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WO2014092141A1 - Matériau d'électrode négative pour batterie secondaire au lithium-ion, feuille d'électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium - Google Patents

Matériau d'électrode négative pour batterie secondaire au lithium-ion, feuille d'électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium Download PDF

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Publication number
WO2014092141A1
WO2014092141A1 PCT/JP2013/083288 JP2013083288W WO2014092141A1 WO 2014092141 A1 WO2014092141 A1 WO 2014092141A1 JP 2013083288 W JP2013083288 W JP 2013083288W WO 2014092141 A1 WO2014092141 A1 WO 2014092141A1
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Prior art keywords
negative electrode
lithium ion
secondary battery
ion secondary
artificial graphite
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English (en)
Japanese (ja)
Inventor
大輔 原田
武内　正隆
石井　伸晃
明央 利根川
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Resonac Holdings Corp
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Showa Denko KK
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Priority to JP2014552077A priority Critical patent/JPWO2014092141A1/ja
Priority to CN201380064298.6A priority patent/CN104838526B/zh
Publication of WO2014092141A1 publication Critical patent/WO2014092141A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • 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 negative electrode material that can be a lithium ion secondary battery excellent in high-speed charging characteristics while maintaining high output and high energy density. Moreover, this invention relates to the negative electrode sheet for lithium ion secondary batteries using the negative electrode material, and a lithium secondary battery.
  • Lithium ion secondary batteries are used as power sources for portable electronic devices, and in recent years, they are also used as power sources for electric tools and electric vehicles.
  • electric vehicles such as battery electric vehicles (BEV) and hybrid electric vehicles (HEV)
  • BEV battery electric vehicles
  • HEV hybrid electric vehicles
  • a high volumetric energy density is required to extend the cruising range.
  • a plug-in hybrid vehicle (PHEV) has a smaller battery capacity than EV and has to be trickle charged by driving a motor with a low-capacity battery.
  • carbon-based materials such as graphite have been mainly used as the negative electrode material, but recently, metal-based negative electrode materials have also been developed.
  • cycle life and stability and many problems still remain.
  • Carbon-based materials can be broadly divided into graphite materials with high crystallinity and amorphous carbon materials with low crystallinity, both of which can be used for negative electrode active materials because they can undergo lithium insertion and desorption reactions. it can.
  • Graphite materials include natural graphite and artificial graphite. Natural graphite is known to be spherically granulated.
  • Patent Document 1 describes a graphite material obtained by coating artificial carbon with the surface of natural graphite formed into a spherical shape. Lithium ion secondary batteries using this graphite material have some performance required as a power source for portable electronic devices, but they have sufficiently reached the performance required as a power source for electric vehicles and power tools. Not.
  • a highly crystalline graphite material is not sufficient in charge characteristics in spite of stable cycle characteristics.
  • rapid charge / discharge is performed, the insertion / extraction reaction of lithium ions on the negative electrode active material side is not in time, the battery voltage suddenly reaches the lower limit or upper limit, and the reaction does not proceed further. Is remarkable for highly crystalline graphite materials.
  • high crystalline graphite materials are widely used as negative electrode materials at present because of the capacity of graphite, such as the theoretical battery capacity phase, and the stability of cycle characteristics.
  • Amorphous carbon materials are known to be able to be used for rapid charge and discharge because they can be charged from a low potential region that cannot be charged with graphite, but they have the drawbacks of significant cycle deterioration, large irreversible capacity, and small capacity.
  • Patent Document 2 discloses a technique in which a carbon material serving as a core material is immersed in tar or pitch and dried or heat-treated at 900 to 1300 ° C.
  • Patent Document 3 discloses a technique in which a carbon precursor such as pitch is mixed on the surface of graphite particles obtained by granulating natural graphite or scaly artificial graphite, and fired in a temperature range of 700 to 2800 ° C. in an inert gas atmosphere. Has been.
  • Patent Document 4 spherical graphite particles obtained by granulating spheroidized graphite having d (002) of 0.3356 nm, R value of around 0.07, and Lc of about 50 nm by mechanical external force, phenol resin, etc.
  • composite graphite particles formed by coating a heated carbide of the above resin are used as a negative electrode active material.
