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WO2017111542A1 - Matériau actif d'anode pour une batterie rechargeable au lithium et anode pour une batterie rechargeable au lithium comprenant ce dernier - Google Patents

Matériau actif d'anode pour une batterie rechargeable au lithium et anode pour une batterie rechargeable au lithium comprenant ce dernier Download PDF

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Publication number
WO2017111542A1
WO2017111542A1 PCT/KR2016/015195 KR2016015195W WO2017111542A1 WO 2017111542 A1 WO2017111542 A1 WO 2017111542A1 KR 2016015195 W KR2016015195 W KR 2016015195W WO 2017111542 A1 WO2017111542 A1 WO 2017111542A1
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Prior art keywords
artificial graphite
negative electrode
active material
electrode active
secondary battery
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Ceased
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PCT/KR2016/015195
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English (en)
Korean (ko)
Inventor
최희원
우상욱
정동섭
김동혁
김은경
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020160176723A external-priority patent/KR102088491B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to PL16879409T priority Critical patent/PL3297073T3/pl
Priority to JP2018528931A priority patent/JP6621926B2/ja
Priority to EP16879409.7A priority patent/EP3297073B1/fr
Priority to CN201680040848.4A priority patent/CN107851795B/zh
Priority to US15/737,652 priority patent/US10439221B2/en
Publication of WO2017111542A1 publication Critical patent/WO2017111542A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 negative electrode active material for a lithium secondary battery and a negative electrode for a lithium secondary battery comprising the same, and more particularly, to a negative electrode active material for a lithium secondary battery including two kinds of artificial graphite having a large particle size and a small particle size, and a charge by including the same.
  • the present invention relates to a negative electrode for a lithium secondary battery having reduced charge transfer resistance (CTR).
  • the carbon-based active material various types of carbon-based materials including artificial graphite, natural graphite, and hard carbon have been applied.
  • the graphite-based active material that can guarantee the life characteristics of a lithium secondary battery with excellent reversibility is most widely used. have. Since the graphite-based active material has a low discharge voltage of -0.2V compared to lithium, the battery using the graphite-based active material may exhibit a high discharge voltage of 3.6V, and thus provides many advantages in terms of energy density of the lithium battery.
  • the charge transfer resistance is increased due to the polycrystallization of the nanostructure, or by the components of the cylindrical solid electrolyte interphase (SEI) film formed on the electrode surface (organic coating, inorganic coating). Insertion and desorption reactions of lithium ions become difficult, and thus, charge transfer resistance increases, resulting in deterioration of lithium ion battery performance.
  • SEI cylindrical solid electrolyte interphase
  • the first technical problem of the present invention is to provide a negative electrode active material for lithium secondary batteries comprising two kinds of artificial graphite having a large particle size and a small particle size.
  • Another object of the present invention is to provide a negative electrode including the negative electrode active material for a lithium secondary battery.
  • Another object of the present invention is to provide a lithium secondary battery including the negative electrode.
  • the first artificial graphite (A) includes secondary artificial graphite particles in which one or more primary artificial graphite particles are aggregated, and a carbon coating layer formed on a surface of the secondary artificial graphite particles,
  • the weight ratio of the first artificial graphite to the second artificial graphite is 85:15 to 95: 5 to provide a negative electrode active material for a lithium secondary battery.
  • the average particle diameter (D50) of the primary artificial graphite particles included in the first artificial graphite (A) is 8 ⁇ m to 10 ⁇ m, and the average particle diameter (D50) of the secondary artificial graphite particles is 14 ⁇ m to 20 ⁇ m.
  • the porosity of the secondary artificial graphite particles is about 1% to 20%, and the BET specific surface area of the secondary artificial graphite particles may be 2m 2 / g to 10m 2 / g.
  • the weight ratio of the secondary artificial graphite particles and the carbon coating layer included in the first artificial graphite (A) is 70:30 to 95: 5.
  • first artificial graphite (A) there may be a second void, which is an empty space existing between the secondary artificial graphite particles formed by aggregation of primary artificial graphite particles and the carbon coating layer.
  • the porosity of the first artificial graphite is from about 5% to 15%, wherein (A) the BET specific surface area of the first artificial graphite may be 2 m 2 / g to 30m 2 / g.
  • the negative electrode active material of the present invention may include a third gap according to the particle size of the (A) first artificial graphite and (B) the second artificial graphite.
  • the porosity of the cathode active material is about 5 to 20%, BET specific surface area of the negative active material may be 2 m 2 / g to 30m 2 / g.
  • the average particle diameter (D50) of the negative electrode active material may be 12 ⁇ m to 20 ⁇ m, specifically 15 ⁇ m to 20 ⁇ m.
  • a negative electrode for a lithium secondary battery comprising a current collector and a negative electrode mixture layer coated on the current collector,
  • the negative electrode mixture layer provides a negative electrode for a lithium secondary battery including the negative electrode active material of the present invention.
