WO2015152089A1 - Matériau carboné pour électrode négative de batterie secondaire à électrolyte non aqueux, électrode négative pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et véhicule - Google Patents

Matériau carboné pour électrode négative de batterie secondaire à électrolyte non aqueux, électrode négative pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et véhicule Download PDF

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Publication number
WO2015152089A1
WO2015152089A1 PCT/JP2015/059769 JP2015059769W WO2015152089A1 WO 2015152089 A1 WO2015152089 A1 WO 2015152089A1 JP 2015059769 W JP2015059769 W JP 2015059769W WO 2015152089 A1 WO2015152089 A1 WO 2015152089A1
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Prior art keywords
negative electrode
secondary battery
electrolyte secondary
carbonaceous material
aqueous electrolyte
Prior art date
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PCT/JP2015/059769
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English (en)
Japanese (ja)
Inventor
誠 今治
佳余子 岡田
靖浩 多田
直弘 園部
真友 小松
Original Assignee
株式会社クレハ
株式会社クレハ・バッテリー・マテリアルズ・ジャパン
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Priority to JP2016511638A priority Critical patent/JPWO2015152089A1/ja
Publication of WO2015152089A1 publication Critical patent/WO2015152089A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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.
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery negative electrode carbonaceous material having a high discharge capacity per volume and excellent storage characteristics, a negative electrode for a non-aqueous electrolyte secondary battery, and a negative electrode for the non-aqueous electrolyte secondary battery.
  • a nonaqueous electrolyte secondary battery and a vehicle including the vehicle are provided.
  • the present inventors have found that in true density ([rho Bt) is a carbonaceous material is less than 1.70 g / cm 3 or more 2.10 g / cm 3 as determined by the butanol method, the average particle diameter (Dv 50) is 1 ⁇ m or more 15 ⁇ m
  • the difference (YX) from the discharge capacity (Y) of the negative electrode of 1.5V to 0V when CV charge is performed at 0V is 240 mAh / cm 3 or less, the discharge capacity per volume is high.
  • the inventors have found that a carbonaceous material having low hygroscopicity and, as a result, excellent storage characteristics is provided, and the present invention has been completed. Specifically, the present invention provides the following.
  • True density ( ⁇ Bt ) determined by butanol method is 1.70 g / cm 3 or more and less than 2.10 g / cm 3
  • average particle size (Dv 50 ) is 1 ⁇ m or more and 15 ⁇ m or less, and determined by X-ray diffraction method.
  • the (002) plane average layer spacing d 002 is 0.340 nm or more and 0.375 nm or less,
  • the discharge capacity (X) of the negative electrode of 1.5V to 0.025V when CV charge is performed at 0.025V based on the lithium reference electrode standard, and the negative electrode capacity of 1.5V to 0V when CV charge is performed at 0V A carbonaceous material for a negative electrode of a nonaqueous electrolyte secondary battery, wherein a difference (YX) from a discharge capacity (Y) is 240 mAh / cm 3 or less.
  • a negative electrode for a non-aqueous electrolyte secondary battery comprising the carbonaceous material for a non-aqueous electrolyte secondary battery negative electrode according to any one of (1) to (3) above.
  • a nonaqueous electrolyte secondary battery comprising the negative electrode for a nonaqueous electrolyte secondary battery described in (4) above.
  • a carbonaceous material having a true density ( ⁇ Bt ) determined by a butanol method of 1.70 g / cm 3 or more and less than 2.10 g / cm 3 an average particle diameter of 1 ⁇ m or more and 15 ⁇ m or less
  • the average layer spacing d 002 of the (002) plane determined by the diffraction method is 0.340 to 0.375 nm, and 1.5 V to 0.025 V when CV charging is performed at 0.025 V with a lithium reference electrode standard.
  • the difference (Y ⁇ X) between the discharge capacity (X) of the negative electrode and the discharge capacity (Y) of the negative electrode of 1.5 V to 0 V when CV charging is performed at 0 V is 240 mAh / cm 3 or less, Although the discharge capacity is high, the hygroscopic property is low, and as a result, a carbonaceous material having excellent storage characteristics is provided.
  • Non-aqueous electrolyte secondary battery negative electrode carbonaceous material has a true density ( ⁇ Bt ) of 1.70 g / cm 3 or more 2 determined by the butanol method.