  • the composite graphite particles are obtained by performing pretreatment for carbonization at 1000 ° C. in a nitrogen atmosphere and carbonizing at 3000 ° C.
  • Patent Document 5 discloses that a mixed carbon material obtained by mixing a graphite-based carbon material having an average particle size of 15 ⁇ m and a low crystalline carbon surface and a low crystalline carbon having an average particle size of 10 ⁇ m is used as the negative electrode active material. Yes.
  • JP 2005-285633 A Japanese Patent No. 2976299 (EP0861804A) Japanese Patent No. 3193342 (EP0917228A) Japanese Patent Laid-Open No. 2004-210634 JP 2006-338977 A
  • Patent Documents 1 to 4 None of the carbon materials described in Patent Documents 1 to 4 have sufficient charge characteristics. Moreover, the cycle characteristics were insufficient.
  • the carbon material described in Patent Document 5 has good low-temperature characteristics, but has insufficient discharge characteristics.
  • the negative electrode material for a lithium ion secondary battery, the negative electrode sheet for a lithium ion secondary battery using the negative electrode material, and the lithium secondary battery in a preferred embodiment of the present invention are as follows.
  • the (002) plane spacing (d (002)) of the graphite structure measured by powder X-ray diffraction method is in the range of 0.335 to 0.339 nm, and the particle size distribution measured by laser diffraction method
  • Artificial graphite (A) having a particle diameter (D50) of 4 to 10 ⁇ m with a volume cumulative frequency of 50%, and d (002) of 0.340 nm or more, D50 of 7 to 17 ⁇ m, and D50 Carbon material larger than D50 of artificial graphite (A)
  • B The negative electrode material for lithium ion secondary batteries characterized by including the mixture of these.
  • the negative electrode material for a lithium ion secondary battery as described in 1 above wherein the composition ratio between the artificial graphite (A) and the carbon material (B) is in the range of 8: 2 to 2: 8 in terms of mass ratio.
  • the negative electrode material for a lithium ion secondary battery as described in 1 above, wherein the artificial graphite (A) is obtained by heat treating petroleum-based and / or coal-based coke at 2500 ° C. or higher.
  • the negative electrode material for a lithium ion secondary battery as described in 1 above, wherein the artificial graphite (A) comprises particles having a carbon coating layer on the surface of artificial graphite particles as a core material.
  • the artificial graphite (A) is obtained by attaching an organic compound to particles of artificial graphite as a core material and then heat-treating at a temperature of 500 ° C. to 2000 ° C.
  • the negative electrode material for lithium ion secondary batteries in any one.
  • the organic compound is at least one compound selected from the group consisting of petroleum pitch, coal pitch, phenol resin, polyvinyl alcohol resin, furan resin, cellulose resin, polystyrene resin, polyimide resin, and epoxy resin.
  • a negative electrode sheet for a lithium ion secondary battery obtained by applying a negative electrode paste containing the negative electrode material for a lithium ion secondary battery according to any one of the above 1-11, a binder, and a dispersion medium onto a current collector foil, drying, and pressing.
  • a negative electrode sheet for a lithium ion secondary battery A negative electrode sheet for a lithium ion secondary battery.
  • a lithium ion battery comprising the negative electrode sheet for a lithium ion secondary battery as described in 12 or 13 above as a constituent element.
  • a lithium secondary battery excellent in charge / discharge characteristics and cycle characteristics and its performance balance can be obtained. it can. Further, the cycle characteristics can be further improved by using the artificial graphite having a carbon coating layer on the surface of the graphite particles.
  • the negative electrode material for a lithium ion secondary battery includes artificial graphite (A) and a carbon material having a larger average particle diameter (D50, see below) and lower crystallinity than the artificial graphite (A).
  • a mixture with (B) is included.
  • the artificial graphite (A) preferably has a (002) plane spacing (d (002)) in the range of 0.335 to 0.339 nm as measured by powder X-ray diffraction.
  • d (002) is in the range of 0.335 to 0.337 nm.
  • the thickness (Lc) of the crystallite in the c-axis direction is preferably 50 nm or more.