  • the embodiment of the present invention includes a negative electrode, a positive electrode, a separator and an electrolyte interposed between the negative electrode and the positive electrode, and the negative electrode provides a lithium secondary battery including the negative electrode of the present invention.
  • a negative electrode active material comprising two kinds of artificial graphite having a large particle size and a small particle size
  • CTR charge transfer resistance
  • FIG. 1 is a graph illustrating a result of measuring a charge transfer resistance value of a lithium secondary battery according to Experimental Example 1 of the present invention.
  • Figure 2 is a graph showing the results of measuring the output characteristics of the lithium secondary battery at room temperature according to Experimental Example 2 of the present invention.
  • the present invention provides a negative electrode active material having a bi-modal structure and a negative electrode including the same, in which two kinds of artificial graphite having different particle sizes are mixed in order to reduce the resistance transfer resistance of the electrode.
  • the present invention provides a lithium secondary battery having the negative electrode.
  • the first artificial graphite (A) includes secondary artificial graphite particles in which one or more primary artificial graphite particles are aggregated, and a carbon coating layer formed on a surface of the secondary artificial graphite particles,
  • the weight ratio of the first artificial graphite to the second artificial graphite is 85:15 to 95: 5 to provide a negative electrode active material for a lithium secondary battery.
  • the first artificial graphite (A) having a large particle diameter is secondary artificial graphite particles (a ') formed by agglomeration of one or more primary artificial graphite particles (a) and the secondary It may include a carbon coating layer (b) coated on the surface of the artificial graphite particles (a ').
  • the average particle diameter (D50) of the primary artificial graphite particles (a) may be 8 to 10 ⁇ m.
  • the average particle diameter of the first artificial graphite particles (a) is less than 8 ⁇ m, the orientation index is lowered and the discharge capacity of the artificial graphite is lowered.
  • the average particle diameter of the first artificial graphite particles (a) exceeds 10 ⁇ m, the average particle size of the secondary mixed artificial graphite particles (a ′) may be increased, thereby degrading rapid charging performance.
  • the average particle diameter (D50) of the secondary artificial graphite particles (a ') may be 14 ⁇ m to 20 ⁇ m, specifically 17 ⁇ m.
  • the orientation index is lowered and the discharge capacity of the artificial graphite is lowered.
  • the average particle diameter of the second artificial graphite particles exceeds 20 ⁇ m, there is a disadvantage in that the rapid filling performance is lowered as the orientation index increases.
  • the average particle diameter (D50) of the primary artificial graphite particles and the secondary artificial graphite particles may be defined as the particle size at 50% of the particle size distribution of the particles.
  • the average particle diameter (D50) of the artificial graphite particles according to an embodiment of the present invention can be measured using, for example, a laser diffraction method.
  • the laser diffraction method can measure the particle diameter of several mm from the submicron region, and high reproducibility and high resolution can be obtained.
  • the secondary artificial graphite particles are made of a collection of primary artificial graphite particles as described above, the first void may be present in the secondary artificial graphite particles.
  • the first void may be an empty space between the primary artificial graphite particles as described above, may be amorphous, and may exist at least two.
  • the first pores may have various forms such as extended to the surface of the secondary artificial graphite particles and exposed to the outside, or may exist only inside the secondary particles.
  • the first void that did not exist in the conventional negative electrode active material It may include.
  • the contact area between the negative electrode active material and the lithium ions may be widened, thereby further improving the capacity characteristics and the cycle life characteristics.
  • the secondary artificial graphite particles including the first pores may have a porosity of about 1% to 20%, specifically 2% to 10%.
  • the porosity may be defined as a percentage of the volume occupied by all the pores present in the secondary particles, based on the total volume of the secondary particles.
  • the porosity of the secondary artificial graphite particles may be defined as follows:
  • Porosity pore volume per unit mass / (specific volume + pore volume per unit mass)
  • the measurement of the porosity is not particularly limited, and according to an embodiment of the present invention, for example, Brunauer-Emmett-Teller (BET) measuring method using BELSORP (BET equipment) of BEL JAPAN using an adsorption gas such as nitrogen or Mercury penetration can be measured by Hg porosimetry.
  • BET Brunauer-Emmett-Teller
  • the secondary artificial graphite particles may have a BET specific surface area.
  • the BET specific surface area of the secondary particles may be 2m 2 / g to 10m 2 / g. Secondary artificial graphite particles having a BET specific surface area in this range may have excellent capacity characteristics and cycle life characteristics.
  • the specific surface area of the secondary grained graphite particles can be measured by the Brunauer-Emmett-Teller (BET) method.
  • BET Brunauer-Emmett-Teller
  • it can be measured by BET 6-point method by nitrogen gas adsorption distribution method using a porosimetry analyzer (Bell Japan Inc, Belsorp-II mini).
  • a carbon coating layer (b) may be present on the surface of the secondary artificial graphite particles to further improve conductivity.
