WO2016104489A1 - Matériau à base de carbone pour électrode négative de cellule secondaire, substance active pour électrode négative de cellule secondaire, électrode négative de cellule secondaire et cellule secondaire - Google Patents

Matériau à base de carbone pour électrode négative de cellule secondaire, substance active pour électrode négative de cellule secondaire, électrode négative de cellule secondaire et cellule secondaire Download PDF

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WO2016104489A1
WO2016104489A1 PCT/JP2015/085798 JP2015085798W WO2016104489A1 WO 2016104489 A1 WO2016104489 A1 WO 2016104489A1 JP 2015085798 W JP2015085798 W JP 2015085798W WO 2016104489 A1 WO2016104489 A1 WO 2016104489A1
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Prior art keywords
negative electrode
secondary battery
carbon
carbon material
secondary cell
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PCT/JP2015/085798
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English (en)
Japanese (ja)
Inventor
保明 三井
竹内　健
栄造 東▲崎▼
炭山　宜也
哲志 小野
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住友ベークライト株式会社
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Priority claimed from JP2015052628A external-priority patent/JP2016122641A/ja
Application filed by 住友ベークライト株式会社 filed Critical 住友ベークライト株式会社
Publication of WO2016104489A1 publication Critical patent/WO2016104489A1/fr

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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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 material for a secondary battery negative electrode, an active material for a secondary battery negative electrode, a secondary battery negative electrode, and a secondary battery.
  • hard carbon is excellent in terms of high cycle characteristics and is expected as a carbon material for secondary battery negative electrodes.
  • the present invention has been made in view of the above problems. That is, the present invention provides a carbon material for a secondary battery negative electrode that suppresses an increase in electrical resistance during charge and discharge when used in a low temperature environment and can ensure sufficient battery performance.
  • the present invention also provides a secondary battery negative electrode active material produced by including the secondary battery negative electrode carbon material, a secondary battery negative electrode composed of the secondary battery negative electrode active material, and the second battery negative electrode active material.
  • a secondary battery using a secondary battery negative electrode is provided.
  • the carbon material for a secondary battery negative electrode of the present invention is characterized by containing carbon particles having a surface area per unit volume determined from a particle size distribution on a number basis in a range of 10,000 cm ⁇ 1 to 16000 cm ⁇ 1 .
  • the active material for secondary battery negative electrode of the present invention is characterized by containing the carbon material for secondary battery negative electrode of the present invention.
  • the secondary battery negative electrode of the present invention includes a secondary battery negative electrode active material layer containing the secondary battery negative electrode active material of the present invention, and a negative electrode current collector in which the secondary battery negative electrode active material layer is laminated. It is characterized by having.
  • the secondary battery of the present invention is characterized by comprising the secondary battery negative electrode of the present invention, an electrolytic layer, and a secondary battery positive electrode.
  • a carbon material for a secondary battery negative electrode, an active material for a secondary battery negative electrode, and a secondary battery negative electrode capable of suppressing an increase in electrical resistance during charging and discharging of the secondary battery in a low temperature environment.
  • a secondary battery negative electrode capable of suppressing an increase in electrical resistance during charging and discharging of the secondary battery in a low temperature environment.
  • FIG. 1 It is a schematic diagram which shows an example of a lithium ion secondary battery provided with the negative electrode manufactured using the carbon material of this invention.
  • the inventors examined the electrical characteristics of the secondary battery negative electrode in a low temperature environment. As a result, it was found that the conventional secondary battery negative electrode has a possibility that the electrical resistance during charging / discharging is remarkably increased and the battery characteristics are deteriorated as compared with that at normal temperature. As a result of further detailed studies, the present inventors have found that secondary battery negative electrodes used in a low temperature environment have the following problems. That is, in a low temperature environment below freezing point, in particular, -10 ° C or lower, particularly -20 ° C or lower, the electrolyte is frozen or the viscosity rises even if it is not frozen.
  • the secondary battery negative electrode carbon material of the present invention (hereinafter also simply referred to as carbon material), secondary battery negative electrode active material (hereinafter also simply referred to as negative electrode active material), secondary battery negative electrode (hereinafter simply referred to as negative electrode). And the secondary battery will be described in order.
  • the secondary battery in which the carbon material of the present invention, the negative electrode active material, or the negative electrode is used
  • the secondary battery of the present invention for example, an alkali metal secondary such as a lithium ion secondary battery or a sodium ion secondary battery is used.
  • a battery can be mentioned.
  • the secondary battery is not limited to this, and includes various types such as a secondary battery that occludes and releases other charge carriers, a non-aqueous electrolyte secondary battery, or a solid secondary battery.
  • a lithium ion secondary battery will be described as an example of a secondary battery.
  • the carbon material of the present invention comprises carbon particles having a surface area per unit volume (hereinafter, also simply referred to as a surface area per unit volume) determined from the particle size distribution on a number basis within a range of 10000 cm ⁇ 1 to 16000 cm ⁇ 1. Including.
  • the lower limit of the surface area per unit volume may be further 12000 cm ⁇ 1 or more. Further, the upper limit of the surface area per unit volume may be further 15500 cm ⁇ 1 or less, or 14000 cm ⁇ 1 or less.
  • the carbon material of the present invention is a carbon material that can be used as a material for an active material for a negative electrode.
  • the carbon material of the present invention has an effect of suppressing an increase in electric resistance (hereinafter also referred to as an electric resistance suppressing effect) during charging / discharging of the secondary battery in a low temperature environment.
  • an electric resistance suppressing effect an increase in electric resistance
  • the reason why the electrical resistance suppressing effect is exhibited in the carbon material of the present invention is not clear, but the present inventors infer as follows. That is, the carbon material of the present invention is configured such that the particle diameter is moderately small and the surface area per unit volume is sufficiently large.
  • the carbon material of the present invention has a high efficiency of occlusion and release of lithium ions, and even when the operation of lithium ions becomes dull in a low temperature environment, the occlusion and release are performed smoothly.
  • the carbon material of the present invention covers a decrease in the mobility of lithium ions in a low temperature environment by significantly increasing the surface area of the particles, which are the occlusion / release regions of lithium ions, as compared to conventional carbon materials. It is assumed that the increase in electrical resistance is suppressed.
