WO2015152093A1 - Matériau carboné pour les électrodes négatives des batteries rechargeables à électrolyte non aqueux, électrode négative pour des batteries rechargeables à électrolyte non aqueux, batterie rechargeable à électrolyte non aqueux et véhicule - Google Patents

Matériau carboné pour les électrodes négatives des batteries rechargeables à électrolyte non aqueux, électrode négative pour des batteries rechargeables à électrolyte non aqueux, batterie rechargeable à électrolyte non aqueux et véhicule Download PDF

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Publication number
WO2015152093A1
WO2015152093A1 PCT/JP2015/059773 JP2015059773W WO2015152093A1 WO 2015152093 A1 WO2015152093 A1 WO 2015152093A1 JP 2015059773 W JP2015059773 W JP 2015059773W WO 2015152093 A1 WO2015152093 A1 WO 2015152093A1
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Prior art keywords
electrolyte secondary
carbonaceous material
negative electrode
secondary battery
bet
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PCT/JP2015/059773
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English (en)
Japanese (ja)
Inventor
佳余子 岡田
誠 今治
靖浩 多田
直弘 園部
真友 小松
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Kureha Corp
Kureha Battery Materials Japan Co Ltd
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Kureha Corp
Kureha Battery Materials Japan Co Ltd
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Priority to JP2016511849A priority Critical patent/JP6605451B2/ja
Publication of WO2015152093A1 publication Critical patent/WO2015152093A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • H01M4/13—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2006/10—Solid density
    • 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
    • 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 carbonaceous material for a nonaqueous electrolyte secondary battery negative electrode, a negative electrode for a nonaqueous electrolyte secondary battery, a nonaqueous electrolyte secondary battery, and a vehicle.
  • non-aqueous electrolyte secondary batteries for example, lithium ion secondary batteries
  • a combination of an electric vehicle (EV) driven only by a motor or an internal combustion engine and a motor taking advantage of the small size and light weight.
  • EV electric vehicle
  • PHEV plug-in hybrid vehicles
  • HEV hybrid electric vehicles
  • In-vehicle lithium-ion secondary batteries are expected to improve the energy density for extending the cruising range with a single charge and to improve the input characteristics of the batteries necessary for improving the energy regeneration efficiency to further improve vehicle fuel efficiency. It is rare. In consideration of the fact that automobiles are used in cold regions, it is required to maintain high input characteristics even in a low temperature environment.
  • Non-graphitic carbon materials are broadly classified into graphitizable carbon (SC) and non-graphitizable carbon (HC), and the potential changes more slowly depending on the charging rate than graphite materials. For this reason, non-graphitic carbon materials have a wide range that can be charged with a noble potential compared to the charging potential of graphite materials, and are excellent in input characteristics, so they are suitable for secondary batteries for automotive applications that aim to improve and improve fuel efficiency. Yes.
  • Patent Document 1 discloses a nonaqueous electrolyte secondary battery in which output characteristics are improved by controlling the interparticle voids of the negative electrode by adjusting the particle size distribution.
  • Patent Document 1 does not show a result regarding a rapid input characteristic like a vehicle-mounted battery and does not intend to improve the characteristic at a low temperature.
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery negative electrode carbonaceous material having improved input characteristics per volume even in a low-temperature environment, a non-aqueous electrolyte secondary battery negative electrode, and the non-aqueous electrolyte secondary battery use
  • An object of the present invention is to provide a nonaqueous electrolyte secondary battery and a vehicle including a negative electrode.
  • the inventors have a true density ( ⁇ Bt ) determined by a butanol method of 1.50 to 2.10 g / cm 3 , a volume average particle diameter (D V50 ) of 1 to 15 ⁇ m, and adsorption of nitrogen gas.
  • the specific surface area (BET) determined by the BET method according to the above is 7.0 m 2 / g or more, the specific surface area (CAL) calculated from the particle size distribution, and the specific surface area determined by the BET method by adsorption of the nitrogen gas ( BET) ratio (CAL / BET) is 1.0 or less, it has been found that a carbonaceous material for a non-aqueous electrolyte secondary battery negative electrode having high input characteristics per volume even in a low temperature environment can be provided. It came to complete. Specifically, the present invention provides the following.
  • BET method based on adsorption of nitrogen gas with true density ( ⁇ Bt ) determined by butanol method of 1.50-2.10 g / cm 3 and volume average particle diameter (D V50 ) of 1-15 ⁇ m
  • the specific surface area (BET) determined by the above is 7.0 m 2 / g or more, the specific surface area (CAL) calculated from the particle size distribution, and the specific surface area (BET) determined by the BET method by adsorption of the nitrogen gas
  • Average layer spacing d 002 of was determined by X-ray diffraction method (002) plane is less than 0.400nm than 0.365 nm, the (1) or (2) a non-aqueous electrolyte secondary battery negative electrode according to Carbonaceous materials for use.
  • the average layer spacing d 002 of the (002) plane obtained by X-ray diffraction method is 0.340 nm or more and 0.375 nm or less, and the optically anisotropic structure observed with a 1000 times polarization microscope has a major axis of 10 ⁇ m.
  • a nonaqueous electrolyte secondary battery provided with the negative electrode described in (7) above.
  • the true density ( ⁇ Bt ) determined by the butanol method is 1.50 to 2.10 g / cm 3
  • the volume average particle diameter (D V50 ) is 1 to 15 ⁇ m
  • the adsorption of nitrogen gas The specific surface area (BET) determined by the BET method according to the above is 7.0 m 2 / g or more
  • the specific surface area (CAL) calculated from the particle size distribution
  • Carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery of the present invention has a true density ( ⁇ Bt ) determined by a butanol method of 1.50 to 2.10 g / cm 3 , the volume average particle diameter (D V50 ) is 1 to 15 ⁇ m, the specific surface area (BET) determined by the BET method by adsorption of nitrogen gas is 7.0 m 2 / g or more, and the particle size distribution The ratio between the calculated specific surface area (CAL) and the specific surface area (BET) obtained by the BET method by adsorption of nitrogen gas is 1.0 or less.