  • the carbon coating layer is provided with at least one material selected from the group consisting of secondary coal-tar pitch, rayon and polyacrylonitrile-based resins or precursors of the material to the surface of the secondary particles, and then pyrolyzed them. It can be formed by. Alternatively, the carbon coating layer may be formed by chemical vapor deposition of carbon on the particle surface.
  • the weight ratio of the secondary artificial graphite particles and the carbon coating layer may be 70:30 to 95: 5. If the content of the secondary artificial graphite particles (a ') is less than 70% by weight, or the content of the carbon coating layer (b) is more than 30% by weight, carbon having a relatively low crystallinity compared to graphite is excessively coated. The capacity of the negative electrode active material is lowered, and the artificial graphite particles are hardened by the carbon coating layer, thereby making it difficult to press the electrode.
  • a second void which is an empty space existing between the secondary artificial graphite particles formed by aggregation of the primary artificial graphite particles and the carbon coating layer.
  • the second void may be an empty space between the secondary artificial graphite particles in which the primary artificial graphite particles are aggregated and the carbon coating layer, and may exist at least two.
  • the second void may have various forms, such as extending to the surface of the first artificial graphite (A) and being exposed to the outside, or present only inside the first artificial graphite.
  • the porosity of the first artificial graphite (A) including the second void may be about 5 to 15%.
  • the porosity may be defined as a percentage of the volume occupied by all the pores present in the first artificial graphite based on the total volume of the first artificial graphite.
  • the BET specific surface area of the first artificial graphite (A) may be 2 m 2 / g to 30 m 2 / g.
  • the porosity and specific surface area of the above (A) first artificial graphite can be measured by the method as described above.
  • the first artificial graphite (A) is to produce the primary artificial graphite particles, and then agglomerated one or more primary artificial graphite particles (a) to secondary particles, the second It can be prepared by mixing the artificial graphite (a ') and the carbon-based pitch granulated and heat-treated.
  • the step of obtaining the secondary artificial graphite particles is the primary artificial graphite particles are put into the reactor, and then operated, that is, the primary artificial graphite particles by spinning (spinning) the primary artificial graphite particles by centrifugal force Aggregate with each other to form secondary artificial graphite particles.
  • the first artificial graphite (A) of the present invention is a first artificial graphite (A) of the present invention.
  • the process of high-temperature heat treatment of the needle coke-based artificial graphite can be appropriately adjusted according to the size of the primary artificial graphite particles to be formed, specifically 1 minute to 5 hours at 3000 to 5000 °C, the average particle diameter ( Primary artificial graphite particles having a D50) of 8 ⁇ m to 10 ⁇ m.
  • the step of agglomerating the primary artificial graphite particles is a pitch and a resin binder is added to the reactor together, at a speed of 2000 rpm to 4000 rpm, specifically 3000 rpm at a temperature of about 1400 to 1600 °C, specifically 1500 °C temperature It can carry out while rotating.
  • the pitch is a component added to improve the cohesive effect of the primary artificial graphite particles, it may be added in an amount of 1 to 10% by weight based on the total weight of the primary artificial graphite particles.
  • the resin binder is a component used in the manufacture of a conventional electrode, it is added in 1 to 5% by weight based on the total weight of the primary artificial graphite particles.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluor Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers thereof, and the like.
  • the primary artificial graphite particles are spherical to obtain secondary artificial graphite particles in which primary artificial graphite particles are agglomerated, and then further heat treatment may be performed on the secondary graphite particle particles. Since the bonding or rearrangement is possible between the primary artificial graphite particles by the heat treatment process, it is possible to obtain an advantage of improving the microstructure of the secondary artificial graphite particles.
  • the conditions of the heat treatment process will vary depending on the size of secondary artificial graphite particles to be formed, etc., for example, in the range of 1000 ° C to 3000 ° C and in the range of 1 hour to 10 hours in a reducing atmosphere and / or an inert atmosphere. Can be selected within.
  • the heat treatment process for forming the carbon coating layer may be carried out in a temperature range of 1000 to 4000 °C.
  • the first artificial graphite (A) of the present invention prepared by this method may have a large particle diameter of 15 ⁇ m to 20 ⁇ m in average particle diameter (D50).
  • the average particle diameter of the first artificial graphite is less than 15 ⁇ m, the average particle diameter of the artificial graphite constituting the negative electrode active material is atomized, so that the discharge capacity is lowered.
  • the average particle diameter of the first artificial graphite exceeds 20 ⁇ m, the particle size of the negative electrode active material is increased, there is a disadvantage that the low-temperature, low-temperature output performance of the negative electrode.
  • the second artificial graphite (B) of the small particle diameter included to prepare the negative electrode active material of the present invention is a by-product generated during the process of manufacturing the first artificial graphite, and manufactured similarly to the first artificial graphite production method. do.
  • the second artificial graphite (B) forms a needle coke-based artificial graphite by coking a petroleum pitch, a by-product produced after petroleum extraction, and then heat-processes the needle coke-based artificial graphite at a high temperature of 3000 ° C. or higher.
  • Particle size among the first granulated graphite particles generated after oxidization is small and is a by-product classified as a loss product during the process.