  • the carbon material of the present invention has a surface area per unit volume of 10,000 cm ⁇ 1 or more, the total area of the particle surface, which is a lithium ion storage / release region, is sufficiently large. Thereby, the carbon material of this invention is excellent in the occlusion / release capability of lithium ion compared with the conventional carbon material, and exhibits an electrical resistance inhibitory effect also in a low temperature environment.
  • the carbon material of the present invention has a surface area per unit volume in the range of 16000 cm ⁇ 1 or less, and extremely minute carbon material particles are excluded.
  • the carbon material of the present invention specifies the upper limit of the surface area per unit volume as 16000 cm ⁇ 1 , thereby suppressing a significant increase in the self-discharge and maintaining good coatability.
  • the electrical resistance in a low temperature environment can be determined by the magnitude of the value of DC resistance (DC-IR) measured under a predetermined low temperature environment condition (for example, an environment of ⁇ 20 ° C.).
  • DC-IR DC resistance
  • the particle size distribution based on the number means the particle size distribution based on the number obtained by the laser diffraction / scattering method.
  • the particle size distribution can be measured with a laser diffraction / scattering particle size distribution measuring apparatus.
  • it can be measured by LA-920 manufactured by Horiba, Ltd.
  • the particle diameter means the diameter of the particle.
  • the surface area per unit volume determined from the particle size distribution on the basis of the number is the data obtained from the particle size distribution on the basis of the number measured by an arbitrary laser diffraction / scattering particle size distribution measuring device, It can be calculated by equation (1).
  • Area per unit volume (cm ⁇ 1 ) total surface area (cm 2 ) / total volume (cm 3 ) (1)
  • total surface area is the sum of values obtained by multiplying the surface area when particles of each particle size in the particle size distribution are converted into true spheres by the frequency (%) of particles at each particle size.
  • total volume is the sum of values obtained by multiplying the volume of particles of each particle size in the particle size distribution into true spheres by the frequency (%) of particles at each particle size.
  • Frequency is the ratio of particles at each particle diameter to the total number of particles subjected to measurement.
  • a method for obtaining a carbon material including carbon particles having a surface area per unit volume in a preferable range specified in the present invention is not particularly limited, and as an example, a pulverization treatment is appropriately performed in the process of manufacturing the carbon material. It is done. Details of the grinding process will be described later.
  • the carbon material of the present invention preferably has an average square radius (hereinafter also simply referred to as an average square radius) determined from the particle size distribution described above in a range of 1 ⁇ m 2 or more and 4 ⁇ m 2 or less. That is, when the mean square radius is 1 ⁇ m 2 or more, carbon particles contained in the carbon material are excluded from those having a remarkably small particle diameter, and deterioration of self-discharge in a high temperature environment is prevented. Maintains good coatability on electrical objects. In addition, when the mean square radius is 4 ⁇ m 2 or less, it is easy to select carbon particles whose surface area per unit volume falls within a preferable range specified by the present invention.
  • the upper limit of the mean square radius is more preferably 3 ⁇ m 2 or less, and even more preferably 2 ⁇ m 2 or less.
  • the sum of the squares of the radii of each particle ( ⁇ m 2 ) is a value that is a half of each particle diameter in the particle size distribution, and the value obtained by squaring this value is the particle at each particle diameter. The sum of the values multiplied by the frequency (%).
  • One of the preferable aspects of the carbon material of the present invention is such that the true specific gravity of the carbon particles contained in the carbon material is in the range of 1.5 g / cm 3 or more and 1.7 g / cm 3 or less.
  • the true specific gravity of the carbon particles contained in the carbon material is in the range of 1.5 g / cm 3 or more and 1.7 g / cm 3 or less.
  • the true specific gravity can be determined by a true specific gravity measurement method using butanol.
  • the method for adjusting the carbon particles contained in the carbon material of the present invention to have a true specific gravity within the above preferable range is not particularly limited. It is possible to adjust the specific gravity.
  • the carbon material of the present invention contains carbon as a main material, and may further contain components other than carbon as necessary.
  • carbon is a main material” means that carbon is contained in an amount of 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more when the carbon material is 100% by mass.
  • the carbon contained in the carbon material in the present invention is carbon particles that are substantially granular.
  • the carbon material in the present invention may contain the carbon particles and an optional additive, or may be substantially composed only of carbon particles.
  • the optional component other than carbon in the carbon material is not particularly limited, and examples thereof include nitrogen and phosphorus.
  • nitrogen in the carbon material electrical characteristics suitable for the carbon material (particularly, carbon material containing hard carbon) can be imparted due to the electronegativity of nitrogen. Thereby, occlusion / release of the lithium ion with respect to a carbon material is accelerated
  • phosphorus is contained in a carbon material (particularly, a carbon material containing hard carbon), it is possible to increase the occlusion amount of lithium ions in the negative electrode active material containing the carbon material.
  • any additive such as a curing agent and an additive can be appropriately used in addition to the carbon material, and a part of the additive remains in the carbon material. It is not excluded that the present invention.
  • the carbon used as the main material can be appropriately selected and used as long as it is a material of the negative electrode active material and can absorb and release chemical species such as lithium ions. Specific examples include hard carbon and graphite, but are not limited thereto.
  • the carbon particles contained in the carbon material are obtained by an X-ray diffraction method using CuK ⁇ rays as a radiation source, and an average interplanar spacing d 002 of (002) planes. May contain hard carbon having a thickness of 0.340 nm or more.
  • Hard carbon is a carbon material obtained by firing a polymer that does not easily develop a graphite crystal structure, and is an amorphous substance.
  • the hard carbon is a carbon material that does not have a graphene structure or carbon that only partially has a graphene structure, and has the specific average interplanar spacing d 002 .
  • the average interplanar spacing d 002 of hard carbon is 0.340 nm or more, especially 0.360 nm or more, the shrinkage / expansion between layers due to occlusion of lithium ions is difficult to occur. it can.
  • the upper limit of the average interplanar distance d 002 is not particularly defined, but can be set to 0.390 nm or less, for example.
  • the average spacing d 002 is 0.390nm or less, particularly when it is 0.380nm or less performed smoothly absorbing and releasing lithium ions, it is possible to suppress the deterioration of the charge-discharge efficiency.
  • the hard carbon has a crystallite size Lc of 0.8 nm or more and 5 nm or less in the c-axis direction ((002) plane orthogonal direction).
  • Lc By setting Lc to 0.8 nm or more, particularly 0.9 nm or more, there is an effect that a space between carbon layers capable of occluding and releasing lithium ions is formed, and a sufficient charge / discharge capacity can be obtained.