  • Artificial graphite (A) has a particle diameter (D50) (sometimes referred to as an average particle diameter in this specification) having a volume cumulative frequency of 50% as measured by a laser diffraction method of 4 to 10 ⁇ m. Is preferred. D50 is more preferably 4 to 8 ⁇ m, still more preferably 4 to 6 ⁇ m. When D50 is in the above range, lithium ions can efficiently react with the electrolytic solution and exhibit excellent discharge characteristics, and the capacity and cycle characteristics can be maintained high. If D50 is too small, the number of particles that cannot efficiently participate in the electrochemical reaction with lithium ions increases, and the capacity and cycle characteristics tend to be reduced.
  • D50 particle diameter
  • D50 is more preferably 4 to 8 ⁇ m, still more preferably 4 to 6 ⁇ m.
  • the artificial graphite (A) desirably has 90% or more of particles in the range of 4 to 10 ⁇ m in the number-based cumulative particle size distribution in the particle size distribution measurement by laser diffraction method. Since graphite in the above range efficiently reacts with the electrolytic solution, it exhibits excellent charge / discharge characteristics.
  • the particle size distribution can be adjusted by crushing and classification.
  • the pulverizer include a hammer mill, a jaw crusher, and a collision pulverizer.
  • the classification can be performed by an airflow classification method or a sieve classification method.
  • the air classifier include a turbo classifier and a turboplex.
  • the artificial graphite (A) has a BET specific surface area of preferably 0.5 to 5 m 2 / g, more preferably 0.5 to 3.5 m 2 / g.
  • the BET specific surface area is in the above range, the coulombic efficiency is good, and the graphite having a good balance between cycle and output characteristics is obtained. If the BET specific surface area is too large, the surface activity of the particles increases, the Coulomb efficiency decreases due to decomposition of the electrolyte, and the cycle characteristics tend to decrease. On the other hand, if the BET specific surface area is too small, the contact area with the electrolytic solution decreases, and the output characteristics tend to deteriorate.
  • the artificial graphite (A) may have a carbon coating layer on the particle surface.
  • the same material as the artificial graphite (A) described above can be used.
  • composite graphite composed of a core material and a coating layer, input / output characteristics can be improved.
  • Those composed of carbon having a ratio I D / I G (R value) of 0.1 or more are preferred.
  • a more preferable R value is 0.20 or more.
  • the carbon raw material used for the production of artificial graphite (A) has a heating loss (for example, volatile content of hydrocarbons accompanying carbonization) of 5 to 20% by mass when heated from 300 ° C. to 1200 ° C. in an inert atmosphere. It is preferable. If the amount of heat loss is small, the particle shape tends to be plate-like after pulverization, and the pulverized surface (edge portion) is exposed, and the specific surface area tends to increase and side reactions tend to increase. On the other hand, if the amount of heat loss is large, many particles are bound in the process of graphitization, which tends to affect the yield.
  • the carbon raw material having such a heat loss is selected from petroleum pitch coke or coal pitch coke.
  • the carbon raw material for artificial graphite (A) is preferably selected from raw coke which is a kind of petroleum coke. Since raw coke is undeveloped, it becomes spherical when pulverized and its specific surface area tends to be small. Accordingly, the carbon raw material is preferably non-needle-like coke.
  • Petroleum coke is a black, porous solid residue obtained by cracking or cracking distillation of petroleum or bituminous oil. Petroleum coke includes fluid coke and delayed coke depending on the coking method. However, fluid coke is in the form of powder and is not used for much as it is used for private fuel in refineries, and what is generally called petroleum coke is delayed coke. Delayed coke includes raw coke and calcined coke.
  • Raw coke is the raw coke collected from the coking device, and calcined coke is further baked to remove volatiles. Since raw coke has a high possibility of causing a dust explosion, in order to obtain fine-grained petroleum coke, raw coke was calcined to remove volatile matter and then pulverized. Conventionally, calcined coke has been generally used for electrodes and the like. Since raw coke has less ash than coal coke, it has only been used for carbon materials in casting industry, coke for casting, coke for alloy iron, and the like.
  • this carbon raw material is pulverized.
  • a known jet mill, hammer mill, roller mill, pin mill, vibration mill or the like is used for pulverizing the carbon raw material.