  • the second artificial graphite (B) has undergone graphitization but is in the form of primary particles, has a small particle size, a problem due to irreversible capacity according to the particle size, and a decrease in initial efficiency. Substance.
  • manufacturing cost can be reduced by using such a 2nd artificial graphite.
  • the average particle diameter (D50) of the second artificial graphite (B) may be 3 ⁇ m to 5 ⁇ m, when the average particle diameter of the second artificial graphite is less than 3 ⁇ m, disadvantages that the capacity decrease due to irreversible There is this.
  • the average particle diameter of the first artificial graphite exceeds 5 ⁇ m, the average particle size increases, and thus the effect of reducing the charge transfer resistance and improving the output performance of the finely divided artificial graphite having a small particle size is insufficient.
  • first artificial graphite having an average particle diameter (D50) of 15 ⁇ m to 20 ⁇ m and (B) second artificial graphite having an average particle diameter (D50) of 3 ⁇ m to 5 ⁇ m 85:15 to 95: It provides a negative electrode active material comprising a weight ratio of 5.
  • the negative electrode active material of the present invention preferably includes a first artificial graphite having the average particle diameter and content as described above.
  • a third void may exist in the negative electrode active material of the present invention according to the particle size of the (A) first artificial graphite and (B) the second artificial graphite.
  • the third void may be an empty space between the first artificial graphite particles and the second artificial graphite particles, and may exist at least two.
  • the third void may have various forms such as extended to the surface of the negative electrode active material and exposed to the outside or may exist only inside the negative electrode active material.
  • the porosity of the negative electrode active material of the present invention including the third pore may be about 5 to 20%.
  • the BET specific surface area of the negative electrode active material may be 2 m 2 / g to 30m 2 / g.
  • the specific surface area of the negative electrode active material exceeds 30 m 2 / g, it may be difficult to control the side reaction with the electrolyte due to the large specific surface area, and when less than 2 m 2 / g, sufficient pores are not formed in the negative electrode active material, It is not preferable because it may be difficult to effectively accommodate volume expansion during charging and discharging.
  • the average particle diameter of the negative electrode active material is 12 ⁇ m to 20 ⁇ m, specifically 15 ⁇ m to 20 ⁇ m.
  • the average particle diameter of the negative electrode active material is less than 12 ⁇ m, it may be difficult to disperse in the negative electrode active material slurry, or there may be a problem in that the negative electrode active material in the electrode aggregates.
  • One reaction is difficult and the life characteristics and thickness expansion suppression characteristics can be greatly reduced.
  • the negative electrode active material of the present invention may be prepared by mixing the first artificial graphite and the second artificial graphite in a TK Mixer at a speed of 50 rpm (Rotation per minute) or more.
  • a negative electrode for a lithium secondary battery comprising a current collector and a negative electrode mixture layer coated on the current collector,
  • the negative electrode mixture layer provides a negative electrode for a lithium secondary battery including the negative electrode active material of the present invention.
  • the porosity inside the negative electrode mixture layer may be 20% or more, specifically 20% to 40%.
  • the negative electrode mixture layer may be prepared by applying a negative electrode active material slurry containing a negative electrode active material and optionally a binder, a conductive material and a solvent on the electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material may include the negative electrode active material of the present invention in which two kinds of artificial graphite having different particle sizes are mixed.
  • the negative electrode active material in addition to the negative electrode active material of the present invention, other active materials capable of reversible intercalation and deintercalation of lithium, specifically natural graphite, artificial graphite, carbonaceous materials; Metals such as lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals; Oxides of the above metals; And one or two or more negative electrode active materials selected from the group consisting of metals and composites with carbon.
  • LTO lithium-containing titanium composite oxide
  • Si silicon, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe
  • Alloys composed of the metals Oxides of the above metals
  • one or two or more negative electrode active materials selected from the group consisting of metals and composites with carbon.
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the negative electrode mixture.
  • the negative electrode mixture layer of the present invention may optionally further include at least one additive selected from the group consisting of a binder, a thickener and a conductive material.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the negative electrode mixture.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluor Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various
  • thickener all thickeners conventionally used in lithium secondary batteries may be used, and for example, carboxymethyl cellulose (CMC).
  • CMC carboxymethyl cellulose
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of the negative electrode mixture.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack and EC, which are acetylene black series. Family (Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and Super P (manufactured by Timcal).
  • the solvent may include an organic solvent such as water or NMP (N-methyl-2-pyrrolidone), and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material, and optionally a binder and a conductive material.
  • concentration of the negative electrode active material and, optionally, the solid content including the binder and the conductive material may be 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the negative electrode provides a lithium secondary battery comprising the negative electrode of the present invention.
  • the lithium secondary battery of the present invention may be prepared by injecting the nonaqueous electrolyte of the present invention into an electrode structure composed of a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
  • the positive electrode, the negative electrode, and the separator constituting the electrode structure may be used all those conventionally used in the manufacture of a lithium secondary battery.