  • the thickness By setting the thickness to 0.5 nm or less, it is possible to suppress the collapse of the carbon laminate structure due to the occlusion and release of lithium ions and the reductive decomposition of the electrolytic solution, and to suppress the decrease in charge / discharge efficiency and charge / discharge cycleability.
  • Lc is calculated as follows. It was determined from the half width of the 002 plane peak and the diffraction angle in the spectrum obtained from the X-ray diffraction measurement using the following Scherrer equation.
  • Lc 0.94 ⁇ / ( ⁇ cos ⁇ ) (Scherrer equation)
  • Lc crystallite size
  • ⁇ wavelength of characteristic X-ray K ⁇ 1 output from the cathode
  • ⁇ half width of peak (radian)
  • ⁇ Reflection angle of spectrum
  • the X-ray diffraction spectrum of hard carbon can be measured by, for example, an X-ray diffraction apparatus “XRD-7000” manufactured by Shimadzu Corporation.
  • the method for measuring the average spacing in hard carbon is as follows.
  • the average interplanar spacing d can be calculated from the following Bragg equation as follows.
  • the carbon particles, which are hard carbon, have the property that lithium ions can be occluded and released over the entire surface. Therefore, the carbon material containing the carbon particles of hard carbon having a surface area per unit volume in the above-described range exhibits a remarkable effect of being excellent in the ability to occlude and release lithium ions by increasing the surface area. That is, the carbon material of the present invention containing carbon particles that are hard carbon sufficiently enjoys the action produced by the configuration of the present invention and exhibits excellent effects.
  • carbon particles which are hard carbon
  • the carbon particles, which are hard carbon contained in the carbon material of the present invention are finely divided to such an extent that the surface area per unit volume is sufficiently increased. can do.
  • the carbon particles that are hard carbon have a remarkable improvement in the ability to occlude and release lithium ions.
  • the carbon particles in the present invention may contain 90% by mass or more of hard carbon.
  • the raw material of the hard carbon is not particularly limited, and examples thereof include a resin material such as a thermosetting resin or a thermoplastic resin.
  • the raw materials include petroleum-based tar or pitch produced as a by-product during ethylene production, coal tar produced during coal dry distillation, heavy component or pitch obtained by distilling off low-boiling components of coal tar, and tar obtained by coal liquefaction. Examples thereof include petroleum-based or coal-based materials such as pitch, and those obtained by crosslinking the above-described petroleum-based or coal-based materials.
  • the hard carbon raw materials described above can be used alone or in combination of two or more. Also, plant materials such as coconut shells can be used as raw materials for hard carbon.
  • thermosetting resin is not particularly limited, and examples thereof include phenolic resins such as novolac type phenolic resin and resol type phenolic resin, epoxy resins such as bisphenol type epoxy resin and novolac type epoxy resin, melamine resin, urea resin, and aniline. Examples thereof include resins, cyanate resins, furan resins, ketone resins, unsaturated polyester resins, and urethane resins.
  • the carbon material may be a modified product obtained by modifying these materials with various components.
  • thermoplastic resin is not particularly limited.
  • polyethylene polystyrene, polyacrylonitrile, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polypropylene, vinyl chloride, methacrylic resin, polyethylene terephthalate
  • AS acrylonitrile-styrene
  • ABS acrylonitrile-butadiene-styrene
  • polypropylene vinyl chloride
  • methacrylic resin polyethylene terephthalate
  • examples include polyamide, polycarbonate, polyacetal, polyphenylene ether, polybutylene terephthalate, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, polyamide imide, polyimide, and polyphthalamide.
  • thermosetting resin is preferable as the main resin used for hard carbon. Thereby, the residual carbon rate of hard carbon can be raised more.
  • thermosetting resins a resin selected from a novolak-type phenol resin, a resol-type phenol resin, a melamine resin, a furan resin, an aniline resin, or a modified product thereof is preferable as a resin that is a main component of hard carbon.
  • the curing agent can be used in combination.
  • curing agent is not specifically limited, A well-known hardening
  • curing agent in the case of a novolac type phenol resin, hexamethylenetetramine, resol type phenol resin, polyacetal, paraformaldehyde, or the like can be used as a curing agent.
  • epoxy resins use polyamine compounds such as aliphatic polyamines and aromatic polyamines, acid anhydrides, imidazole compounds, dicyandiamide, novolac-type phenol resins, bisphenol-type phenol resins, or resole-type phenol resins as curing agents. Can do.
  • nitrogen is contained in the carbon material
  • one kind of hexamethylenetetramine, aliphatic polyamine, aromatic polyamine, dicyandiamide, amine compound, ammonium salt nitrate, or nitro compound is used together with the above-described carbon material raw material. Two or more types may be used in combination.
  • a phosphorus-containing compound such as phosphoric acid, phosphate, phosphorus pentoxide, or phosphate ester may be blended together with the above-described carbon material raw material.
  • a phosphorus-containing compound such as phosphoric acid, phosphate, phosphorus pentoxide, or phosphate ester
  • phosphate ester Daihachi Chemical Industry which is a phosphate triester such as triphenyl phosphate, cresyl diphenyl phosphate or cresyl di 2,6-xylenyl phosphate, or a commercially available aromatic condensed phosphate ester Mention may be made of condensed phosphate esters such as a flame retardant “trade name: PX-200” manufactured by Co., Ltd.
  • Graphite is one of the allotropes of carbon, and is a hexagonal hexagonal plate crystal material that forms a layered lattice made of layers of six-carbon rings. It has a so-called graphene structure.
  • the graphite includes natural graphite and artificial graphite.
  • Graphite has a desirable property that there is little voltage change from the beginning of discharge to the end of discharge, and can maintain a stable high voltage until the end of discharge.
  • Part or all of the carbon particles contained in the carbon material of the present invention may be composed of graphite.
  • the carbon particles in the carbon material of the present invention may contain hard carbon and graphite from the viewpoint of providing a well-balanced carbon material by utilizing the advantages of hard carbon and graphite.
  • the aspect of the present invention that includes both hard carbon and graphite as carbon particles is the case where the hard carbon particles and the graphite particles are individually observed in the microscopic observation, and the two are fused or bound, and apparently , When observed integrally.
  • a raw material or a composition containing the raw material is prepared.
  • the said raw material is 1 type (s) or 2 or more types selected from resin or plant material etc. which become the raw material of the hard carbon mentioned above.