  • the carbon raw material is preferably pulverized with a carbon raw material having a thermal history as low as possible.
  • the carbon raw material is easily pulverized, and the crack direction at the time of crushing becomes almost random and the aspect ratio tends to be small.
  • the probability that the edge portion exposed to the pulverized surface is repaired in the subsequent heating process is increased, and there is an effect that side reactions during charging and discharging can be reduced.
  • the pulverized carbon raw material can be fired at a low temperature of about 500 to 1200 ° C. in a non-oxidizing atmosphere before being graphitized.
  • gas generation in the next graphitization treatment can be reduced, and since the bulk density can be lowered, the graphitization treatment cost can be reduced.
  • the graphitization treatment of the pulverized carbon raw material is desirably performed in an atmosphere in which the carbon raw material is not easily oxidized.
  • a heat treatment method in an atmosphere such as argon gas, a heat treatment method in an Atchison furnace (non-oxidizing graphitization process), and the like can be given.
  • the non-oxidizing graphitization process is preferable from the viewpoint of cost.
  • the lower limit of the temperature in the graphitization treatment is usually 2000 ° C, preferably 2500 ° C, more preferably 2900 ° C, and most preferably 3000 ° C.
  • the upper limit of the temperature in the graphitization treatment is not particularly limited, but is preferably 3300 ° C. from the viewpoint that a high discharge capacity is easily obtained.
  • the powder is crushed or pulverized after the graphitization treatment, the smooth surface may be damaged and the performance may be deteriorated.
  • the obtained artificial graphite can be used as a negative electrode material as it is. Further, the artificial graphite can be used as a core material, and the surface thereof can be coated with a carbon material and combined to be used as a negative electrode material.
  • the compounding can be performed according to a known method. For example, stirring is performed while spraying an organic compound on the obtained artificial graphite. Further, the artificial graphite and the organic compound can be mixed with an apparatus such as a hybridizer manufactured by Nara Machinery, and then can be naturally adhered to the surface of the graphite at the stage of heat treatment to be combined.
  • a preferable coating layer is obtained by heat-treating an organic compound at 200 ° C. or higher and 3000 ° C. or lower, preferably 500 ° C. or higher and 2000 ° C. or lower. If the final heat treatment temperature is too low, carbonization is not sufficiently completed and hydrogen or oxygen remains, which may adversely affect battery characteristics. Further, if the treatment temperature is too high, the crystallization of graphite may proceed excessively and the charging characteristics may be lowered.
  • the organic compound is not particularly limited, but isotropic pitch, anisotropic pitch, resin, resin precursor or monomer is preferable.
  • a resin precursor or monomer it is preferable to polymerize the resin precursor or monomer to make a resin.
  • Suitable organic compounds include at least one compound selected from the group consisting of petroleum pitch, coal pitch, phenol resin, polyvinyl alcohol resin, furan resin, cellulose resin, polystyrene resin, polyimide resin and epoxy resin. It is done.
  • the amount of the organic compound used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of artificial graphite.
  • the heat treatment is preferably performed in a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere include an atmosphere filled with an inert gas such as argon gas or nitrogen gas.
  • the artificial graphite is fused and becomes a lump, so that it is atomized for use as an electrode active material. Since the thickness of the coating layer is on the order of nm, the particle diameter of the composite artificial graphite is almost equal to the particle diameter of the core material. That is, D50 of the composite graphite is preferably 4 to 10 ⁇ m, more preferably 4 to 8 ⁇ m, and further preferably 4 to 6 ⁇ m.
  • the composite graphite it is desirable that 90% or more of the total number of particles is in the range of 4 to 10 ⁇ m in the same manner as the uncomposited artificial graphite (A). Also, the d (002) and BET specific surface area of the composite graphite are preferably in the same range as that of the uncomposited artificial graphite (A).
  • the ratio between the artificial graphite as the core material and the coating layer is not particularly limited, but when the core material is 100 parts by mass, the coating layer is preferably 0.05 to 10 parts by mass, 1 to 10 parts by mass is more preferable. If the amount of the coating layer is too small, the effect based on the formation of the coating layer cannot be obtained. If the amount of the coating layer is too large, the battery capacity may be reduced. The amount of the coating layer can be calculated from the amount when an organic compound is used.