  • the cathode may be prepared by coating a cathode active material slurry including a cathode active material and optionally a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like), lithium-manganese-cobal
  • LiCoO 2 , LiMnO 2 , LiNiO 2 , and lithium nickel manganese cobalt oxides may be improved in capacity and stability of the battery.
  • the lithium composite metal oxide may be Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , in view of the remarkable improvement effect according to the type and content ratio of the member forming the lithium composite metal oxide.
  • the cathode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of each cathode mixture.
  • the binder is a component that assists in bonding the active material and the conductive material and bonding to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the positive electrode mixture.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • the conductive material is typically added in an amount of 1 to 30% by weight based on the total weight of the positive electrode mixture.
  • Such a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used. Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack and EC, which are acetylene black series. Family (Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and Super P (manufactured by Timcal).
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the cathode active material, and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the positive electrode active material and, optionally, the solid content including the binder and the conductive material may be included in an amount of 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the separator separates the negative electrode and the positive electrode and provides a movement path of lithium ions, and can be used without particular limitation as long as it is normally used as a separator in a lithium secondary battery. It is preferable that it is resistance and excellent in electrolyte solution moisture-wetting ability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. It doesn't happen.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent include ester solvents such as methyl acetate, ethyl acetate, gamma-butyrolactone and ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Carbonate solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiCl, LiI, LiB (C 2 O 4 ) 2, and the like may be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included. In this case, the additive may be included in 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention ratio, and therefore, portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles (HEVs). It is useful in the field of electric vehicles, etc., and it can be used suitably especially as a constituent battery of a medium-large battery module. Accordingly, the present invention also provides a medium-large battery module including the secondary battery as a unit cell.
  • the medium-large battery module may be preferably applied to a power source that requires high output and large capacity, such as an electric vehicle, a hybrid electric vehicle, and a power storage device.
  • the primary artificial graphite particles, the pitch and the binder (PVDF) (98: 1: 1 weight ratio) were introduced into a mixing reactor, aggregated while rotating at 1500 rpm at 1500 ° C., and the secondary artificial graphite particles having a size of 15 ⁇ m. (20% porosity, BET specific surface area of 8 m 2 / g) was prepared.
  • the secondary artificial graphite particles and the carbon-based pitch were mixed at a weight ratio of 70:30 and heat-treated at 3000 ° C., and the average particle diameter (D50) including the carbon coating layer coated on the surface of the secondary artificial graphite particles was 20 ⁇ m.
  • Monographite (A) (porosity 10%, BET specific surface area 4 m 2 / g) was prepared.
  • the second artificial graphite (B) having a mean particle diameter (D50), which is a by-product generated during the heat treatment process for preparing the first artificial graphite particles having a diameter of 20 ⁇ m and 4 ⁇ m, is 4 ⁇ m.
  • the primary artificial graphite particles, the pitch and the binder (PVDF) (98: 1: 1 weight ratio) were introduced into a mixing reactor, aggregated while rotating at a speed of 3200 rpm at 1500 ° C., and the secondary artificial graphite particles having a size of 17 ⁇ m. (Porosity 15%, BET specific surface area 6 m 2 / g) were prepared.
  • the secondary artificial graphite particles and the carbon-based pitch were mixed at a weight ratio of 95: 5 and heat-treated at 3000 ° C., and the average particle diameter (D50) including the carbon coating layer coated on the surface of the secondary artificial graphite particles was 19 ⁇ m.
  • Monographite (A) (porosity 10%, BET specific surface area 3 m 2 / g) was prepared.
  • the second artificial graphite (B) having a mean particle diameter (D50) of 5 ⁇ m which is a by-product generated during the heat treatment process for producing the first artificial graphite (A) having 19 ⁇ m and the first artificial graphite particles, was 95: A mixture of 5% by weight, and a mixture of TK Mixer to prepare a negative electrode active material (porosity 10%, BET specific surface area of 5 m 2 / g) having an average particle diameter (D50) of 16 ⁇ m (see Table 1 below) ).
  • the primary artificial graphite particles, the pitch and the binder (PVDF) (98: 1: 1 weight ratio) were charged to a mixing reactor, and agglomerated while rotating at 1500 ° C. at a speed of 2900 rpm, and the secondary artificial graphite particles having a size of 14 ⁇ m. (Porosity 15%, BET Specific Surface Area 7 m 2 / g) were prepared.
  • the secondary artificial graphite particles and the carbon-based pitch were mixed at a weight ratio of 80:20 and heat-treated at 3000 ° C., and the average particle diameter (D50) including the carbon coating layer coated on the surface of the secondary artificial graphite particles was 15 ⁇ m.
  • Monographite (A) (porosity 10%, BET specific surface area 9 m 2 / g) was prepared.
  • D50 mean particle diameter
  • Example 1 In the same manner as in Example 1 except that the first artificial graphite (A) of 20 ⁇ m and the fine powder of the second artificial graphite (B) of 4 ⁇ m in a 90:10 weight ratio in Example 1, A negative electrode active material (20% porosity, 5 m 2 / g BET specific surface area) having a particle diameter (D50) of 20 ⁇ m was prepared (see Table 1 below).