  • the said composition contains the said raw material and arbitrary additives.
  • a method for producing a carbon material using the composition will be described in detail. However, the curing treatment, the pulverization treatment of the cured product, and the carbonization treatment described later are substantially performed using only raw materials. The same applies to the case of manufacturing.
  • the apparatus for preparing the composition is not particularly limited.
  • a kneading apparatus such as a kneading roll, a uniaxial or biaxial kneader can be used.
  • a mixing device such as a Henschel mixer or a disperser can be used, and when performing pulverization and mixing, for example, a device such as a hammer mill or a jet mill can be used. Can do.
  • metals, pigments, lubricants, antistatic agents are prepared during the preparation of the above composition or after the curing treatment described later and before the carbonization treatment. Additives such as additives and antioxidants may be further added.
  • the composition prepared as described above is cured.
  • the raw materials contained in the composition can be cured and infusible.
  • the crushed composition or resin is prevented from being re-fused during the carbonization treatment, and carbon particles having a desired particle diameter are efficiently obtained. Obtainable.
  • the conditions for the curing treatment are not particularly limited, for example, heating can be performed for 1 hour or more and 10 hours or less at a temperature (for example, 200 ° C. or more and 600 ° C. or less) at which a raw material contained in the composition can cause a curing reaction.
  • the heating device used in the curing process is not particularly limited, and a large continuous furnace, a medium batch furnace, or a small furnace can be appropriately selected and used.
  • the pulverization treatment is generally performed after the above curing treatment and before the carbonization treatment described later. However, in the production of the carbon material of the present invention, the curing treatment is omitted, and after the preparation of the raw material or the composition, the carbonization treatment is performed. A pulverization process can also be performed before.
  • a carbon material containing carbon particles having a surface area per unit volume within a predetermined range specified by the present invention can be produced.
  • the pulverization conditions may be appropriately changed depending on the type of raw materials used, and are not limited to the predetermined conditions.
  • prescribed range can be easily manufactured by performing a grinding
  • the pulverization method in the pulverization process is not particularly limited, and for example, an arbitrary pulverizer can be used.
  • the pulverizer include impact mills such as ball mills, vibrating ball mills, rod mills, and bead mills, and airflow pulverizers such as cyclone mills, jet mills, and dry air pulverizers. It is not limited.
  • these devices may be used alone or in combination of two or more, or may be used by pulverizing a plurality of times with one device.
  • classification may be appropriately performed using a sieve or a pulverization apparatus having a classification function may be used.
  • the carbonization process In order to produce a carbon material containing hard carbon, the composition or a cured product of the composition is carbonized.
  • the carbonization treatment may be performed once or twice or more.
  • the pre-carbonization treatment may be performed at a relatively low temperature (for example, 200 ° C. or more and less than 800 ° C.), and then the carbonization treatment may be performed at a high temperature (for example, 800 ° C. or more and 3000 ° C. or less).
  • the conditions for the carbonization treatment are not particularly limited.
  • the temperature is raised from normal temperature to a temperature increase rate in the range of 1 ° C./hour to 200 ° C./hour, and the temperature in the range of 800 ° C. to 3000 ° C. is set for 0.1 hour. It can be carried out by holding for not less than 50 hours, preferably not less than 0.5 hours and not more than 10 hours.
  • the atmosphere during the carbonization treatment is not particularly limited.
  • a reducing gas atmosphere mainly containing.
  • the carbon material of the present invention containing hard carbon carbon particles can be produced by the above production method.
  • the carbon material of the present invention containing hard carbon and graphite can be produced by preliminarily blending graphite with a composition as a raw material.
  • the carbon material of the present invention containing hard carbon and graphite is mixed with the carbon material containing hard carbon carbon particles obtained as described above and mixed with graphite pulverized to an appropriate particle size. It can also be manufactured.
  • the negative electrode active material of the present invention including the carbon material of the present invention
  • the secondary battery negative electrode of the present invention including the negative electrode active material layer including the negative electrode active material
  • the present invention including the secondary battery negative electrode.
  • the secondary battery will be described.
  • the active material for secondary battery negative electrode of the present invention contains the carbon material for secondary battery negative electrode of the present invention described above.
  • the negative electrode active material of the present invention suppresses a significant increase in electrical resistance in a low temperature environment of the negative electrode, and has excellent charge and discharge efficiency.
  • the negative electrode active material refers to a material that can occlude and release chemical species as a charge carrier in a secondary battery negative electrode. Examples of the chemical species include lithium ions or sodium ions in an alkali metal ion secondary battery.
  • the negative electrode active material is a substance that can occlude and release chemical species such as alkali metal ions (for example, lithium ions or sodium ions) in a secondary battery such as an alkali metal ion battery.
  • alkali metal ions for example, lithium ions or sodium ions
  • the negative electrode active material described in this specification means a material containing a carbon material produced using the resin composition or the like of the present invention.
  • the negative electrode active material may be substantially composed of only the carbon material of the present invention, but may further include a material different from the carbon material.
  • examples of such materials include materials generally known as negative electrode materials such as silicon, silicon monoxide, and other graphite materials.
  • the particle size (average particle size) at 50% accumulation in the volume-based particle size distribution of the graphite material used is preferably 2 ⁇ m or more and 50 ⁇ m or less, more preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the secondary battery negative electrode of the present invention is a negative electrode current collector in which a secondary battery negative electrode active material layer including the above-described secondary battery negative electrode active material of the present invention and a secondary battery negative electrode active material layer are laminated. And is configured. Moreover, the secondary battery of this invention is comprised including the secondary battery negative electrode of this invention mentioned above, an electrolysis layer, and a secondary battery positive electrode.
  • the negative electrode of the present invention is configured using the negative electrode active material of the present invention, thereby exhibiting an effect of suppressing electrical resistance in a low temperature environment.
  • the secondary battery of the present invention including the negative electrode of the present invention reflects the above-described effects of the negative electrode, and can suppress an increase in battery resistance even under a low temperature environment, and can exhibit excellent input / output characteristics and cycle characteristics.
  • the secondary battery examples include, but are not limited to, alkali metal secondary batteries such as lithium ion secondary batteries and sodium ion secondary batteries.
  • the secondary battery includes various types using different electrolytes such as a non-aqueous electrolyte secondary battery and a solid secondary battery. In the following description, a lithium ion secondary battery will be described as an example of a secondary battery.