  • the true density ([rho Bt) as determined by the butanol method is less than 1.50 g / cm 3 or more 2.10 g / cm 3.
  • This true density is exhibited by an amorphous carbon material in a range lower than the true density of graphite.
  • Such a carbon material has a gentle slope of a charge / discharge curve in a potential range most used in an in-vehicle lithium ion secondary battery of 0.2 V to 1.1 V based on a lithium reference electrode. This is practically suitable in that the potential difference between the negative electrode and the positive electrode can be kept high and high input characteristics per volume can be provided in a practical state that is used in a charging range of around 50%.
  • the true density ( ⁇ Bt ) is too small, it becomes difficult to improve the electrode density, so the input density per volume becomes small and sufficient input characteristics cannot be obtained, so 1.50 g / cm 3 or more is required. preferable. More preferably, it is 1.60 g / cm 3 or more.
  • the crystal structure approaches that of the graphite material, the (002) -plane average inter-layer spacing (d 002 ) is small, and the crystallite size (Lc) in the c-axis direction is large. Since the cycle characteristics of capacity due to repeated expansion and contraction of the crystal accompanying the discharge cycle characteristics deteriorate, 2.10 g / cm 3 or less is preferable. More preferably, it is 2.00 g / cm 3 or less.
  • the carbonaceous material of the present invention has a volume average particle diameter (D V50 ) of 1 to 15 ⁇ m.
  • D V50 volume average particle diameter
  • the average particle diameter is preferably 1 to 15 ⁇ m, more preferably 1 to 10 ⁇ m, and still more preferably 1 to 5 ⁇ m.
  • the carbonaceous material of the present invention has a specific surface area (BET) determined by a BET method by adsorption of nitrogen gas of 7.0 m 2 / g or more.
  • the specific surface area (BET) determined by the BET method by nitrogen adsorption reflects the specific surface area in the particles to which nitrogen gas molecules can enter. Since it is considered that there is a good correlation between the specific surface area (BET) and the wetted area between the carbon material and the electrolyte due to the electrolyte entering the carbon material, if the specific surface area (BET) is large, the lithium ion The liquid contact area related to occlusion and release is increased, and rapid charging / discharging is possible, thereby improving the input characteristics.
  • the specific surface area (BET) is preferably 7.0 m 2 / g or more, more preferably 8.0 m 2 / g or more, and still more preferably 10.0 m 2 / g or more.
  • the carbonaceous material of the present invention has a ratio of the specific surface area (CAL) calculated from the particle size distribution to the specific surface area (BET) determined by the BET method by adsorption of nitrogen gas is 1.0 or less.
  • the specific surface area varies depending on the degree of containing a small particle size powder and its particle size distribution. In the present invention, assuming that the particles are true spheres, the particle size distribution is divided into n in each volume particle diameter range, the surface area of the particles corresponding to each volume particle diameter is obtained, and the specific surface area is obtained by adding them. (CAL) was calculated.
  • the ratio (CAL / BET) between the specific surface area per unit mass (CAL) and the specific surface area (BET) determined by the BET method by nitrogen adsorption was calculated by the following formula.
  • the result of particle size distribution was used for the sphere equivalent volume particle size ( ⁇ m) and the number frequency.
  • (CAL / BET) is 1.0, which suggests that there are no pores into which nitrogen gas molecules can enter the carbon. At this time, the number of pores into which lithium can enter is reduced, which is considered to indicate that the proportion of the pores related to occlusion and release of lithium is reduced. Such a carbonaceous material is not preferable because rapid charging / discharging becomes difficult.
  • the ratio (CAL / BET) is preferably 1.0 or less. Further, in the process of carbonization from the raw material, the remaining volatile matter tends to adhere to the particle surface, and the particle diameter becomes relatively large. Alternatively, the adhered substance functions as an adhesive and tends to generate a lump of particles.
  • this deposit obstructs the pores related to the occlusion and release of lithium, lowers the BET, and increases the resistance of the electrode, thus deteriorating the input characteristics.
  • the carbonaceous material of the present invention since the carbonaceous material of the present invention has a small amount of residual volatile matter, it has the merit that it prevents particle size increase and pore clogging due to volatile matter and prevents deterioration of input characteristics.
  • the amount of particles having a volume particle diameter of 30 ⁇ m or more is 1.0% by volume or less.
  • the present invention having a volume average particle diameter (D V50 ), specific surface area (BET), and specific surface area ratio (CAL / BET) in a predetermined range is composed of a relatively small particle diameter powder. When large particles are contained, it is difficult to satisfy these ranges, so it is preferable that a large amount of particles with a large particle size is not included. In order to improve the input characteristics, although not particularly limited, it is effective to make the active material layer of the negative electrode thin.
  • the above-mentioned carbonaceous material can be closely packed, but if so, the gaps formed between the carbonaceous powders of the negative electrode are reduced, and the movement of lithium in the electrolyte is suppressed, which affects the input characteristics.
  • the active material layer of the negative electrode is thin, the diffusion process of lithium ions is shortened. As a result, the merit of increasing the capacity per volume exceeds the disadvantage of suppressing the migration of lithium ions due to close packing. It becomes easy. From the viewpoint of forming such a thin and smooth active material layer, it is preferable that a large amount of particles having a large particle diameter is not contained. Specifically, the amount of particles having a volume particle diameter of 30 ⁇ m or more is 1.0% by volume. Or less, more preferably 0.5% by volume or less, and still more preferably 0% by volume. Such adjustment to the particle size distribution can be adjusted by adjusting the pulverization conditions in the production process or by classification after pulverization.
  • the average layer spacing of the (002) plane of the carbonaceous material shows a smaller value as the crystal perfection is higher, that of an ideal graphite structure shows a value of 0.3354 nm, and the value increases as the structure is disturbed. Tend. Therefore, the average layer spacing is effective as an index indicating the carbon structure.