  • the carbon material (B) preferably has d (002) of 0.340 nm or more. Further preferred d (002) is 0.342 nm or more. When d (002) becomes narrower than 0.340 nm, the acceptability of lithium ions decreases, and the charging efficiency decreases. Lc is preferably 10 nm or less.
  • the carbon material (B) preferably has a D50 of 7 to 17 ⁇ m.
  • D50 is in the above range, lithium ions can efficiently react with the electrolytic solution and exhibit excellent discharge characteristics, and the capacity and cycle characteristics can be maintained high. If D50 is too small, the specific surface area becomes large, so that the reaction active point with the electrolytic solution increases, leading to a decrease in the initial efficiency. When D50 is too large, the contact area with the electrolytic solution becomes small, and the resistance value and the input / output characteristics become small.
  • D50 of a carbon material (B) is larger than D50 of the said artificial graphite (A).
  • the upper limit value of the BET specific surface area of the carbon material (B) is preferably 7 m 2 / g, more preferably 6 m 2 / g.
  • the lower limit value of the BET specific surface area is preferably 0.5 m 2 / g, more preferably 1.0 m 2 / g. If the BET specific surface area is too large, the contact area with the electrolytic solution increases, so the irreversible capacity tends to be large and the cycle characteristics tend to deteriorate. Moreover, the mixture (slurry) containing a carbon material (B) with a large specific surface area has a high viscosity, and there exists a tendency for applicability
  • both graphitizable carbon (soft carbon) and non-graphitizable carbon (hard carbon) can be used.
  • the raw material for the carbon material (B) is coal-based or petroleum-based raw coke, calcined coke, resin, resin precursor, or monomer. When using a resin precursor and a monomer, it is preferable to polymerize it into a resin. Suitable resins include phenol resins, polyvinyl alcohol resins, furan resins, cellulose resins, polystyrene resins, polyimide resins, and epoxy resins, and these can be used alone or in combination.
  • raw materials are preferably heat-treated in advance in an autoclave or the like and pulverized.
  • a known jet mill, hammer mill, roller mill, pin mill, vibration mill or the like is used for pulverization.
  • the crushed material is fired at about 700-1500 ° C. in a non-oxidizing atmosphere.
  • the preferred heat treatment temperature varies depending on the type of material, but if the final heat treatment temperature is too low, carbonization does not proceed sufficiently, and hydrogen, oxygen, etc. may remain and adversely affect battery performance. preferable. In the case of graphitizable carbon, if the heat treatment temperature is too high, the crystallization of graphite may proceed excessively and the charging characteristics may be deteriorated.
  • graphitizable carbon refers to a carbon material obtained by heat-treating an easily graphitizable organic substance at 700 ° C. or more and 2000 ° C. or less.
  • non-graphitizable carbon refers to a carbon material obtained by heat-treating a non-graphitizable organic substance.
  • the negative electrode material for a lithium ion secondary battery in a preferred embodiment of the present invention can be produced by mixing the artificial graphite (A) and the carbon material (B).
  • the mixing method is not particularly limited.
  • a high-speed chopper such as a Henschel mixer or a Spartan Luzer, a Nauter mixer, a ribbon mixer, or the like can be used to perform uniform mixing at high speed.
  • the mixing ratio of the artificial graphite (A) and the carbon material (B) varies depending on the required characteristics.
  • the artificial graphite (A) is preferably 30 to 80% by mass
  • the carbon material (B) is preferably 70 to 20% by mass
  • the artificial graphite (A) is 50 to 80% by mass. More preferably, the carbon material (B) is 50 to 20% by mass.
  • the artificial graphite (A) is preferably 20 to 60% by mass
  • the carbon material (B) is preferably 80 to 40% by mass
  • the artificial graphite (A) is 20 to 40% by mass.
  • the carbon material (B) is more preferably 80 to 60% by mass.
  • the proportion of the artificial graphite (A) is less than 20% by mass, the electrode density, the battery capacity, and the output density are lowered, and the cycle characteristics tend to be lowered.