  • FIG. 1 is a schematic diagram showing an example of a lithium ion secondary battery 100 including the carbon material of the present invention.
  • the lithium ion secondary battery 100 includes a negative electrode 10, a positive electrode 20, a separator 30, and an electrolytic layer 40.
  • the negative electrode 10 includes a negative electrode active material layer 12 and a negative electrode current collector 14.
  • the negative electrode active material layer 12 contains the above-described carbon material (not shown) of the present invention.
  • the negative electrode current collector 14 is not particularly limited, and a current collector that can be used for the negative electrode can be appropriately selected and used. For example, a copper foil or a nickel foil can be used, but is not limited thereto.
  • the negative electrode 10 can be manufactured as follows, for example.
  • organic polymer binders for example, fluoropolymers such as polyvinylidene fluoride and polytetrafluoroethylene, styrene-butadiene rubber, butyl rubber, 1 to 30 parts by mass of a rubbery polymer such as butadiene rubber
  • a viscosity adjusting solvent N-methyl-2-pyrrolidone, dimethylformamide, alcohol, water, etc.
  • a electrically conductive material further with respect to the active material for negative electrodes mentioned above as needed.
  • the conductive material for example, any one of acetylene black, ketjen black, vapor grown carbon fiber, or a combination of two or more thereof can be used.
  • the compounding quantity of a electrically conductive material is not specifically limited, For example, 2 mass parts or more and 10 mass parts or less are preferable with respect to 100 mass parts of negative electrode active materials, More preferably, they are 3 mass parts or more and 7 mass parts or less. Although it can be used outside these ranges, if the amount of the conductive agent is too large, the amount of the negative electrode active material present in the electrode may be reduced more than necessary, and the electric capacity of the negative electrode may be reduced. .
  • the obtained slurry can be formed into a sheet shape, a pellet shape, or the like by compression molding, roll molding, or the like, and the negative electrode active material layer 12 can be obtained.
  • the negative electrode 10 can be obtained by laminating the negative electrode active material layer 12 and the negative electrode current collector 14 thus obtained. Moreover, the negative electrode 10 can also be manufactured by apply
  • the electrolytic layer 40 fills between the positive electrode 20 and the negative electrode 10, and is a layer in which lithium ions move by charge / discharge.
  • Electrolytic layer 40 is not particularly limited, and can be generally formed by filling a known electrolyte.
  • a known electrolyte for example, a nonaqueous electrolytic solution in which a lithium salt serving as an electrolyte is dissolved in a nonaqueous solvent is used.
  • non-aqueous solvent examples include cyclic esters such as propylene carbonate, ethylene carbonate, and ⁇ -butyrolactone; chain esters such as dimethyl carbonate and diethyl carbonate; chain ethers such as dimethoxyethane; or a mixture thereof. Can be used.
  • electrolytes generally be a known electrolyte, for example, it may be used lithium metal salt such as LiClO 4, LiPF 6.
  • the electrolytic layer 40 has a gel polymer electrolyte containing a polymer material such as polyethylene oxide or polyacrylonitrile, or a solid such as zirconia.
  • a polymer material such as polyethylene oxide or polyacrylonitrile
  • a solid such as zirconia
  • the separator 30 is not particularly limited, and can be a member that is permeable to chemical species such as lithium ions, and a generally known separator can be used.
  • a porous film constituted by using polyethylene or polypropylene, Nonwoven fabrics can be mentioned.
  • the positive electrode 20 includes a positive electrode active material layer 22 and a positive electrode current collector 24. It does not specifically limit as the positive electrode active material layer 22, Generally, it can form with a well-known positive electrode active material. Is not particularly limited as the cathode active material include lithium cobalt oxide (LiCoO 2), lithium nickel oxide (LiNiO 2), composite oxides such as lithium manganese oxide (LiMn 2 O 4); polyaniline, polypyrrole, etc. Or the like can be used.
  • the positive electrode active material contains an organic polymer binder and a conductive material in the same manner as the negative electrode active material described above. The blending amounts of the organic polymer binder and the conductive material in the positive electrode active material are not particularly limited, and may be the same as the negative electrode active material or may be blended in an amount different from the negative electrode active material.
  • the positive electrode current collector 24 is not particularly limited, and generally known positive electrode current collectors can be used.
  • aluminum foil, stainless steel foil, titanium foil, nickel foil, copper foil, and the like can be used.
  • the positive electrode 20 in the present embodiment can be manufactured by a generally known positive electrode manufacturing method.
  • the lithium ion secondary battery 100 has been described above as an example, but the above does not exclude that the carbon material of the present invention, the negative electrode active material, and the negative electrode are used for secondary batteries other than lithium ion secondary batteries. Absent.
  • the carbon material of the present invention can also be used for a secondary battery using alkali ions other than lithium ions such as sodium ions as chemical species.
  • each alkaline ion secondary battery may be configured using a member similar to the member used for the lithium ion secondary battery 100 described above, or may be configured using a different member.
  • an aluminum foil can be selected in addition to the negative electrode current collector exemplified above.
  • the secondary battery can be formed by appropriately disposing the negative electrode 10, the positive electrode 20, the separator 30, and the electrolytic layer 40 in a case suitable for the secondary battery.
  • the type of the secondary battery is not specified, and examples thereof include a cylindrical type, a coin type, a square type, and a film type.
  • FIG. 1 an example in which the negative electrode active material layer 12 is formed on one surface of the negative electrode current collector 14 and the positive electrode active material layer 22 is formed on one surface of the positive electrode current collector 24. Indicated. As a modification, the negative electrode active material layer 12 is formed on both surfaces of the negative electrode current collector 14, the positive electrode active material layer 22 is formed on both surfaces of the positive electrode current collector 24, and these are interposed via the separator 30 and the electrolytic layer 40. You may comprise a secondary battery by making it oppose. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
  • a carbon material for a secondary battery negative electrode (hereinafter, also referred to as a carbon material) used in Examples or Comparative Examples was prepared as follows.
  • a resin (carbon material raw material) blended in a resin composition used for producing a carbon material was prepared as follows. (Synthesis of aniline resin) 100 parts of aniline, 697 parts of 37% formaldehyde aqueous solution, and 2 parts of oxalic acid were placed in a three-necked flask equipped with a stirrer and a condenser, reacted at 100 ° C. for 3 hours, and dehydrated to obtain 110 parts of aniline resin.