  • a carbonaceous material having an average (002) plane spacing of 0.365 nm or more and 0.400 nm or less obtained by X-ray diffraction can be used. This includes, for example, non-graphitizable carbon.
  • the lower limit value of the average layer spacing is more preferably 0.370 nm or more.
  • the upper limit is more preferably 0.395 nm or less, and still more preferably 0.390 nm or less.
  • a carbonaceous material having an average (002) plane spacing of 0.340 nm or more and 0.375 nm or less determined by X-ray diffraction can be used.
  • the lower limit value of the average layer spacing is more preferably 0.345 nm or more.
  • the upper limit is preferably 0.370 nm or less, and more preferably 0.365 nm or less.
  • the structure of the optically anisotropic structure observed with a 1000 times polarizing microscope shows a fine mosaic structure composed of anisotropic units having a major axis of 10 ⁇ m or less.
  • a secondary battery including a negative electrode composed of such a carbonaceous material has good charge / discharge cycle characteristics.
  • the dimension of the anisotropic unit constituting the optically anisotropic structure is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • specific surface area (BET) (unit: m 2 / g) determined by BET method by adsorption of nitrogen gas, volume average particle diameter (D v50 ) (unit: ⁇ m), and true value determined by butanol method Using the density ( ⁇ Bt ) (unit: g / cm 3 ), the specific surface area ratio (CALC) (m 2 / g) determined from the calculation formula “6 / (D v50 ⁇ ⁇ Bt )” (m 2 / g) BET / CALC) is preferably greater than 5.5.
  • BET relates to pores into which nitrogen gas can enter
  • CALC relates to pores that are relatively large enough to allow butanol to enter because it depends on ⁇ Bt .
  • the large BET / CALC reflects the large number of pores that can enter butanol but not nitrogen, and such pores are considered to be highly involved in the insertion and release of Li. It is done. If BET / CALC is less than 5.5, rapid charge / discharge becomes difficult, which is not preferable. In this respect, it is preferably more than 5.5, more preferably 8 or more, and still more preferably 11 or more.
  • the carbonaceous material of the present invention is preferably as small as the ratio of hydrogen atoms to carbon atoms (H / C) measured by elemental analysis. Since the hydrogen content of the carbonaceous material decreases as the degree of carbonization increases, H / C tends to decrease. Therefore, H / C is effective as an index representing the degree of carbonization. Although H / C of the carbonaceous material of this invention is not limited, it is 0.10 or less, More preferably, it is 0.08 or less, Most preferably, it is 0.05 or less. When H / C exceeds 0.10, there are many functional groups in the carbonaceous material, and the irreversible capacity may increase due to reaction with lithium, which is not preferable.
  • the carbonaceous material for the negative electrode of the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but the firing conditions should be optimized while being based on a manufacturing method similar to the conventional carbon negative electrode material for the nonaqueous electrolyte secondary battery. Can be manufactured satisfactorily. Specifically, it is as follows.
  • the carbonaceous material of the present invention is produced from a carbon precursor.
  • the carbon precursor include petroleum pitch or tar, coal pitch or tar, thermoplastic resin, or thermosetting resin.
  • the thermoplastic resin polyacetal, polyacrylonitrile, styrene / divinylbenzene copolymer, polyimide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyarylate, polysulfone, polyphenylene sulfide, fluororesin, polyamideimide, or polyether Mention may be made of ether ketones.
  • thermosetting resin examples include phenol resin, amino resin, unsaturated polyester resin, diallyl phthalate resin, alkyd resin, epoxy resin, and urethane resin.
  • the “carbon precursor” means a carbonaceous material from an untreated carbonaceous material stage to a pre-stage of a carbonaceous material for a nonaqueous electrolyte secondary battery finally obtained. That is, it means all the carbonaceous matter that has not finished the final process.
  • Crosslinking treatment When petroleum pitch or tar, coal pitch or tar, or a thermoplastic resin is used as the carbon precursor, a crosslinking treatment is performed.
  • the method for the crosslinking treatment is not particularly limited, and can be performed using, for example, an oxidizing agent.
  • the oxidizing agent is not particularly limited, but as the gas, O 2 , O 3 , SO 3 , NO 2 , a mixed gas obtained by diluting these with air, nitrogen or the like, or an oxidizing gas such as air is used.
  • an oxidizing liquid such as sulfuric acid, nitric acid, or hydrogen peroxide, or a mixture thereof can be used.
  • the oxidation temperature is not particularly limited, but is preferably 120 to 400 ° C, and more preferably 150 to 350 ° C. If the temperature is lower than 120 ° C., a sufficient crosslinked structure cannot be formed and the particles are fused in the heat treatment step. On the other hand, when the temperature exceeds 400 ° C., the decomposition reaction is more than the crosslinking reaction, and the yield of the obtained carbon material is lowered.
  • Firing uses a carbon precursor as a carbonaceous material for a negative electrode of a nonaqueous electrolyte secondary battery.
  • the temperature may be once lowered after the pre-baking, pulverized, and main baking may be performed.
  • Pre-baking and main baking can be performed by a known method in the field of the present invention. For example, it can carry out according to the procedure of the main baking described below, or the procedure of preliminary baking and main baking.
  • the pulverization may be performed after the crosslinking treatment, but it is preferable to perform the pulverization after preliminary firing.
  • the carbonaceous material of the present invention is produced by a step of pulverizing a carbon precursor and a step of firing the carbon precursor.
  • the pre-baking step in the present invention is performed by baking the carbon source at 300 ° C. or higher and lower than 900 ° C.
  • volatile components such as CO 2 , CO, CH 4 , and H 2 and tar components are removed, and in the main baking, their generation can be reduced and the burden on the baking apparatus can be reduced.
  • the pre-baking temperature is less than 300 ° C., detarring becomes insufficient, and there is a large amount of tar and gas generated in the main baking process after pulverization, which may adhere to the particle surface. This is not preferable because it cannot be maintained and the battery performance is lowered.