  • the carbonaceous material is a high density of the true density ([rho Bt) is 1.70 g / cm 3 or more 2.10 g / cm less than 3 as determined by the butanol method were CV charging at 0.025V lithium reference electrode reference
  • the difference (Y ⁇ X) between the negative electrode discharge capacity (X) of 1.5V to 0.025V and the negative electrode discharge capacity (Y) of 1.5V to 0V when CV charging is performed at 0V is If the current is 240 mAh / cm 3 or less, the slope of the discharge curve per volume in the potential range frequently used in an in-vehicle lithium ion secondary battery of 0.025 V or more on the basis of the lithium reference electrode becomes gentle. It was understood by the person.
  • the capacity per unit volume is calculated by the product of the capacity per unit mass and the true density ( ⁇ Bt ) determined by the butanol method.
  • non-aqueous electrolyte secondary batteries for automobiles it is not a usage pattern in which full charge and complete discharge are repeated, but an area where the input characteristics and output characteristics are always balanced, that is, 50% when the full charge is 100%.
  • the use form which repeats charging / discharging so that a battery state may be located in the charge area before and behind is preferable.
  • the negative electrode material a material in which the potential (E) changes greatly with a certain slope with respect to the discharge capacity (mAh).
  • the carbonaceous material composed of relatively small particles having an average particle diameter (D v50 ) of 1 ⁇ m or more and 15 ⁇ m or less can be closely packed, the discharge capacity per unit volume of the battery is further increased.
  • the discharge capacity (X) of the negative electrode of 1.5V to 0.025V when CV charge is performed at 0.025V based on the lithium reference electrode standard, and the negative electrode capacity of 1.5V to 0V when CV charge is performed at 0V the difference between the discharge capacity (Y) (Y-X) is a viewpoint of providing high volumetric per discharge capacity is preferably 240 mAh / cm 3 or less, more preferably, 220 mAh / cm 3 or less, more preferably, 200 mAh / cm 3 or less.
  • ⁇ Bt is related to the abundance of pores into which butanol can enter, there is a balance between increasing the number of fine pores, increasing hygroscopicity and easily impairing storage stability, and improving discharge capacity per volume.
  • 1.70 g / cm 3 or more more preferably 1.75 g / cm 3 or more and 1.80 g / cm 3 or more, preferably less than 2.10 g / cm 3 , More preferably, it is 2.05 g / cm 3 or less.
  • the discharge capacity of the negative electrode in the practical range of 1.5 V to 0.025 V with respect to the lithium reference electrode is increased.
  • the discharge capacity (X) of the negative electrode of 1.5 V to 0.025 V when CV charging is performed at 0.025 V on the basis of the lithium reference electrode is preferably more than 410 mAh / cm 3 .
  • 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.
  • the average layer spacing d 002 of the (002) plane determined by the X-ray diffraction method is 0.340 to 0.375 nm.
  • a carbonaceous material having a graphite structure in which d 002 is less than 0.340 nm or a crystallite size Lc (002) in the c-axis direction exceeds 15 nm is obtained by using such a carbonaceous material as a negative electrode material.
  • the carbonaceous material is easily collapsed or the electrolytic solution is decomposed due to the doping or dedoping of the active material, and the charge / discharge cycle characteristics of the battery are inferior.
  • a carbonaceous material having d 002 exceeding 0.375 nm increases the irreversible capacity of an active material such as lithium, and decreases the utilization rate of the active material.
  • d 002 is preferably 0.340 to 0.375 nm, more preferably 0.345 to 0.370 nm, and 0.350 to 0.370 nm.
  • the crystallite size Lc (002) in the c-axis direction is 15 nm or less. Preferably it is 10 nm or less, More preferably, it is 5 nm or less.
  • the active material layer of the electrode In order to improve the output characteristics, it is important to make the active material layer of the electrode thin, and for that purpose, it is important to reduce the average particle size (D v50 ). However, if the average particle size is too small, the amount of fine powder increases and safety is lowered, which is not preferable. On the other hand, if the particles are too small, the amount of binder necessary to form an electrode increases and the resistance of the electrode increases. On the other hand, when the average particle size is increased, it is difficult to apply a thin electrode, and further, the lithium free diffusion process in the particles is increased, so that rapid charge / discharge is difficult.
  • the average particle diameter D v50 (that is, the particle diameter at which the cumulative volume becomes 50%) is preferably 1 to 15 ⁇ m, more preferably 2 ⁇ m or more and 3 ⁇ m or more, while 13 ⁇ m or less and 11 ⁇ m or less. .