  • Example 1 A resin composition obtained by blending 10 parts of hexamethylenetetramine with 100 parts of the above aniline resin and pulverizing and mixing with a vibration ball mill was used at room temperature to 100 under a nitrogen atmosphere using a large continuous furnace. The temperature was raised at a rate of temperature rise of °C / hour, and after reaching 550 ° C., the fired state was maintained for 1.5 hours to carry out the curing treatment.
  • Example 2 The curing process was performed under the same first firing conditions as in Example 1.
  • Example 3 To 100 parts of the novolak type phenol resin, 10 parts of triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: TPP) and 3 parts of hexamethylenetetramine were blended, and a vibration ball mill was used. The resin composition obtained by pulverization and mixing was heated from room temperature to a temperature increase rate of 100 ° C./hour in a nitrogen atmosphere using a medium-sized batch furnace. After reaching 550 ° C., the fired state was maintained for 1.5 hours. It was held and cured.
  • Example 4 A curing treatment was performed under the same first firing conditions as in Example 3.
  • Example 5 After performing infusibilization treatment on coconut shells, the temperature was increased from room temperature to 100 ° C./hour in a nitrogen atmosphere using a medium-sized batch furnace, and after reaching 550 ° C., the firing state was 1 Curing treatment was carried out for 5 hours.
  • Comparative Example 1 The curing treatment was performed under the same first firing conditions as in Example 1.
  • Comparative Example 2 The curing process was performed under the same first firing conditions as in Example 1.
  • Comparative Example 3 The curing process was performed under the same first firing conditions as in Example 3.
  • Comparative Example 4 The curing treatment was performed under the same first firing conditions as in Example 3.
  • Comparative Example 5 Curing treatment was performed under the same first firing conditions as in Example 3.
  • Comparative Example 6 Curing treatment was performed under the same first firing conditions as in Example 3.
  • Comparative Example 7 The curing process was performed under the same first firing conditions as in Example 5.
  • Example 1 Using an ACM pulverizer, pulverization was performed under the conditions of a powder supply rate of 1000 g / min, an air volume of 20 m 3 / min, a pulverization rotor rotation speed of 6500 rpm, and a classification rotor rotation speed of 4500 rpm, and further pulverization using a jet mill.
  • a pulverized intermediate obtained by pulverizing under the conditions of a supply amount of 80 g / min, a pulverization pressure of 0.8 MPa, and a repetition rate of 2 Pass was obtained by removing coarse particles through a sieve having an opening of 75 ⁇ m.
  • Example 2 Using an ACM pulverizer, pulverization was performed under the conditions of a powder supply rate of 1000 g / min, an air volume of 20 m 3 / min, a pulverization rotor rotation speed of 6500 rpm, and a classification rotor rotation speed of 4500 rpm, and further pulverization using a jet mill.
  • a pulverized intermediate obtained by pulverizing under the conditions of a supply amount of 80 g / min, a pulverization pressure of 0.8 MPa, and a repetition rate of 2 Pass was obtained by removing coarse particles through a sieve having an opening of 75 ⁇ m.
  • Example 3 Using a cyclone mill crusher, obtained by crushing under the conditions of powder feed rate 50 g / min, air flow rate 0.5 m 3 / min, first crushing impeller rotation speed 15000 rpm, second crushing impeller rotation speed 15000 rpm The pulverized intermediate was passed through a sieve having an opening of 75 ⁇ m to obtain a pulverized product from which coarse particles were removed.
  • Example 4 Coarse particles obtained by placing powder in a container containing 5000 g of ⁇ 15 mm alumina balls and 900 g of ⁇ 10 mm alumina balls in a ball mill pulverizer and passing through a sieve having an opening of 75 ⁇ m are coarse particles. A pulverized product from which was removed was obtained.
  • Example 5 Using an ACM pulverizer, pulverization was performed under the conditions of a powder supply rate of 1000 g / min, an air volume of 20 m 3 / min, a pulverization rotor rotation speed of 6500 rpm, and a classification rotor rotation speed of 4500 rpm, and further pulverization using a jet mill.
  • a pulverized intermediate obtained by pulverizing under the conditions of a supply amount of 80 g / min, a pulverization pressure of 0.8 MPa, and a repetition rate of 2 Pass was obtained by removing coarse particles through a sieve having an opening of 75 ⁇ m.
  • Comparative Example 1 A pulverized intermediate obtained by pulverization using an ACM pulverizer under the conditions of a powder supply rate of 1000 g / min, an air volume of 20 m 3 / min, a pulverization rotor rotation speed of 6500 rpm, and a classification rotor rotation speed of 4500 rpm, A pulverized product from which coarse particles were removed was obtained through a sieve having an opening of 75 ⁇ m.
  • Comparative Example 2 A pulverized intermediate obtained by pulverization using an ACM pulverizer under the conditions of a powder supply rate of 1000 g / min, an air volume of 20 m 3 / min, a pulverization rotor rotation speed of 6500 rpm, and a classification rotor rotation speed of 4500 rpm, A pulverized product from which coarse particles were removed was obtained through a sieve having an opening of 75 ⁇ m.
  • Comparative Example 3 Obtained by pulverization using a cyclone mill pulverizer under the conditions of a powder supply rate of 30 g / min, an air flow rate of 0.8 m 3 / min, a first pulverization impeller rotation speed of 13000 rpm, and a second pulverization impeller rotation speed of 13000 rpm.
  • the pulverized intermediate was passed through a sieve having an opening of 75 ⁇ m to obtain a pulverized product from which coarse particles were removed.
  • Comparative Example 4 Obtained by pulverization using a cyclone mill pulverizer under the conditions of a powder supply rate of 30 g / min, an air volume of 0.8 m 3 / min, a first pulverization impeller rotation speed of 13000 rpm, and a second pulverization impeller rotation speed of 13000 rpm.
  • the pulverized intermediate was passed through a sieve having an opening of 75 ⁇ m to obtain a pulverized product from which coarse particles were removed.
  • Comparative Example 5 obtained by pulverization using a cyclone mill pulverizer under the conditions of a powder supply rate of 30 g / min, an air volume of 0.8 m 3 / min, a first pulverization impeller rotation speed of 13000 rpm, and a second pulverization impeller rotation speed of 13000 rpm.
  • the pulverized intermediate was passed through a sieve having an opening of 75 ⁇ m to obtain a pulverized product from which coarse particles were removed.