  • the pre-baking temperature is preferably 300 ° C.
  • the pre-baking temperature is 900 ° C. or higher, more preferably 500 ° C. or higher, particularly preferably 550 ° C. or higher.
  • the pre-baking temperature is 900 ° C. or higher, the tar generation temperature region is exceeded, and the energy efficiency to be used is lowered, which is not preferable.
  • the generated tar causes a secondary decomposition reaction, which adheres to the carbon precursor and may cause a decrease in performance, which is not preferable.
  • the pre-baking temperature is too high, carbonization proceeds and the carbon precursor particles become too hard, and when pulverizing after pre-firing, it may be difficult to pulverize such as scraping the inside of the pulverizer. It is not preferable.
  • Pre-baking is performed in an inert gas atmosphere, and examples of the inert gas include nitrogen and argon. Pre-baking can also be performed under reduced pressure, for example, 10 kPa or less.
  • the pre-baking time is not particularly limited, but can be performed, for example, in 0.5 to 10 hours, and more preferably 1 to 5 hours.
  • the pulverization step in the present invention is performed in order to make the particle diameter of the carbon precursor uniform. Although it can be pulverized after carbonization by main calcination, the carbon precursor becomes hard as the carbonization reaction proceeds, and it becomes difficult to control the particle size distribution by pulverization. Is preferred.
  • the pulverizer used for pulverization is not particularly limited, and for example, a jet mill, a ball mill, a hammer mill, or a rod mill can be used.
  • classification include classification with a sieve, wet classification, and dry classification.
  • the wet classifier include a classifier using a principle such as gravity classification, inertia classification, hydraulic classification, or centrifugal classification.
  • Examples of the dry classifier include a classifier using the principle of sedimentation classification, mechanical classification, or centrifugal classification.
  • pulverization and classification can be performed using one apparatus.
  • pulverization and classification can be performed using a jet mill having a dry classification function.
  • an apparatus in which the pulverizer and the classifier are independent can be used. In this case, pulverization and classification can be performed continuously, but pulverization and classification can also be performed discontinuously.
  • the main firing step in the present invention can be performed according to a normal main firing procedure, and a carbonaceous material for a nonaqueous electrolyte secondary battery negative electrode can be obtained by performing the main firing.
  • the firing temperature is 900 to 2000 ° C. If the main calcination temperature is less than 900 ° C., many functional groups remain in the carbonaceous material and the H / C value becomes high, and the irreversible capacity increases due to reaction with lithium, which is not preferable.
  • the lower limit of the main firing temperature of the present invention is 900 ° C. or higher, more preferably 1000 ° C. or higher, and particularly preferably 1100 ° C. or higher.
  • the upper limit of the firing temperature of the present invention is 2000 ° C. or less, more preferably 1500 ° C. or less, and particularly preferably 1450 ° C. or less.
  • the main firing is preferably performed in a non-oxidizing gas atmosphere. Examples of the non-oxidizing gas include helium, nitrogen, and argon, and these can be used alone or in combination. Furthermore, the main calcination can be performed in a gas atmosphere in which a halogen gas such as chlorine is mixed with the non-oxidizing gas.
  • this baking can also be performed under reduced pressure, for example, can also be performed at 10 kPa or less.
  • the time for the main baking is not particularly limited, it can be performed, for example, in 0.1 to 10 hours, preferably 0.3 to 8 hours, and more preferably 0.4 to 6 hours.
  • a method for the crosslinking treatment there are a method using a crosslinking agent, a treatment with an oxidizing agent such as air, and the like.
  • a cross-linking agent a carbon precursor is obtained by adding a cross-linking agent to petroleum tar or pitch, or coal tar or pitch and heating and mixing to proceed with a cross-linking reaction.
  • the crosslinking agent polyfunctional vinyl monomers such as divinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate, or N, N-methylenebisacrylamide that undergo a crosslinking reaction by radical reaction can be used.
  • the crosslinking reaction with the polyfunctional vinyl monomer is started by adding a radical initiator.
  • a radical initiator ⁇ , ⁇ ′ azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauroyl peroxide, cumene hydroperoxide, 1-butyl hydroperoxide, hydrogen peroxide, or the like can be used. .
  • a carbon precursor when the crosslinking reaction is advanced by treatment with an oxidizing agent such as air, it is preferable to obtain a carbon precursor by the following method. That is, to a petroleum pitch or coal pitch, a bicyclic to tricyclic aromatic compound having a boiling point of 200 ° C. or higher or a mixture thereof is added as an additive and heated and mixed, and then molded to obtain a pitch molded body. Next, the additive is extracted and removed from the pitch molded body with a solvent having low solubility with respect to pitch and high solubility with respect to the additive to form a porous pitch, which is then oxidized with an oxidizing agent, and then carbon precursor. Get the body.
  • the purpose of the aromatic additive is to extract and remove the additive from the molded pitch molded body to make the molded body porous, to facilitate crosslinking treatment by oxidation, and to obtain a carbonaceous material obtained after carbonization. To make it porous.
  • the additive can select from 1 type, or 2 or more types of mixtures, such as naphthalene, methyl naphthalene, phenyl naphthalene, benzyl naphthalene, methyl anthracene, phenanthrene, or biphenyl, for example.
  • the amount of the aromatic additive added to the pitch is preferably in the range of 30 to 70 parts by mass with respect to 100 parts by mass of the pitch.
  • Mixing of pitch and additives is performed in a molten state by heating in order to achieve uniform mixing.
  • the mixture of pitch and additive is preferably carried out after forming the particles into particles having a particle diameter of 1 mm or less so that the additive can be easily extracted from the mixture.
  • Molding may be performed in a molten state, or may be performed by a method such as pulverizing the mixture after cooling.