  • the ratio ( ⁇ He / ⁇ Bt ) between the true density ( ⁇ He ) determined by the helium substitution method and the true density ( ⁇ Bt ) determined by the butanol method is excessively hygroscopic and increases storage stability. It is preferably 1.15 or less, more preferably 1.10 or less, and still more preferably 1.07 or less, from the balance between the point of being easily damaged and the point of improving the discharge capacity per volume.
  • This ratio reflects the number of pores large enough to allow butanol to penetrate but not helium, and these pores are more effective in absorbing and releasing Li than the degree of moisture absorption in the atmosphere. The degree of involvement is considered high.
  • the discharge capacity of the battery tends to be small, so that it is 1.0 m 2 / g or more, preferably 1. It is 6 m 2 / g or more, more preferably 2.0 m 2 / g or more, 3.0 m 2 / g or more, 4.0 m 2 / g or more.
  • the BET specific surface area is too large, the irreversible capacity of the obtained battery tends to increase, and therefore, 25 m 2 / g or less is preferable. More preferably, it is 20 m 2 / g or less.
  • the slope 0.9 / Z (Vg / Ah) of the discharge curve calculated from the discharge capacity Z (Ah / g) corresponding to 0.2 V to 1.1 V on the lithium reference electrode standard and the potential difference 0.9 (V) is It is preferably 0.70 or less, and the slope of the discharge curve per volume in the potential range most used in the in-vehicle lithium ion secondary battery of 0.2 V to 1.1 V based on the lithium reference electrode becomes gentle. Thereby, in the practical state, the potential difference between the negative electrode and the positive electrode is kept high, and a high discharge capacity per volume can be exhibited. From the viewpoint of providing a high discharge capacity per volume, it is more preferably 0.65 or less.
  • the ratio H / C of hydrogen atoms to carbon atoms of the carbonaceous material of the present invention is measured by elemental analysis of hydrogen atoms and carbon atoms.
  • 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. Especially preferably, it is 0.05 or less. If the ratio H / C of hydrogen atoms to carbon atoms exceeds 0.1, many functional groups are present 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 is based on a manufacturing method similar to the conventional carbonaceous material for the negative electrode of the nonaqueous electrolyte secondary battery. By optimizing the conditions, it 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 the carbonaceous material from the untreated carbonaceous material stage to the previous stage of the carbonaceous material for the negative electrode of the 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., the crosslinked structure cannot be sufficiently formed and the structure is controlled. 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 an easily graphitizable 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.
  • the pulverization step may be performed after the oxidation treatment step, but is preferably performed after preliminary firing.
  • the main baking can be performed by a known method in the field of the present invention. For example, it can be carried out according to the procedure of the main firing described below.
  • 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. Pre-firing removes volatile components such as CO 2 , CO, CH 4 , and H 2 , and tar components, and reduces the generation of these components in the main firing, thereby reducing the burden on the calciner. .
  • 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.
  • 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 rate of temperature increase in the pre-firing is preferably 1 ° C / h or more and 150 ° C / h or less, more preferably 5 ° C / h or more and 100 ° C / h or less, and 10 ° C / h or more. 50 ° C./h or less is more preferable.
  • Carbon precursors with a true density ( ⁇ Bt ) determined by the butanol method of 1.70 g / cm 3 or more to less than 2.10 g / cm 3 have a large amount of tar generated during pre-firing, and gradually volatilize these volatile components.
  • a carbonaceous material having a suitable pore diameter can be prepared, and a high discharge capacity is developed.
  • the present invention is not limited by the above description.
  • the pulverization step in the present invention is performed in order to make the particle size of the graphitizable carbon precursor uniform. It can also grind
  • the pulverizer used for pulverization is not particularly limited. For example, a jet mill, a ball mill, a hammer mill, or a rod mill can be used. However, a jet mill having a classification function in that fine powder is generated less. Is preferred.
  • classification when using a ball mill, a hammer mill, a rod mill or the like, fine powder can be removed by classification after pulverization.
  • classification include classification with a sieve, wet classification, and dry classification.
  • wet classifier include a classifier using a principle such as gravity classification, inertia classification, hydraulic classification, or centrifugal classification.
  • 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 1600 ° 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 main calcination temperature of the present invention is 1600 ° 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.
  • 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 the pitch and the additive is preferably performed after being formed 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.
  • oxidation is preferably performed at a temperature of 120 to 400 ° C. using an oxidizing agent.