  • Example 1 In the same manner as in Example 1 except that the first artificial graphite (A) of 20 ⁇ m and the finely divided second artificial graphite (B) of 4 ⁇ m in the 85: 1 weight ratio in Example 1, A negative electrode active material (20% porosity, 5 m 2 / g BET specific surface area) having a particle diameter (D50) of 20 ⁇ m was prepared (see Table 1 below).
  • the primary artificial graphite particles, the pitch and the binder (PVDF) (98: 1: 1 weight ratio) were charged to a mixing reactor, and agglomerated while rotating at 1500 ° C. at a speed of 2900 rpm, and the secondary artificial graphite particles having a size of 14 ⁇ m. (Porosity 10%, BET Specific Surface Area 5 m 2 / g) were prepared.
  • the first artificial graphite (A) having an average particle diameter (D50) prepared in Comparative Example 1 and the fine powder having an average particle diameter (D50), which is a byproduct generated during the heat treatment process for preparing the primary artificial graphite particles, is 4 ⁇ m.
  • Comparative Example 2 the average was mixed in the same manner as in Comparative Example 1, except that the first artificial graphite (A) having a thickness of 20 ⁇ m and the second artificial graphite (B) having a diameter of 4 ⁇ m were mixed at a weight ratio of 82:18.
  • An anode active material having a particle diameter (D50) of 20 ⁇ m (a porosity of 10% and a BET specific surface area of 4 m 2 / g) was prepared (see Table 1 below).
  • the primary artificial graphite particles, the pitch and the binder (PVDF) (98: 1: 1 weight ratio) were introduced into a mixing reactor, aggregated while rotating at a speed of 3200 rpm at 1500 ° C., and the secondary artificial graphite particles having a size of 17 ⁇ m. (Porosity 15%, BET specific surface area 6 m 2 / g) were prepared.
  • the secondary artificial graphite particles and the carbon-based pitch are mixed at a weight ratio of 80:20 and heat-treated at 3000 ° C., and the average particle diameter (D50) including the carbon coating layer coated on the surface of the secondary artificial graphite particles is 25 ⁇ m.
  • Monographite (A) (porosity 15%, BET specific surface area 8 m 2 / g) was prepared.
  • the primary artificial graphite particles, the pitch and the binder (PVDF) (98: 1: 1 weight ratio) were introduced into a mixing reactor, and agglomerated while rotating at 1500 ° C. at a speed of 2700 rpm, and the secondary artificial graphite particles having a size of 13 ⁇ m. (Porosity 10%, BET Specific Surface Area 12 m 2 / g) were prepared.
  • the secondary artificial graphite particles and the carbon-based pitch were mixed at a weight ratio of 97: 3 and heat-treated at 3000 ° C., and the average particle diameter (D50) including the carbon coating layer coated on the surface of the secondary artificial graphite particles was 14 ⁇ m.
  • Monographite (A) (porosity 10%, BET specific surface area 4 m 2 / g) was prepared.
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the negative electrode slurry was applied to a copper foil at a thickness of 65 ⁇ m, and vacuum dried and rolled at about 130 ° C. for 8 hours to prepare a negative electrode having 1.4875 cm 2. At this time, the loading of the negative electrode was prepared to be 3.60 mAh / cm 2 .
  • Li metal was used as the negative electrode and the counter electrode, and a polyolefin separator was interposed between the negative electrode and the Li metal, and then ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3: 7.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a coin-type half cell was prepared by injecting an electrolyte solution in which 1 M LiPF 6 was dissolved in a nonaqueous electrolyte solvent.
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the slurry was applied in large quantities to a copper foil at a thickness of 65 ⁇ m using a coater, and vacuum dried and rolled at about 130 ° C. for 8 hours to prepare a monocell-sized negative electrode.
  • the monocell size of the negative electrode was set to 3.4 cm x 5.1 cm.
  • the loading of the negative electrode was prepared to be 3.60 mAh / cm2.
  • ethylene carbonate (EC) and ethyl methyl carbonate ( EMC) was injected into the non-aqueous electrolyte solvent mixed in a volume ratio of 3: 7 to 0.7M LiPF 6 , 0.3M LIFSI dissolved electrolyte to prepare a two-electrode full cell.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Example 6, except that the negative electrode active material of Example 2 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Example 7, except that the negative electrode active material of Example 2 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Example 6, except that the negative electrode active material of Example 3 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Example 7, except that the negative electrode active material of Example 3 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Example 6, except that the negative electrode active material of Example 4 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a two-electrode full cell were prepared in the same manner as in Example 7, except that the negative electrode active material of Example 4 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Example 6, except that the negative electrode active material of Example 5 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Example 7, except that the negative electrode active material of Example 5 was used instead of the negative electrode active material of Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Example 6, except that the negative electrode active material of Comparative Example 1 was used instead of the negative electrode active material of Example 1.