  • Solvents for extracting and removing the additive from the mixture of pitch and additive include aliphatic hydrocarbons such as butane, pentane, hexane, or heptane, mixtures mainly composed of aliphatic hydrocarbons such as naphtha or kerosene, methanol, Aliphatic alcohols such as ethanol, propanol or butanol are preferred.
  • aliphatic hydrocarbons such as butane, pentane, hexane, or heptane
  • mixtures mainly composed of aliphatic hydrocarbons such as naphtha or kerosene
  • methanol methanol
  • Aliphatic alcohols such as ethanol, propanol or butanol are preferred.
  • the resulting porous pitch is then oxidized with an oxidizing agent, preferably at a temperature of 120 to 400 ° C.
  • an oxidizing agent O 2 , O 3 , NO 2 , a mixed gas obtained by diluting these with air, nitrogen, or the like, or an oxidizing gas such as air, or an oxidizing liquid such as sulfuric acid, nitric acid, or hydrogen peroxide water is used.
  • a gas containing oxygen such as air or a mixed gas of air and other gas such as combustion gas as an oxidizing agent. Is also advantageous.
  • the pitch used preferably has a softening point of 150 ° C. or higher.
  • the carbon precursor of the present invention can be obtained by carbonizing the carbon precursor subjected to the crosslinking treatment as described above at 900 ° C. to 2000 ° C. in a non-oxidizing gas atmosphere after preliminary firing. Can do.
  • the carbonaceous material of the present invention can also be obtained by carbonizing at 900 ° C. to 2000 ° C. using a resin as a precursor.
  • a resin As the resin, a phenol resin, a furan resin, or the like, or a thermosetting resin obtained by partially modifying the functional group of these resins can be used. It can also be obtained by pre-calcining the thermosetting resin at a temperature lower than 900 ° C., if necessary, pulverizing, and carbonizing at 900 ° C. to 2000 ° C.
  • an oxidation treatment may be performed at a temperature of 120 to 400 ° C. as necessary.
  • the oxidizing agent O 2 , O 3 , NO 2 , a mixed gas obtained by diluting these with air, nitrogen, or the like, or an oxidizing gas such as air, or an oxidizing liquid such as sulfuric acid, nitric acid, or hydrogen peroxide water is used.
  • a carbon precursor obtained by crosslinking a thermoplastic resin such as polyacrylonitrile or a styrene / divinylbenzene copolymer can also be used.
  • a monomer mixture obtained by mixing a radically polymerizable vinyl monomer and a polymerization initiator is added to an aqueous dispersion medium containing a dispersion stabilizer and suspended by stirring to suspend the monomer mixture into fine droplets. Then, it can be obtained by proceeding radical polymerization by raising the temperature.
  • the obtained resin can be made into a spherical carbon precursor by developing a crosslinked structure by a crosslinking treatment.
  • the crosslinking treatment can be performed in a temperature range of 120 to 400 ° C., particularly preferably 170 to 350 ° C., and more preferably 220 to 350 ° C.
  • the oxidizing agent O 2 , O 3 , SO 3 , NO 2 , a mixed gas obtained by diluting these with air, nitrogen, or the like, or an oxidizing gas such as air, or an oxidizing property such as sulfuric acid, nitric acid, hydrogen peroxide water, or the like Liquid can be used.
  • the carbon precursor that is infusible to heat as described above is pre-fired as necessary, pulverized, and carbonized at 900 ° C. to 2000 ° C. in a non-oxidizing gas atmosphere.
  • the carbonaceous material of the present invention can be obtained.
  • the pulverization step can be performed after carbonization, since the carbon precursor becomes hard as the carbonization reaction proceeds, it becomes difficult to control the particle size distribution by pulverization. It is preferable before the main baking later.
  • Negative electrode for nonaqueous electrolyte secondary battery includes the carbonaceous material for a negative electrode of a nonaqueous electrolyte secondary battery of the present invention.
  • a binder (binder) is added to the carbonaceous material, and an appropriate solvent is added and kneaded to form an electrode mixture. It can be produced by pressure molding after coating and drying.
  • an electrode having high conductivity can be produced without particularly adding a conductive additive, but for the purpose of imparting higher conductivity, an electrode is used as necessary.
  • a conductive additive can be added during preparation of the mixture.
  • the conductive assistant conductive carbon black, vapor grown carbon fiber (VGCF), nanotube, etc. can be used, and the amount added varies depending on the type of conductive assistant used, but the amount added is too small.
  • the binder is not particularly limited as long as it does not react with an electrolytic solution such as PVDF (polyvinylidene fluoride), polytetrafluoroethylene, and a mixture of SBR (styrene-butadiene rubber) and CMC (carboxymethylcellulose).
  • PVDF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • CMC carbboxymethylcellulose
  • the amount of the binder added is preferably 3 to 13% by mass, more preferably 3 to 10% by mass for the PVDF binder, although it varies depending on the type of binder used.
  • a binder using water as a solvent is often used by mixing a plurality of binders such as a mixture of SBR and CMC, and the total amount of all binders used is preferably 0.5 to 5% by mass. The amount is preferably 1 to 4% by mass.
  • the electrode active material layer is basically formed on both sides of the current collector plate, but may be on one side if necessary. A thicker electrode active material layer is preferable for increasing the capacity because fewer current collector plates and separators are required, but if the electrode layer is too thick, the larger the electrode area facing the counter electrode, the better the input characteristics. This is not preferable because the input characteristics deteriorate.
  • the thickness of the electrode layer is preferably 10 to 60 ⁇ m, more preferably 10 to 55 ⁇ m, and particularly preferably 10 to 50 ⁇ m.
  • Nonaqueous electrolyte secondary battery of the present invention includes the negative electrode for a nonaqueous electrolyte secondary battery of the present invention.
  • non-aqueous electrolyte secondary batteries Manufacture of non-aqueous electrolyte secondary batteries
  • other materials constituting the battery such as a positive electrode material, a separator, and an electrolytic solution are not particularly limited, and are nonaqueous solvents.
  • Various materials conventionally used or proposed as a secondary battery can be used.