  • the proportion of the carbon material (B) is less than 20% by mass, the lithium ion acceptability of the electrode is lowered, and a sufficient charging property improvement effect cannot be obtained.
  • the negative electrode paste in a preferred embodiment of the present invention includes the negative electrode material, a binder, and a dispersion medium.
  • This negative electrode paste may contain a conductive additive.
  • This negative electrode paste can be obtained by kneading the negative electrode material, a binder, and a dispersion medium.
  • the negative electrode paste can be formed into a sheet shape, a pellet shape, or the like.
  • the binder include polyethylene, polypropylene, ethylene propylene terpolymer, butadiene rubber, styrene butadiene rubber, butyl rubber, and a polymer compound having high ionic conductivity.
  • polymer compound having a high ionic conductivity examples include polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphasphazene, polyacrylonitrile and the like.
  • the mixing ratio of the composite graphite and the binder is preferably 0.5 to 20 parts by mass of the binder with respect to 100 parts by mass of the composite graphite.
  • the dispersion medium is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, dimethylformamide, isopropanol, and water.
  • a binder that uses water as a dispersion medium it is preferable to use a thickener together.
  • the amount of the dispersion medium is adjusted so that the viscosity is easy to apply to the current collector.
  • vapor grown carbon fiber having high crystallinity and high thermal conductivity is preferable.
  • the blending amount is preferably about 0.01 to 20 parts by mass when the negative electrode material (negative electrode active material) is 100 parts by mass.
  • the negative electrode paste can be obtained by applying the negative electrode paste on a current collector, drying, and press-molding.
  • the current collector include foils such as nickel and copper, and meshes.
  • the method for applying the paste is not particularly limited.
  • the coating thickness of the paste is usually 50 to 200 ⁇ m. When the coating thickness becomes too large, the negative electrode cannot be accommodated in a standardized battery container, and the internal resistance of the battery increases due to an increase in the lithium ion diffusion distance.
  • Examples of the pressure molding method include molding methods such as roll pressing and press pressing. The pressure during pressure molding is preferably about 100 MPa to about 300 MPa (about 1 to 3 t / cm 2 ).
  • the negative electrode thus obtained is suitable for a lithium secondary battery.
  • the electrode density after pressure molding is desirably 1.1 to 1.6 g / cm 3 .
  • the electrode density is less than 1.1 g / cm 3
  • the battery has a small volume energy density.
  • the electrode density is greater than 1.6 g / cm 3 , the voids in the electrode are reduced and the penetration of the electrolyte solution deteriorates. There is a problem that the diffusion of the liquid becomes worse and the charge / discharge characteristics become smaller.
  • Lithium secondary battery A lithium secondary battery can be manufactured using the negative electrode as a constituent element.
  • a lithium-containing transition metal oxide is usually used as the positive electrode active material, and preferably at least one selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mo and W.
  • An oxide mainly containing a transition metal element and lithium is used, and a compound having a molar ratio of lithium to the transition metal element of 0.3 to 2.2 is used, and more preferably V, Cr, Mn, Fe
  • An oxide mainly containing at least one transition metal element selected from Co and Ni and lithium and having a molar ratio of lithium to transition metal of 0.3 to 2.2 is used.
  • Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, or the like may be contained in a range of less than 30 mole percent with respect to the transition metal present mainly.
  • the value of x is a value before the start of charging / discharging, and increases / decreases by charging / discharging.
  • the average particle size of the positive electrode active material is not particularly limited, but is preferably 0.1 to 50 ⁇ m.
  • the volume of particles of 0.5 to 30 ⁇ m is preferably 95% or more. More preferably, the volume occupied by a particle group having a particle size of 3 ⁇ m or less is 18% or less of the total volume, and the volume occupied by a particle group of 15 ⁇ m or more and 25 ⁇ m or less is 18% or less of the total volume.
  • the particle size here is calculated by the volume-based cumulative particle size distribution in the particle size distribution measurement by the laser diffraction method, and the average particle size is the particle size at a cumulative 50%.
  • the specific surface area is not particularly limited, but is preferably 0.01 ⁇ 50m 2 / g by BET method, particularly preferably 0.2m 2 / g ⁇ 10m 2 / g.