  • 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. be able to. It is simple and economical to oxidize at 120 to 400 ° C. and carry out a crosslinking treatment using 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 subjected to the crosslinking treatment as described above is pre-fired and then carbonized at 900 ° C. to 1600 ° C. in a non-oxidizing gas atmosphere to obtain the carbonaceous material of the present invention. Can do.
  • the carbonaceous material of the present invention can also be obtained by carbonizing at 900 ° C. to 1600 ° 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 1600 ° 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 subjecting a thermoplastic resin such as polyacrylonitrile or a styrene / divinylbenzene copolymer to an oxidation treatment 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 oxidation treatment.
  • the oxidation treatment can be performed in a temperature range of 120 to 400 ° C., particularly preferably 170 ° C. to 350 ° C., more preferably 220 to 350 ° C.
  • the oxidation reaction may proceed rapidly to form a non-uniform structure, which is not preferable. If the temperature of the oxidation treatment is too low, the oxidation reaction becomes too slow, leading to a decrease in productivity.
  • the oxidation treatment can be performed in the range of 0.1 to 10 hours, preferably 0.5 to 6 hours. If the oxidation treatment time is too short, the oxidation reaction does not sufficiently penetrate into the inside of the particles, and a uniform carbonaceous material cannot be obtained. When the oxidation treatment time is excessively long, productivity is lowered. The lower the temperature for the oxidation treatment, the longer the time required for the oxidation treatment.
  • 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 is pre-fired as necessary, pulverized, and carbonized at 900 ° C. to 1600 ° C. in a non-oxidizing gas atmosphere to obtain the carbonaceous material of the present invention. it can.
  • 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.
  • Nonaqueous electrolyte secondary battery negative electrode contains the carbonaceous material for a nonaqueous electrolyte secondary battery negative electrode 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.
  • a conductive aid can be added.
  • 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. However, the larger the electrode area facing the counter electrode, the better the input / output characteristics, and the thicker the active material layer. Too much is not preferable because the input / output characteristics deteriorate.
  • the thickness of the active material layer (per side) is preferably 10 to 80 ⁇ m, more preferably 20 to 75 ⁇ m, and still more preferably 20 to 60 ⁇ m.
  • Nonaqueous electrolyte secondary battery includes the negative electrode of the 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 ( ⁇ Bt , ⁇ He , BET specific surface area, average particle diameter (D v50 ), hydrogen / carbon atomic ratio (H / C) of the non-aqueous electrolyte secondary battery negative electrode of the present invention are as follows: d 002 , Lc (002) , charge capacity, discharge capacity, irreversible capacity, moisture absorption) are described, but the physical property values described in this specification including the examples are determined by the following methods. It is based on the value.
  • 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.
  • the measuring device has a sample chamber and an expansion chamber, and the sample chamber has a pressure gauge for measuring the pressure in the chamber.
  • the sample chamber and the expansion chamber are connected by a connecting pipe having a valve.
  • a helium gas introduction pipe having a stop valve is connected to the sample chamber, and a helium gas discharge pipe having a stop valve is connected to the expansion chamber.
  • the volume of the sample chamber (V CELL ) and the volume of the expansion chamber (V EXP ) are measured in advance using a calibration sphere with a known volume.
  • the sample is placed in the sample chamber, fills the system with helium, the system pressure at that time and P a. Then closing the valve, is increased to a pressure P 1 added sample chamber only helium gas. After that, when the valve is opened and the expansion chamber and the sample chamber are connected, the system pressure decreases to P 2 due to expansion.
  • the volume of the sample (V SAMP ) is calculated by the following equation.
  • 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 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 by the Bragg formula.
  • Dv50 Average particle diameter by laser diffraction method
  • a dispersing agent cationic surfactant “SN Wet 366” (manufactured by San Nopco)
  • SALD-3000S particle size distribution measuring instrument
  • a negative electrode mixture prepared by adding water to 96 parts by mass, 3 parts by mass of SBR, and 1 part by mass of CMC was prepared.
  • the negative electrode mixture was uniformly applied on the copper foil. After drying, it was punched out from a copper foil 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-desorption) of the battery active material.
  • a lithium secondary battery is configured using the electrode obtained above, using lithium metal with stable characteristics as a counter electrode, Its characteristics were evaluated.
  • 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 is performed at 0.5 mA / cm 2 until the terminal voltage reaches 0.025 V or 0 V, and the terminal voltage is set to 0.025 V or After reaching 0 V, constant voltage (CV) charging was performed at a terminal voltage of 0.025 V or 0 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.