  • a layered oxide system represented as LiMO 2 , where M is a metal: for example, LiCoO 2 , LiNiO 2 , LiMnO 2 , or LiNi x Co y Mo z O 2 (where x, y and z represent composition ratios)
  • olivine system represented by LiMPO 4 , M is metal: for example, LiFePO 4, etc.
  • spinel system represented by LiM 2 O 4 , M is a metal: for example, LiMn 2 O 4, etc.
  • the composite metal chalcogen compound is preferable, and these chalcogen compounds may be mixed if necessary.
  • These positive electrode materials are molded together with an appropriate binder and a carbon material for imparting conductivity to the electrode, and are electrically conductive.
  • the positive electrode is formed by forming a layer on the conductive current collector.
  • the nonaqueous solvent electrolyte used in combination of these positive electrode and negative electrode is generally formed by dissolving an electrolyte in a nonaqueous solvent.
  • the non-aqueous solvent include organic solvents such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, diethoxyethane, ⁇ -butyllactone, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or 1,3-dioxolane. These can be used alone or in combination of two or more.
  • the electrolyte LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiCl, LiBr, LiB (C 6 H 5 ) 4 , or LiN (SO 3 CF 3 ) 2 is used.
  • the positive electrode layer and the negative electrode layer formed as described above are generally immersed in an electrolytic solution with a liquid-permeable separator made of nonwoven fabric or other porous material facing each other as necessary. It is formed by.
  • a non-woven fabric usually used for a secondary battery or a permeable separator made of another porous material can be used.
  • a solid electrolyte made of a polymer gel impregnated with an electrolytic solution can be used instead of or together with the separator.
  • the lithium ion secondary battery of the present invention is suitable as a battery (typically a lithium ion secondary battery for driving a vehicle) mounted on a vehicle such as an automobile.
  • the vehicle according to the present invention can be targeted without particular limitation, such as a vehicle normally known as an electric vehicle, a hybrid vehicle with a fuel cell or an internal combustion engine, and at least a power supply device including the battery, An electric drive mechanism that is driven by power supply from the power supply device and a control device that controls the electric drive mechanism are provided. Further, a power generation brake or a regenerative brake may be provided, and a mechanism for converting the energy generated by braking into electricity and charging the lithium ion secondary battery may be provided. Since the hybrid vehicle has a particularly low degree of freedom in battery volume, the battery of the present invention is useful.
  • the physical property values (true density ( ⁇ Bt ), volume average particle diameter (D v50 ), BET specific surface area, specific surface area calculated from the particle diameter distribution (CALC) of the carbonaceous material for nonaqueous electrolyte secondary batteries of the present invention are as follows. ), Hydrogen / carbon atomic ratio (H / C), d 002 , charge capacity, discharge capacity, irreversible capacity, input characteristics) are described in this specification including examples.
  • the physical property values are based on values obtained by the following method.
  • the true density was measured by a butanol method according to a method defined in JIS R 7212.
  • the mass (m 1 ) of a specific gravity bottle with a side tube having an internal volume of about 40 mL is accurately measured.
  • the sample is placed flat on the bottom so as to have a thickness of about 10 mm, and its mass (m 2 ) is accurately measured.
  • light vibration is applied to the specific gravity bottle, and it is confirmed that large bubbles are not generated.
  • the bottle is placed in a vacuum desiccator and gradually evacuated to 2.0 to 2.7 kPa.
  • d is the specific gravity (0.9946) of water at 30 ° C.
  • volume average particle diameter by laser diffraction method (Volume average particle diameter by laser diffraction method ( Dv50 )) Three drops of a dispersant (cationic surfactant SN wet 366 (manufactured by San Nopco)) are added to the sample, and the sample is conditioned with the dispersant. Next, after adding pure water and dispersing with ultrasonic waves, a particle size distribution in the range of 0.02 to 1400 ⁇ m was obtained with a particle size distribution measuring instrument (“Microtrac MT3300EX” manufactured by Nikkiso Co., Ltd.). From the obtained particle size distribution, the volume average particle size Dv50 is defined as the particle size at which the volume-based cumulative volume is 50%. The amount of particles having a volume particle diameter of 30 ⁇ m or more was calculated by subtracting from 100 the cumulative value of the amount of particles having a volume particle diameter of 30 ⁇ m.
  • a dispersant cationic surfactant SN wet 366 (manufactured by San No
  • v m is the adsorption amount necessary for forming a monomolecular layer on the surface of the sample (cm 3 / g)
  • x is a relative pressure.
  • the particle size distribution was divided into n volume particle size ranges, the surface area of the particles corresponding to each volume particle size was determined, and the specific surface area was calculated by adding them.
  • the specific surface area (CAL) per unit mass is calculated by the following formula.
  • the sphere equivalent volume particle size ( ⁇ m) and the number frequency can be calculated from the particle size distribution.
  • the carbonaceous material powder was filled in the sample holder and measured by a symmetrical reflection method using X'Pert PRO manufactured by PANalytical.
  • the scanning range was 8 ⁇ 2 ⁇ ⁇ 50 °, and the applied current / applied voltage was 45 kV / 40 mA.
  • the wavelength of the CuK ⁇ ray is set to 0.15418 nm, and d 002 is calculated according to the Bragg formula described below.
  • Electrode preparation NMP was added to 94 parts by mass of the carbonaceous material and 6 parts by mass of polyvinylidene fluoride (“KF # 9100” manufactured by Kureha Co., Ltd.) to form a paste, which was uniformly applied on the copper foil. After drying, the coated electrode was punched into a disk shape having a diameter of 15 mm, and pressed to obtain an electrode. The amount of carbonaceous material in the electrode was adjusted to about 10 mg.
  • the carbonaceous material of the present invention is suitable for constituting the negative electrode of a non-aqueous electrolyte secondary battery, but the discharge capacity (de-doping amount) and irreversible capacity (non-irreversible capacity) of the battery active material.
