、1C制限の定電流定電圧充電をした後、1Cの定電流で3.0Vまで放電した。次いで、上記充放電を500サイクル繰り返し、放電容量を測定した。そして、1サイクル放電時に対する500サイクル放電時のサイクル後放電容量維持率を計算した。評価結果を表1に示す。
実施例1の炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックB(CBB)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。
実施例1の原料ガス混合比を酸素ガス69体積%、炭化水素ガス31体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックC(CBC)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。
実施例1の原料ガス混合比をアセチレンガス60体積%、酸素ガス2体積%、水蒸気19体積%および炭化水素ガス19体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックD(CBD)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。
実施例1の原料ガス混合比をアセチレンガス55体積%、酸素ガス10体積%、水蒸気10体積%および炭化水素ガスとしてのトルエンガス25体積%に変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックE(CBE)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。
実施例1の原料ガス混合比をアセチレンガス62体積%、酸素ガス18体積%、水蒸気2体積%および炭化水素ガス18体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックF(CBF)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。
実施例1の原料ガス混合比をアセチレンガス25体積%、酸素ガス40体積%、水蒸気17.5体積%および炭化水素ガスとしてのトルエンガス17.5体積%に変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックG(CBG)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。
実施例1の原料ガス混合比をアセチレンガス82体積%、炭化水素ガス18体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックH(CBH)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例1で用いた電池用カーボンブラックの場合、分散性および耐酸化性は良好であるが、電子伝導性に乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の原料ガス混合比をアセチレンガス67体積%、酸素ガス15体積%、水蒸気15体積%および炭化水素ガスとしてのトルエンガス3体積%に変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックI(CBI)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例2で用いた電池用カーボンブラックの場合、分散性に乏しく、粘度も高く、耐酸化性も乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の電池用カーボンブラックを表1に示すBET比表面積、結晶子径(La)、昇温脱離ガス分析法(測定温度50℃~1200℃)による単位表面積あたりのCO2脱離分子数、DBP吸油量および23℃における単位表面積あたりの局在電子スピン密度を持つSuperPLi(イメリス社製)に変更した以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例3で用いた電池用カーボンブラックの場合、分散性および耐酸化性は良好であるが、電子伝導性に乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の電池用カーボンブラックを表1に示すBET比表面積、結晶子径(La)、昇温脱離ガス分析法(測定温度50℃~1200℃)による単位表面積あたりのCO2脱離分子数、DBP吸油量および23℃における単位表面積あたりの局在電子スピン密度を持つECP(ライオン・スペシャリティ・ケミカルズ社製)に変更した以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例4で用いた電池用カーボンブラックの場合、分散性に乏しく、粘度も高く、耐酸化性も乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の原料ガス混合比をアセチレンガス60体積%、酸素ガス2体積%、水蒸気25体積%および炭化水素ガス13体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックJ(CBJ)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例5で用いた電池用カーボンブラックの場合、分散性に乏しく、粘度も高く、耐酸化性も乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の原料ガス混合比をアセチレンガス57体積%、酸素ガス3体積%、水蒸気20体積%および炭化水素ガス20体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックK(CBK)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例6で用いた電池用カーボンブラックの場合、耐酸化性は良好であるが、分散性に乏しく、粘度も高く、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の原料ガス混合比をアセチレンガス80体積%、酸素ガス5体積%、水蒸気7.5体積%および炭化水素ガス7.5体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックL(CBL)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例7で用いた電池用カーボンブラックの場合、分散性および耐酸化性は良好であるが、電子伝導性に乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の原料ガス混合比をアセチレンガス65体積%、酸素ガス16体積%、水蒸気3体積%および炭化水素ガスとしてのトルエンガス16体積%に変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックM(CBM)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例8で用いた電池用カーボンブラックの場合、分散性および耐酸化性は良好であるが、電子伝導性に乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
実施例1の原料ガス混合比をアセチレンガス40体積%、酸素ガス10体積%、水蒸気25体積%および炭化水素ガス25体積%に変更し、前記炭化水素ガスをベンゼンに変更した(該製造条件で製造された電池用カーボンブラックをカーボンブラックN(CBN)とした。)以外は、実施例1と同様な方法で電池用カーボンブラック、電極用導電性組成物、電池用電極および電池を作製し、各評価を実施した。評価結果を表1に示す。比較例9で用いた電池用カーボンブラックの場合、分散性に乏しく、粘度も高く、耐酸化性も乏しく、極板抵抗も高い値を示した。また、電池評価においても3C放電時の放電容量維持率が低い結果となった。
2 リチウムイオン電池負極
3 ポリオレフィン製微多孔膜
4 アルミ製タブ
5 ニッケル製タブ
6 外装
Claims (7)
- BET比表面積が50~220m2/gであり、結晶子径(La)が30~42Åであり、昇温脱離ガス分析法(測定温度50℃~1200℃)による単位表面積あたりのCO2脱離分子数が8.0×1016~15.0×1016個/m2である電池用カーボンブラック。
- DBP吸油量が240~310mL/100gである請求項1に記載の電池用カーボンブラック。
- 23℃における単位表面積あたりの局在電子スピン密度が8.0×1016個/m2以下である請求項1または2に記載の電池用カーボンブラック。
- 前記電池用カーボンブラックがアセチレンブラックである請求項1~3の何れか一項に記載の電池用カーボンブラック。
- 活物質、高分子結着材および請求項1~4の何れか一項に記載の電池用カーボンブラックを含む電極用導電性組成物。
- 請求項1~4の何れか一項に記載の電池用カーボンブラックを含む電池用電極。
- 請求項6記載の電池用電極を備える電池。
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CN109643802B (zh) | 2022-08-19 |
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