  • Example 7 Except for using the negative electrode active material of Comparative Example 1 instead of the negative electrode active material of Example 1, a negative electrode and a two-electrode full cell was prepared in the same manner as in Example 7.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Comparative Example 6, except that the negative electrode active material of Comparative Example 2 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Comparative Example 7, except that the negative electrode active material of Comparative Example 2 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Comparative Example 6, except that the negative electrode active material of Comparative Example 3 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Comparative Example 7, except that the negative electrode active material of Comparative Example 3 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Comparative Example 6, except that the negative electrode active material of Comparative Example 4 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Comparative Example 7, except that the negative electrode active material of Comparative Example 4 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a coin-type half cell were manufactured in the same manner as in Comparative Example 6, except that the negative electrode active material of Comparative Example 5 was used instead of the negative electrode active material of Comparative Example 1.
  • a negative electrode and a two-electrode full cell were manufactured in the same manner as in Comparative Example 7, except that the negative electrode active material of Comparative Example 5 was used instead of the negative electrode active material of Comparative Example 1.
  • Coin-type half-cells prepared in Examples 6, 12, and 14 and Comparative Examples 6 and 8 were charged at 25 ° C. to CC / CV, 0.2 C, 5 mV, 0.005 C cut, discharge CC, 0.2 C, 1.0 V After 3rd cycle, the battery was charged to 0.2C at 50% of SOC.
  • the coin type half secondary battery charged to SOC 50% was measured using an electrochemical impedance spectroscopy (EIS) device to measure the charge transfer resistance (Rct). At this time, as the charge transfer resistance measurement conditions, the frequency was set to 10 6 Hz to 0.05 Hz. The resulting Nyquist plot is shown in FIG.
  • the charge transfer resistance values of the coin-type half cells of Examples 6, 12, and 14 were about 8.56 ⁇ or less, whereas the charge transfer resistance values of the half cells of Comparative Examples 6 and 8 were about 9.83 It can be seen that ⁇ or more. That is, it means that the coin-type half cells of Examples 6, 12, and 14 exhibit lower resistance than the half cells of Comparative Examples 6 and 8.
  • the two-electrode full cell secondary batteries prepared in Examples 7, 13 and 15 and Comparative Examples 7, 9, 11, 13 and 15 were charged at 25 ° C. at CC / CV, 0.2 C, 5 mV, 0.005 C cut, discharge CC, After 3rd cycle up to 0.2 C, 1.0 V, the battery was charged to 0.2 C SOC 50%.
  • the coin type half secondary battery charged to SOC 50% was measured for charge transfer resistance (Rct) using an EIS apparatus. At this time, as the charge transfer resistance measurement conditions, the frequency was set to 10 6 Hz to 0.05 Hz. Using a fitting program to calculate the value of Z '(Ohm) measured by the EIS equipment is shown in Table 3 below.
  • the resistance value of SOC 50% according to the charging at the measured room temperature (25 ° C.) is shown in Table 3 and FIG. 3.
  • the resistance value of SOC 50% according to the discharge at low temperature (-10 °C) is shown in Table 3 below.
  • the resistance values at room temperature and low temperature of the full-cell secondary batteries of Examples 7, 13, and 15 are lower than those of Comparative Examples 7, 9, 11, 13, and 15 (output is Higher).
  • the negative electrode active material of the present invention if the particle size difference between the two negative electrode active materials is sufficiently large, the electrode resistance of the bimodal structure electrode mixed with finely divided artificial graphite in the negative electrode active material occurs, and accordingly, the lithium of the bimodal negative electrode The charge transfer resistance of the ions to enter and exit is reduced, thereby finding an optimized point at which the output is increased.
  • the charge transfer resistance of the electrode of bimodal structure in which the small particle size of artificial graphite (second artificial graphite) was mixed actually decreased, and thus the output characteristics at room temperature and low temperature were improved. Can be.

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Abstract

La présente invention se rapporte à un matériau actif d'anode pour une batterie rechargeable au lithium, à une anode comprenant ce dernier, et à une batterie rechargeable au lithium comportant ce dernier, le matériau actif d'anode comprenant : (A) un premier graphite artificiel dont le diamètre moyen des particules (D50) est compris entre 15 µm et 20 µm ; et (B) un second graphite artificiel dont le diamètre moyen des particules (D50) est compris entre 3 μm et 5 μm, le premier graphite artificiel (A) comprenant des particules du second graphite artificiel, dans lesquelles une ou plusieurs particules du premier graphite artificiel sont agrégées, et une couche de revêtement de carbone, et le rapport pondéral entre le premier graphite artificiel et le second graphite artificiel étant compris entre 85:15 et 95:5.