  • discharge capacity de-doping amount
  • irreversible capacity non-irreversible capacity
  • the lithium electrode was prepared in a glove box in an Ar atmosphere.
  • a 16 mm diameter stainless steel mesh disk is spot-welded to the outer lid of a 2016 coin-sized battery can, and then a 0.8 mm thick metal lithium sheet is punched into a 15 mm diameter disk shape.
  • the electrolyte solution was LiPF 6 at a ratio of 1.4 mol / L in a mixed solvent in which ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate were mixed at a volume ratio of 1: 2: 2.
  • the lithium doping reaction on the carbon electrode will be described as “charging”.
  • “discharge” is a charging reaction in the test battery, but is referred to as “discharge” for convenience because it is a dedoping reaction of lithium from the carbonaceous material.
  • the charging method employed here is a constant current constant voltage method. Specifically, constant current charging was performed at 0.5 mA / cm 2 until the terminal voltage reached 0.025 V, and the terminal voltage reached 0.025 V. Thereafter, constant voltage charging was performed at a terminal voltage of 0.025 V, and charging was continued until the current value reached 20 ⁇ A.
  • the value obtained by dividing the supplied amount of electricity by the mass of the carbonaceous material of the electrode was defined as the charge capacity (mAh / g) per unit mass of the carbonaceous material.
  • the battery circuit was opened for 30 minutes and then discharged.
  • the discharge was a constant current discharge at 0.5 mA / cm 2 and the final voltage was 1.5V.
  • a value obtained by dividing the quantity of electricity discharged at this time by the mass of the carbonaceous material of the electrode is defined as a discharge capacity (mAh / g) per unit mass of the carbonaceous material.
  • the irreversible capacity is calculated as charge capacity-discharge capacity.
  • the charge / discharge capacity and irreversible capacity were determined by averaging the measured values of three test batteries prepared using the same sample.
  • a negative electrode was prepared in the same procedure as in (a) above.
  • the amount of the carbonaceous material in the electrode was adjusted so as to have a prescribed electrode thickness after pressing.
  • the positive electrode was made into a paste by adding NMP to 94 parts by mass of lithium cobaltate (LiCoO 2 ), 3 parts by mass of carbon black, and 3 parts by mass of polyvinylidene fluoride (Kureha KF # 1300) and uniformly applied onto the aluminum foil. . After drying, the coated electrode was punched onto a disk having a diameter of 14 mm and pressed to obtain an electrode.
  • the amount of lithium cobalt oxide in the positive electrode was adjusted to be 95% of the charge capacity of the negative electrode active material.
  • the capacity of lithium cobaltate was calculated as 150 mAh / g.
  • the electrode pair thus prepared was used, and the electrolyte was LiPF at a ratio of 1.4 mol / liter in a mixed solvent in which ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate were mixed at a volume ratio of 1: 2: 2. 6 is added, a borosilicate glass fiber microporous membrane with a diameter of 19 mm is used as a separator, a polyethylene gasket is used, and a 2032 size coin-type nonaqueous electrolyte is used in an Ar glove box.
  • -Based lithium secondary battery was assembled.
  • the input test was started after performing aging by repeating charge and discharge twice at 25 ° C.
  • the constant current and constant voltage conditions adopted in aging are such that the current value is charged at C / 5 until the battery voltage reaches 4.2 V during the first aging, and then the voltage is maintained at 4.2 V ( Charging is continued until the current value reaches C / 100 by continuously changing the current value (while maintaining a constant voltage).
  • the battery circuit was opened for 10 minutes and then discharged. Discharging was performed at a current value of C / 5 until the battery voltage reached 2.75V.
  • the second aging was performed in the same manner as the first time except that the current value was set to 2C / 5.
  • the discharge capacity at the second aging of 2 / 5C was defined as the initial capacity.
  • the test environment After charging to 50% of the initial capacity, the test environment is set to -10 ° C and held sufficiently, then discharged at 0.5C for 10 seconds, opened for 10 minutes, and then charged at 0.5C for 10 seconds. The battery open circuit was released for 10 minutes. The same discharge was performed with the current value set to 1C and 2C. Thereafter, the test environment was set to ⁇ 20 ° C., and after being sufficiently maintained in the same manner, the battery was similarly discharged. Thereafter, the test environment was set to ⁇ 30 ° C., and after being sufficiently held in the same manner, the battery was similarly discharged.
  • Example 1 A 70 kg petroleum pitch with a softening point of 205 ° C. and an H / C atomic ratio of 0.65 and 30 kg of naphthalene are charged into a 300 liter pressure vessel with a stirring blade and an outlet nozzle, and heated, melted and mixed at 190 ° C. After that, the mixture was cooled to 80 to 90 ° C., the inside of the pressure vessel was pressurized with nitrogen gas, and the contents were extruded from the outlet nozzle to obtain a string-like molded body having a diameter of about 500 ⁇ m.
  • this string-like molded body was pulverized so that the ratio (L / D) of the diameter (D) to the length (L) was about 1.5, and the obtained crushed material was heated to 93 ° C. It was put into an aqueous solution in which 53% by mass of polyvinyl alcohol (saponification degree 88%) was dissolved, stirred and dispersed, and cooled to obtain a spherical pitch molded body slurry. After most of the water was removed by filtration, naphthalene in the pitch formed body was extracted and removed with n-hexane having a mass about 6 times that of the spherical pitch formed body.
  • the porous spherical pitch obtained in this way was heated to 270 ° C. while passing through heated air using a fluidized bed, and was maintained at 270 ° C. for 1 hour to oxidize and become porous infusible to heat. Spherical oxidized pitch was obtained.
  • the porous spherical oxide pitch was heated up to 600 ° C. in a nitrogen gas atmosphere (normal pressure) and held at 600 ° C. for 1 hour to carry out preliminary firing to obtain a carbon precursor.
  • the obtained carbon precursor was pulverized with a jet mill to obtain a powdery carbon precursor having an average particle size of 3.8 ⁇ m.