  • Comparative Example 6 obtained by pulverization using a cyclone mill pulverizer under the conditions of a powder supply rate of 30 g / min, an air volume of 0.8 m 3 / min, a first pulverization impeller rotation speed of 13000 rpm, and a second pulverization impeller rotation speed of 13000 rpm.
  • the pulverized intermediate was passed through a sieve having an opening of 75 ⁇ m to obtain a pulverized product from which coarse particles were removed.
  • Comparative Example 7 Using an ACM pulverizer, pulverization was performed under the conditions of a powder supply rate of 1000 g / min, an air volume of 20 m 3 / min, a pulverizing rotor rotational speed of 6500 rpm, and a classification rotor rotational speed of 4500 rpm, and further using a cyclone classifier The pulverized intermediate from which the coarse particles were removed was passed through a sieve having an opening of 75 ⁇ m to obtain a pulverized product from which coarse particles had been removed.
  • the pulverization apparatus used in the above pulverization process is as follows.
  • ACM pulverizer an impact classifier built-in pulverizer (ACM30HC), manufactured by Hosokawa Micron Corporation) was used.
  • ACM30HC impact classifier built-in pulverizer
  • jet mill pulverizer a nano jet mizer (NJ-300 type, manufactured by Aisin Nano Technologies) was used.
  • cyclone mill a dry pulverizer (150BMW type cyclone mill, manufactured by Shizuoka Plant) was used.
  • ball mill crusher a rotary ball mill (1-stage type-B, manufactured by Irie Shokai) was used.
  • Example 1 In a large continuous furnace, firing was performed at room temperature to 100 ° C / hour in a nitrogen atmosphere, and after reaching 1200 ° C, the firing state was maintained for 2 hours for carbonization treatment. 1 carbon material was obtained.
  • Example 2 Carbonization treatment was performed under the same firing conditions as in Example 1 to obtain a carbon material of Example 2.
  • Example 3 Carbonization was performed under the same firing conditions as in Example 1 except that the large continuous furnace was changed to the small continuous furnace, and the carbon material of Example 3 was obtained.
  • Example 4 Carbonization treatment was performed under the same firing conditions as in Example 3 to obtain a carbon material of Example 4.
  • Example 5 Carbonization treatment was performed under the same firing conditions as in Example 3 to obtain a carbon material of Example 5.
  • Comparative Example 1 Carbonization was performed under the same firing conditions as in Example 1 to obtain a carbon material of Comparative Example 1.
  • Comparative Example 2 Carbonization was performed under the same firing conditions as in Example 1 to obtain a carbon material of Comparative Example 2.
  • Comparative Example 3 Carbonization was performed under the same firing conditions as in Example 3 to obtain a carbon material of Comparative Example 3.
  • Comparative Example 4 Carbonization was performed under the same firing conditions as in Example 3 to obtain a carbon material of Comparative Example 4.
  • Comparative Example 5 Carbonization was performed under the same firing conditions as in Example 3 to obtain a carbon material of Comparative Example 5.
  • Comparative Example 6 Carbonization was performed under the same firing conditions as in Example 3 to obtain a carbon material of Comparative Example 6.
  • Comparative Example 7 Carbonization was performed under the same firing conditions as in Example 3 to obtain a carbon material of Comparative Example 7.
  • half-cell lithium ion secondary batteries were prepared.
  • 100 parts of the carbon material obtained in each example and each comparative example 1.5 parts of carboxymethyl cellulose (Daicel Finechem Co., Ltd., CMC Daicel 2200), styrene-butadiene rubber (manufactured by JSR Corporation, TRD-2001) ) 1.5 parts, 2 parts of acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 100 parts of distilled water were added and stirred and mixed with a rotating / revolving mixer to prepare a slurry-like negative electrode mixture.
  • the negative electrode mixture was applied to one side of a 14 ⁇ m thick copper foil (Furukawa Electric Co., Ltd., NC-WS), followed by preliminary drying in air at 60 ° C. for 2 hours, and then at 120 ° C. for 15 hours. Vacuum dried. After vacuum drying, the electrode was pressure-formed by a roll press. This was cut into a disk shape having a diameter of 13 mm to produce a negative electrode.
  • the thickness of the negative electrode material layer was 50 ⁇ m.
  • a 1 mm thick lithium metal was prepared as a working electrode.
  • a porous polyolefin film manufactured by Celgard, trade name: Celgard 2400 was used.
  • LiPF Lithium hexafluorophosphate
  • full-cell lithium ion secondary batteries were prepared.
  • the production method was the same as that in the production method of the half-cell lithium ion secondary battery described above except that the working electrode was changed to the positive electrode.
  • a positive electrode made of LiCoO 2 as an active material and coated on a current collector was used, and a single layer sheet using an aluminum foil as a positive electrode current collector (trade name; Pioxel C, manufactured by Pionics Corporation). ⁇ 100) formed into a disk shape with a diameter of 12 mm was used.
  • Evaluation was performed as follows using each of the examples, the carbon materials of the comparative examples, and the lithium ion secondary batteries prepared using the carbon materials of the examples and the comparative examples.
  • particle size distribution measuring device LA-920 manufactured by Horiba, Ltd.
  • the particle size distribution on the basis of the number of carbon materials of each example and each comparative example was measured by the following procedure.
  • About 20 mg of the carbon material obtained as described above and each comparative example, about 1 ml of surfactant (Tween 20, manufactured by Kishida Chemical Co., Ltd.) diluted to about 1 wt%, and about 5 ml of distilled water are put in one plastic container. Then, the mixture was dispersed by applying ultrasonic waves while mixing with a poly dropper for about 1 minute in an ultrasonic cleaner to obtain a dispersion.
  • surfactant Teween 20, manufactured by Kishida Chemical Co., Ltd.
  • each lithium ion secondary battery is charged to 4.2 V at a constant current of 0.2 C in a temperature environment of 25 ° C., and then the current value is attenuated to 0.02 C at a constant voltage of 4.2 V. Charged until Next, the battery was discharged at a constant current of 0.2 C, adjusted to 50% SOC (State of Charge), and left at 25 ° C. for 1 hour. Subsequently, each full cell type lithium ion secondary battery was allowed to stand for 1 hour in a temperature environment of ⁇ 20 ° C., and the following “low temperature environment charge / discharge treatment” was performed for 3 cycles.