  • 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 equipped with a stirring blade and an outlet nozzle, and heated, melted and mixed at 190 ° C. After cooling 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.
  • the solution was poured 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 thus obtained was heated to 190 ° C. while passing through heated air using a fluidized bed, and was maintained at 190 ° C. for 1 hour for oxidation to obtain a porous spherical oxidized pitch.
  • the oxidation pitch was raised to 600 ° C. at 100 ° C./h in a nitrogen gas atmosphere (normal pressure), held at 600 ° C. for 1 hour, and pre-fired while being melted to obtain a carbon precursor. .
  • the obtained carbon precursor was pulverized to obtain a powdery carbon precursor having an average particle size of 4.1 ⁇ m.
  • Example 2 A carbonaceous material 2 was obtained in the same manner as in Example 1 except that the oxidation treatment temperature was changed to 180 ° C.
  • Example 3 A carbonaceous material 3 was obtained in the same manner as in Example 1 except that the oxidation treatment temperature was changed to 170 ° C.
  • Example 4 A carbonaceous material 4 was obtained in the same manner as in Example 1 except that the oxidation treatment temperature was changed to 165 ° C.
  • Example 5 A carbonaceous material 5 was obtained in the same manner as in Example 1 except that the oxidation treatment temperature was changed to 160 ° C.
  • Example 6 A carbonaceous material 6 was obtained in the same manner as in Example 4 except that the pulverized particle size of the carbon precursor was changed to 9.2 ⁇ m.
  • Example 7 A coal pitch having a softening point of 188 ° C. and an H / C atomic ratio of 0.51 was pulverized by a counter jet mill (Hosokawa Micron Corporation / 100-AFG) at a rotation speed of 6000 rpm to obtain a powdery pitch having an average particle size of 13.2 ⁇ m. . Subsequently, this powdery pitch was placed in a muffle furnace (Denken Co., Ltd.), and oxidation treatment was performed by maintaining at 190 ° C. for 3 hours while circulating air at 20 L / min to obtain an oxidized pitch.
  • a muffle furnace Disken Co., Ltd.
  • 100 g of the obtained oxidation pitch was put in a crucible, heated at a rate of 50 ° C./h up to 600 ° C. in a vertical tubular furnace, held at 600 ° C. for 1 hour and pre-baked to obtain a carbon precursor. It was. Pre-baking was performed in a nitrogen atmosphere with a flow rate of 5 L / min, and the crucible was opened. 10 g of carbon precursor is placed in a horizontal tubular furnace having a diameter of 100 mm, heated to 1200 ° C. at a heating rate of 250 ° C./h, held at 1200 ° C. for 1 hour, and subjected to main firing to prepare carbonaceous material 7 did. The main firing was performed in a nitrogen atmosphere with a flow rate of 10 L / min.
  • Example 8 Polyvinyl chloride having an average degree of polymerization of 700 is oxidized at a temperature of 180 ° C. for 5 hours while passing heated air, and then baked to 600 ° C. at a temperature increase rate of 100 ° C./h in a nitrogen gas atmosphere. Then, it was pulverized with a counter jet mill (Hosokawa Micron Corporation / 100-AFG) to obtain a powdery carbon precursor. 10 g of this carbon precursor is placed in a horizontal tubular furnace having a diameter of 100 mm, heated to 1200 ° C. at a temperature rising rate of 250 ° C./h, held at 1200 ° C. for 1 hour, and subjected to main firing to obtain a carbonaceous material 8. It was.
  • a counter jet mill Hosokawa Micron Corporation / 100-AFG
  • Example 9 In the same manner as in Example 3, except that the carbonaceous material 3 obtained in Example 3 was made of a negative electrode mixture prepared by adding water to 96 parts by mass, 3 parts by mass of SBR, and 1 part by mass of CMC. evaluated.
  • Comparative carbonaceous material 1 was obtained in the same manner as in Example 1 except that the oxidation treatment temperature was changed to 270 ° C.
  • Comparative Example 2 A comparative carbonaceous material 2 was obtained in the same manner as in Example 3 except that the firing temperature of the main firing was changed to 800 ° C.
  • Comparative Example 3 Comparative carbonaceous material 3 was obtained in the same manner as in Example 3 except that the firing temperature for main firing was changed to 2000 ° C.
  • Tables 1 and 2 show the characteristics of the carbonaceous materials obtained in Examples and Comparative Examples, and the measurement results of the electrodes and battery performance produced using the carbonaceous materials.