  • Example 2 A carbonaceous material 2 was obtained in the same manner as in Example 1 except that the oxidation temperature of the porous spherical pitch was changed to 250 ° C.
  • Example 3 A carbonaceous material 3 was obtained in the same manner as in Example 1 except that the oxidation temperature of the porous spherical pitch was changed to 205 ° C.
  • Example 4 A carbonaceous material 4 was obtained in the same manner as in Example 1 except that the oxidation temperature of the porous spherical pitch was changed to 190 ° C.
  • Example 5 A carbonaceous material 4 was obtained in the same manner as in Example 1 except that the oxidation temperature of the porous spherical pitch was changed to 170 ° C.
  • Example 6 A carbonaceous material 4 was obtained in the same manner as in Example 1 except that the oxidation temperature of the porous spherical pitch was changed to 165 ° C.
  • Example 7 A carbon precursor obtained in the same manner as in Example 3 was pulverized with a jet mill, and the classified powder was also mixed to obtain a powdery carbon precursor having an average particle size of 3.0 ⁇ m. The main calcination was performed in the same manner as in Example 1 to obtain a carbonaceous material 7.
  • Comparative Example 1 A comparative carbonaceous material 1 was obtained in the same manner as in Example 1 except that the carbon precursor after the preliminary calcination was pulverized by a ball mill and the volume average particle diameter after pulverization was changed to 9.7 ⁇ m.
  • Comparative Example 2 The porous spherical oxidized pitch obtained under the same conditions as in Example 2 was pulverized by a jet mill to obtain a pulverized carbon precursor having a volume average particle diameter of about 3.8 ⁇ m. Subsequently, 10 g of this powdery carbon precursor was subjected to main firing under the same conditions as in Example 1 to obtain a comparative carbonaceous material 2.
  • Example 4 The petroleum-based pitch of Example 1 was changed to a petroleum-based pitch having a softening point of 210 ° C. and an H / C atomic ratio of 0.63, and petroleum-based pitch of 68 kg and naphthalene of 32 kg were replaced with the stirring blade in the same manner as in Example 1. Charged into a 300 liter pressure vessel, heated to 190 ° C, melted and mixed, then cooled to 80-90 ° C, pressurized inside the pressure vessel with nitrogen gas, and the contents extruded through the outlet nozzle A string-like molded body having a diameter of about 500 ⁇ m was obtained.
  • this string-like molded body was pulverized so that the ratio (L / D) of the diameter (D) to the length (L) was about 1.5, and the obtained crushed material was heated to 93 ° C. It was put into an aqueous solution in which 53% by mass of polyvinyl alcohol (saponification degree 88%) was dissolved, stirred and dispersed, and cooled to obtain a spherical pitch molded body slurry. After most of the water was removed by filtration, naphthalene in the pitch formed body was extracted and removed with n-hexane having a mass about 6 times that of the spherical pitch formed body.
  • the porous spherical pitch porous body thus obtained was oxidized at 160 ° C. for 1 hour while passing heated air to obtain a porous spherical pitch.
  • This porous spherical oxidized pitch was pulverized from a carbon precursor heat-treated at 480 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon precursor having an average particle diameter of about 13.7 ⁇ m.
  • this carbon precursor was carbonized at 1800 ° C. for 1 hour in a nitrogen stream to obtain a comparative carbon material 4.
  • Table 1 shows the characteristics of the carbonaceous materials obtained in Examples 1 to 7 and Comparative Examples 1 to 5, and the measurement results of the electrode and battery performance produced using the carbonaceous materials.
  • Table 2 shows the results of measuring the battery performance using the carbonaceous material of Example 2 while changing the thickness of the negative electrode.
  • each of the carbonaceous materials of Examples 1 to 7 had a high energy density per volume under a low temperature condition, and improved input characteristics even in a low temperature environment.
  • the carbonaceous materials of Comparative Examples 1 to 5 had a low energy density per volume.
  • the true density ( ⁇ Bt ) is included in the scope of the present invention, but both have a small specific surface area, and Comparative Example 2 has a large specific surface area ratio (CAL / BET).
  • the energy density per volume was low.
  • Comparative Example 3 has a large true density ( ⁇ Bt ), average particle diameter (D V50 ) and a small specific surface area (BET), and Comparative Example 4 has a small specific surface area (BET).
  • Example 5 since the true density was smaller than the range of the present invention, the energy density per volume was low.
  • the electrode layer of the negative electrode had a thickness of 10 ⁇ m or more, but as shown in Table 2, the energy density per volume decreased as the electrode layer became thicker. Therefore, it is not preferable that the electrode layer thickness exceeds 60 ⁇ m.

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Abstract

L'invention concerne un matériau carboné pour les électrodes négatives des batteries rechargeables à électrolyte non aqueux, qui présente une capacité élevée par volume et d'excellentes caractéristiques d'entrée, et analogue. Un matériau carboné pour les électrodes négatives des batteries rechargeables à électrolyte non aqueux selon la présente invention présente une densité réelle (ρBt) comprise entre 1,50 et 2,10 % g/cm3, telle que déterminée par un procédé de butanol, un diamètre particulaire moyen (DV50) compris entre 1 et 15 µm, une surface spécifique (BET) égale ou supérieure à 7,0 m2/g telle que déterminée par un procédé BET par adsorption d'azote gazeux, et un rapport entre la surface spécifique (CAL) telle que calculée à partir de la distribution granulométrique, et la surface spécifique (BET) telle que déterminée par un procédé BET d'adsorption d'azote gazeux, à savoir un rapport BET/CAL égal ou inférieur à 1,0.
PCT/JP2015/059773 2014-03-31 2015-03-27 Matériau carboné pour les électrodes négatives des batteries rechargeables à électrolyte non aqueux, électrode négative pour des batteries rechargeables à électrolyte non aqueux, batterie rechargeable à électrolyte non aqueux et véhicule Ceased WO2015152093A1 (fr)

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