  • the low temperature environmental discharge treatment is performed by placing a full-cell type lithium ion secondary battery in a temperature environment of ⁇ 20 ° C., measuring a voltage when charged at a predetermined current value for 10 seconds, and then allowing to stand for 10 minutes. The voltage when discharged for 10 seconds at a predetermined current value is measured, and then left for 10 minutes.
  • the predetermined current value is 1 / 3C, 0.5C, and 1C in order from the first cycle to the third cycle.
  • the upper limit voltage was 4.2 V and the lower limit voltage was 2.5 V.
  • “1C” means a current density at which discharge is completed in one hour.
  • the horizontal axis represents the current value
  • the vertical axis represents the voltage after charging or discharging for 10 seconds
  • the DC resistance during charging and discharging in the battery from the absolute value of the slope of the approximate straight line ( DC-IR) was determined.
  • a low DC-IR means that the electrical resistance is small and the output characteristics are good.
  • the surface area per unit volume satisfied the predetermined range specified in the present invention.
  • the surface area per unit volume is out of the predetermined range.
  • the initial charge / discharge efficiency at 25 ° C. showed a high value of 84% or more, and the DC-IR during charging and discharging at ⁇ 20 ° C. tended to be low.
  • Examples 1 and 2 are compared with Comparative Examples 1 and 2 using the same material as Examples 1 and 2, the DC-IR during charging and discharging in a low temperature environment is different due to the difference in surface area. There was a significant difference.
  • Examples 1 and 2 had a larger surface area and lower DC-IR during charging / discharging than Comparative Examples 1 and 2. The same tendency was confirmed in Examples 3 and 4 and Comparative Examples 3 to 6, and Example 5 and Comparative Example 7. From the above results, in each example, the decrease in the resistance value in the low temperature environment is reduced by including the surface area within the predetermined range, and the good charge / discharge efficiency shown at 25 ° C. is significantly reflected even in the low temperature environment. It was suggested that
  • a carbon material for a secondary battery negative electrode comprising carbon particles having a surface area per unit volume determined from a particle size distribution on a number basis in a range of 10,000 cm ⁇ 1 to 16000 cm ⁇ 1 .
  • the carbon particles include hard carbon having an average interplanar spacing d 002 of (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuK ⁇ rays as a radiation source.
  • the carbon material for secondary battery negative electrode as described in any one of 3).
  • a secondary battery negative electrode active material comprising the carbon material for a secondary battery negative electrode according to any one of (1) to (6) above.
  • a secondary battery negative electrode active material layer comprising the secondary battery negative electrode active material described in (7) above, and a negative electrode current collector in which the secondary battery negative electrode active material layer is laminated.
  • a secondary battery negative electrode comprising: (9) A secondary battery comprising the secondary battery negative electrode described in (8) above, an electrolytic layer, and a secondary battery positive electrode.

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  • Inorganic Chemistry (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un matériau à base de carbone pour une électrode négative de cellule secondaire, dans lequel les augmentations de la résistance électrique pendant la charge et la décharge sont supprimées lors d'une utilisation dans des environnements à basse température, tandis que des caractéristiques de cellule adéquates peuvent être assurées; l'invention concerne également une substance active pour une électrode négative de cellule secondaire qui est obtenue en incluant le matériau à base de carbone pour une électrode négative de cellule secondaire, une électrode négative de cellule secondaire qui est conçue à l'aide de la substance active pour une électrode négative de cellule secondaire, et une cellule secondaire dans laquelle l'électrode négative de cellule secondaire est utilisée. Ce matériau de carbone pour une électrode négative de cellule secondaire comprend des particules de carbone dans laquelle la surface spécifique par unité de volume dérivée de la distribution de la taille des particules sur une base de comptage se situe dans une plage de 10000 cm-1 à 16000 cm-1, tandis que la substance active pour une électrode négative de cellule secondaire contient le matériau à base de carbone pour électrode négative de cellule secondaire. L'électrode négative de cellule secondaire (10) comprend une couche de substance active (12) pour une électrode négative de cellule secondaire qui comprend la substance active pour électrode négative de cellule secondaire, et un collecteur (14) pour électrode négative. La cellule secondaire (100) comprend cette électrode négative de cellule secondaire (10), une couche d'électrolyte (40), et une électrode positive de cellule secondaire (20).
PCT/JP2015/085798 2014-12-24 2015-12-22 Matériau à base de carbone pour électrode négative de cellule secondaire, substance active pour électrode négative de cellule secondaire, électrode négative de cellule secondaire et cellule secondaire WO2016104489A1 (fr)

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JP2014-260833 2014-12-24
JP2014260833 2014-12-24
JP2015052628A JP2016122641A (ja) 2014-12-24 2015-03-16 二次電池負極用炭素材、二次電池負極用活物質、二次電池負極および二次電池
JP2015-052628 2015-03-16

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JP2019160400A (ja) * 2018-03-07 2019-09-19 マクセルホールディングス株式会社 電気化学素子用負極およびリチウムイオン二次電池

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JP2002270159A (ja) * 2001-03-09 2002-09-20 Sony Corp 電 池
JP2012074297A (ja) * 2010-09-29 2012-04-12 Mitsubishi Chemicals Corp 非水系二次電池用複層構造炭素材、及びそれを用いた負極材並びに非水系二次電池
WO2014046077A1 (fr) * 2012-09-18 2014-03-27 株式会社クレハ Liant pour cellule secondaire à électrolyte non aqueux, solution de liant pour cellule secondaire à électrolyte non aqueux, mélange d'anode pour cellule secondaire à électrolyte non aqueux, et utilisations associées

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Publication number Priority date Publication date Assignee Title
JP2002270159A (ja) * 2001-03-09 2002-09-20 Sony Corp 電 池
JP2012074297A (ja) * 2010-09-29 2012-04-12 Mitsubishi Chemicals Corp 非水系二次電池用複層構造炭素材、及びそれを用いた負極材並びに非水系二次電池
WO2014046077A1 (fr) * 2012-09-18 2014-03-27 株式会社クレハ Liant pour cellule secondaire à électrolyte non aqueux, solution de liant pour cellule secondaire à électrolyte non aqueux, mélange d'anode pour cellule secondaire à électrolyte non aqueux, et utilisations associées

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019160400A (ja) * 2018-03-07 2019-09-19 マクセルホールディングス株式会社 電気化学素子用負極およびリチウムイオン二次電池
JP7187156B2 (ja) 2018-03-07 2022-12-12 マクセル株式会社 電気化学素子用負極およびリチウムイオン二次電池

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