  • the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
  • the electrolytic solution used for the lithium secondary battery is not particularly limited.
  • lithium salts such as LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , CH 3 SO 3 Li, CF 3 SO 3 Li, for example, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate
  • organic electrolytes dissolved in non-aqueous solvents such as diethyl carbonate, propylene carbonate, butylene carbonate, acetonitrile, propironitrile, dimethoxyethane, tetrahydrofuran, and ⁇ -butyrolactone, and so-called polymer electrolytes in solid or gel form.
  • an additive exhibiting a decomposition reaction when the lithium secondary battery is initially charged to the electrolytic solution.
  • the additive include vinylene carbonate, biphenyl, propane sultone and the like.
  • the addition amount is preferably 0.01 to 5% by mass.
  • a separator can be provided between the positive electrode and the negative electrode.
  • the separator include non-woven fabric, cloth, microporous film, or a combination thereof, mainly composed of polyolefin such as polyethylene and polypropylene.
  • ⁇ Battery evaluation> Preparation of negative electrode An aqueous dispersion containing styrene-butadiene (SBR) fine particles having a solid content ratio of 40% by adding 1.5 g of carboxymethyl cellulose (CMC) as a thickener and water appropriately to 100 g of the negative electrode material and adjusting the viscosity. 3.8 g was added and stirred and mixed to prepare a slurry-like dispersion having sufficient fluidity. The prepared dispersion was applied onto a copper foil having a thickness of 20 ⁇ m using a doctor blade so as to be uniform at a thickness of 150 ⁇ m, dried on a hot plate, and then dried at 70 ° C. for 12 hours in a vacuum dryer.
  • SBR styrene-butadiene
  • the density of the dried electrode was adjusted by a roll press to obtain a negative electrode for battery evaluation.
  • the applied amount of the obtained electrode was 7 mg / cm 2 , and the electrode density was 1.4 g / cm 3 .
  • a liquid dispersion was prepared.
  • the produced dispersion was applied onto a 20 ⁇ m thick aluminum foil with a roll coater, dried, and then pressure-formed with a roll press.
  • the coating amount of the obtained positive electrode was 10 mg / cm 2 , and the electrode density was 2.0 g / cm 3 .
  • Electrolyte preparation Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3: 7 as a nonaqueous solvent, and 1.0 mol of lithium hexafluorophosphate (LiPF 6 ) was used as an electrolyte salt. / L dissolved was used as an electrolytic solution.
  • EC Ethylene carbonate
  • EMC ethyl methyl carbonate
  • Example 1 70 parts by mass of artificial graphite (A) and 30 parts by mass of the carbon material (B) were placed in a Fuji Panda Spartan Luther and mixed for 5 minutes to obtain a negative electrode material.
  • the obtained negative electrode material had a D50 of 8.2 ⁇ m and a BET specific surface area of 2.6 m 2 / g.
  • An electrode and a battery cell were produced using this negative electrode material, and the battery characteristics were evaluated. The results are shown in Table 1.
  • Example 2 A negative electrode material, an electrode and a battery cell were produced in the same manner as in Example 1 except that the amount of the artificial graphite (A) was changed to 50 parts by mass and the amount of the carbon material (B) was changed to 50 parts by mass.
  • the obtained negative electrode material had a D50 of 9.9 ⁇ m, a BET specific surface area of 2.6 m 2 / g, and the battery characteristics were as shown in Table 1.
  • Example 3 A negative electrode material, an electrode, and a battery cell were produced in the same manner as in Example 1 except that the amount of the artificial graphite (A) was changed to 30 parts by mass and the amount of the carbon material (B) was changed to 70 parts by mass.
  • the obtained negative electrode material had a D50 of 11.4 ⁇ m, a BET specific surface area of 2.5 m 2 / g, and the battery characteristics were as shown in Table 1.
  • Comparative Example 1 Except for the pulverization so that the average particle size (D50) is 16 ⁇ m, the same operation as in the method for producing artificial graphite (A) is carried out, the BET specific surface area is 1.1 m 2 / g, and d (002 ) Obtained artificial graphite having 0.336 nm. 50 parts by mass of the obtained artificial graphite and 50 parts by mass of the carbon material (B) were placed in a Fujipandal Spartan Luther and mixed for 5 minutes to obtain a negative electrode material. The obtained negative electrode material had a D50 of 14.5 ⁇ m and a BET specific surface area of 1.8 m 2 / g. An electrode and a battery cell were produced using this negative electrode material, and the battery characteristics were evaluated. The results are shown in Table 1.