  • the carbonaceous materials of Examples 1 to 9 have a true density ( ⁇ Bt ), an average particle diameter (D v50 ), an average interplanar spacing (d 002 ) within the scope of the present invention, and have a volume per volume and irreversible.
  • the capacity is good, and the difference between the discharge capacity (X) of 1.5V to 0.025V by CV charge of 0.025V and the discharge capacity (Y) of 1.5V to 0V by CV charge of 0V ( YX) was as low as 240 mAh / cm 3 or less. This indicates that the discharge capacity of the negative electrode is increased in a practical range of 1.5V to 0.025V. Furthermore, the hygroscopicity was low.
  • Examples 1 to 9 had good output characteristics and storage characteristics in a practical state.
  • the slope (0.9 / Z) of the discharge curve in a potential region of 0.2 to 1.1 V that is practically used is in a low range of 0.70 or less, and has a gentle slope, High discharge capacity per volume can be obtained in a practical range.
  • the carbonaceous material of Comparative Example 1 has a relatively large proportion of discharge capacity in the vicinity of 0 mV because the true density ( ⁇ Bt ) and the average interfacial layer spacing (d 002 ) are outside the scope of the present invention.
  • the discharge capacity per volume difference (YX) showed a large numerical value. Therefore, the capacity of the inclined region is insufficient.
  • the true density ( ⁇ Bt ) and the average face layer spacing (d 002 ) were out of the range of the present invention, and the irreversible capacity was large and the efficiency (%) was inferior.
  • the true density ( ⁇ Bt ) was higher than the range of the present invention, so the capacity per volume was low.

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  • Inorganic Chemistry (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention fournit : un matériau carboné pour électrode négative de batterie secondaire à électrolyte non aqueux dont la capacité de décharge en termes de volume est élevée, et qui présente d'excellentes caractéristiques de conservation ; une électrode négative pour batterie secondaire à électrolyte non aqueux ; une batterie secondaire à électrolyte non aqueux équipée de cette électrode négative pour batterie secondaire à électrolyte non aqueux ; et un véhicule. Le matériau carboné pour électrode négative de batterie secondaire à électrolyte non aqueux de l'invention, présente une densité vraie (ρBt) obtenue par un procédé butanol supérieure ou égale à 1,70g/cm3 et inférieure à 2,10g/cm3, un diamètre particulaire moyen (DV50) supérieur ou égal à 1µm et inférieur ou égal à 15µm, et une distance moyenne (d002) entre face de couche de faces (002) obtenue par un procédé de diffraction aux rayons X supérieure ou égale à 0,340nm et inférieure ou égale à 0,375nm. La différence (Y-X) entre la capacité de décharge (X) d'une électrode négative de 1,5V à 0,025V pendant une charge CV de 0,025V sur la base d'une électrode de référence au lithium, et la capacité de décharge (Y) d'une électrode négative de1,5V à 0V pendant une charge CV de 0V, est inférieure ou égale à 240mAh/cm3.
PCT/JP2015/059769 2014-03-31 2015-03-27 Matériau carboné pour électrode négative de batterie secondaire à électrolyte non aqueux, électrode négative pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et véhicule WO2015152089A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08279358A (ja) * 1995-02-09 1996-10-22 Kureha Chem Ind Co Ltd 電池電極用炭素質材料、その製造方法、電極構造体および電池
WO2014034431A1 (fr) * 2012-08-29 2014-03-06 住友ベークライト株式会社 Matériau d'électrode négative, matériau actif d'électrode négative, électrode négative et batterie aux ions de métal alcalin
WO2014034858A1 (fr) * 2012-08-30 2014-03-06 株式会社クレハ Matériau carboné pour électrodes négatives de batteries secondaires à électrolyte non aqueux et procédé de production associé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08279358A (ja) * 1995-02-09 1996-10-22 Kureha Chem Ind Co Ltd 電池電極用炭素質材料、その製造方法、電極構造体および電池
WO2014034431A1 (fr) * 2012-08-29 2014-03-06 住友ベークライト株式会社 Matériau d'électrode négative, matériau actif d'électrode négative, électrode négative et batterie aux ions de métal alcalin
WO2014034858A1 (fr) * 2012-08-30 2014-03-06 株式会社クレハ Matériau carboné pour électrodes négatives de batteries secondaires à électrolyte non aqueux et procédé de production associé

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