  • Comparative Example 2 The battery characteristics were evaluated in the same manner as in Example 1 except that only the carbon material (B) was used as the negative electrode active material and the electrode collapsibility was poor and the electrode density of the negative electrode was 1.3 g / cm 2 . The results are shown in Table 1.
  • Fig. 1 shows a charging curve of 5C charging measured with the batteries obtained in Examples 1 to 3. It can be seen that the cell can be charged from a low potential state by mixing the carbon material (B) having low crystallinity. This is considered to be due to the increase in Li ion acceptability at the initial stage of charging due to the carbon material (B), thereby enabling smooth charging.

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Abstract

L'invention concerne un matériau d'électrode négative pour une batterie secondaire au lithium-ion qui est caractérisé en ce qu'il comprend un mélange de : graphite artificiel (A) pour lequel l'espacement (d(002)) de la surface (002) de la structure de graphite, tel que mesuré par diffractométrie des rayons X sur poudre, est dans la plage de 0,335 à 0,339 nm, et le diamètre de particule (D50) pour lequel la fréquence totale volumique de la distribution de taille de particule mesurée par diffractométrie laser est de 50 % est de 4 à 10 µm ; et un matériau carboné (B) pour lequel d(002) est au moins 0,340 nm, et D50 est de 7 à 17 µm et est supérieur au D50 du graphite artificiel (A).
PCT/JP2013/083288 2012-12-13 2013-12-12 Matériau d'électrode négative pour batterie secondaire au lithium-ion, feuille d'électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium Ceased WO2014092141A1 (fr)

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CN201380064298.6A CN104838526B (zh) 2012-12-13 2013-12-12 锂离子二次电池用负极材料、锂离子二次电池用负极片和锂二次电池

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US10923705B2 (en) 2017-05-26 2021-02-16 Toyota Jidosha Kabushiki Kaisha Method of producing negative electrode for nonaqueous electrolyte secondary battery and method of producing nonaqueous electrolyte secondary battery
EP3955348A4 (fr) * 2020-04-30 2022-07-27 Contemporary Amperex Technology Co., Limited Matériau actif d'électrode négative et son procédé de préparation, batterie secondaire et dispositif comprenant une batterie secondaire
CN115699369A (zh) * 2020-06-18 2023-02-03 引能仕株式会社 锂离子二次电池负极用人造石墨材料及其制造方法
JP2023057353A (ja) * 2021-10-11 2023-04-21 株式会社Ｇｓユアサ 非水電解質蓄電素子
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CN112437993B (zh) * 2018-07-11 2024-06-18 株式会社力森诺科 锂离子二次电池用负极材、锂离子二次电池用负极、锂离子二次电池、和锂离子二次电池用负极的制造方法
CN109921098B (zh) * 2018-11-20 2020-12-15 万向一二三股份公司 一种水系超级纳米磷酸铁锂电池的制备方法
WO2021019728A1 (fr) * 2019-07-31 2021-02-04 昭和電工マテリアルズ株式会社 Procédé de fabrication de matière d'électrode négative pour batterie secondaire au lithium-ion, et procédé de fabrication de batterie secondaire au lithium-ion
PL3968416T3 (pl) 2020-06-04 2024-09-23 Ningde Amperex Technology Ltd. Materiał czynny elektrody ujemnej oraz urządzenie elektrochemiczne i urządzenie elektroniczne, w których stosuje się materiał czynny elektrody ujemnej
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EP3955348A4 (fr) * 2020-04-30 2022-07-27 Contemporary Amperex Technology Co., Limited Matériau actif d'électrode négative et son procédé de préparation, batterie secondaire et dispositif comprenant une batterie secondaire
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JP2023057353A (ja) * 2021-10-11 2023-04-21 株式会社Ｇｓユアサ 非水電解質蓄電素子
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