PCT/KR2016/015195 2015-12-23 2016-12-23 Matériau actif d'anode pour une batterie rechargeable au lithium et anode pour une batterie rechargeable au lithium comprenant ce dernier Ceased WO2017111542A1 (fr)

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PL16879409T PL3297073T3 (pl) 2015-12-23 2016-12-23 Materiał aktywny anody dla akumulatora litowego i obejmująca go anoda dla akumulatora litowego
JP2018528931A JP6621926B2 (ja) 2015-12-23 2016-12-23 リチウム二次電池用負極活物質及びこれを含むリチウム二次電池用負極
EP16879409.7A EP3297073B1 (fr) 2015-12-23 2016-12-23 Matériau actif d'anode pour une batterie rechargeable au lithium et anode pour une batterie rechargeable au lithium comprenant ce dernier
CN201680040848.4A CN107851795B (zh) 2015-12-23 2016-12-23 锂二次电池用负极活性材料和包含其的锂二次电池用负极
US15/737,652 US10439221B2 (en) 2015-12-23 2016-12-23 Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery including the same

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190198857A1 (en) * 2017-12-22 2019-06-27 Samsung Sdi Co., Ltd. Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode
CN110400906A (zh) * 2018-04-24 2019-11-01 三星Sdi株式会社 用于可再充电锂电池的负电极和包括其的可再充电锂电池
WO2019239652A1 (fr) * 2018-06-15 2019-12-19 三洋電機株式会社 Accumulateur à électrolyte non aqueux
WO2020013718A1 (fr) * 2018-07-13 2020-01-16 Uniwersytet Warszawski Procédé de fabrication d'une matière carbonée pour constituer une masse anodique d'une pile au lithium-ion ainsi que la matière obtenue à l'aide de ce procédé, procédé de fabrication d'anode de pile au lithium-ion utilisant ladite matière et anode ainsi obtenue
WO2020106106A1 (fr) * 2018-11-22 2020-05-28 에스케이이노베이션 주식회사 Procédé de fabrication d'anode, et batterie rechargeable à performance de charge rapide améliorée, ayant une anode ainsi fabriquée
EP3641029A4 (fr) * 2017-10-30 2020-07-22 LG Chem, Ltd. Matériau actif d'anode destiné à un dispositif électrochimique, anode comportant ledit matériau actif d'anode et dispositif électrochimique comportant ladite anode
JPWO2019239948A1 (ja) * 2018-06-15 2021-06-24 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
CN113097445A (zh) * 2019-12-23 2021-07-09 松下电器产业株式会社 非水电解质二次电池用负极及非水电解质二次电池
CN113659107A (zh) * 2021-07-15 2021-11-16 恒大新能源技术(深圳)有限公司 电池极片及其制备方法、二次电池
CN113728460A (zh) * 2019-04-24 2021-11-30 三洋电机株式会社 非水电解质二次电池
CN114142028A (zh) * 2021-11-30 2022-03-04 蜂巢能源科技有限公司 负极材料、负极片及其制备方法和应用
CN114430864A (zh) * 2019-09-27 2022-05-03 松下知识产权经营株式会社 锂离子二次电池用负极和锂离子二次电池
CN114788048A (zh) * 2019-12-06 2022-07-22 三洋电机株式会社 非水电解液二次电池
CN115336040A (zh) * 2020-07-07 2022-11-11 株式会社Lg新能源 负极和包含所述负极的二次电池
CN115380407A (zh) * 2020-10-30 2022-11-22 株式会社Lg新能源 锂二次电池用负极活性材料、负极和锂二次电池
EP4071849A4 (fr) * 2019-12-06 2023-06-07 SANYO Electric Co., Ltd. Batterie secondaire à électrolyte non aqueux
US11876215B2 (en) 2018-11-22 2024-01-16 Sk On Co., Ltd. Method for manufacturing anode, and secondary battery with improved rapid charging performance, having anode according thereto
US12322802B2 (en) 2019-09-27 2025-06-03 Panasonic Intellectual Property Management Co., Ltd. Negative electrode for lithium ion secondary battery, and lithium ion secondary battery
WO2025112768A1 (fr) * 2023-11-30 2025-06-05 宁德时代新能源科技股份有限公司 Matériau actif d'électrode négative, feuille d'électrode négative, batterie et dispositif électrique
CN120545348A (zh) * 2025-06-03 2025-08-26 青岛龙迪碳材料科技有限公司 锂电池石墨负极材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0927314A (ja) * 1995-07-12 1997-01-28 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP3084256B2 (ja) * 1997-07-03 2000-09-04 日本カーボン株式会社 Ｌｉイオン二次電池の負極用材
JP2013030355A (ja) * 2011-07-28 2013-02-07 Hitachi Vehicle Energy Ltd リチウムイオン二次電池用負極電極及び該負極電極を用いたリチウムイオン二次電池
KR101283962B1 (ko) * 2011-06-16 2013-07-09 (주)포스코켐텍 비수계 리튬이차전지용 음극 활물질 및 그의 제조 방법
KR20140147240A (ko) * 2013-06-19 2014-12-30 주식회사 엘지화학 탄소계 음극 활물질, 이를 채용한 음극 및 전기화학소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0927314A (ja) * 1995-07-12 1997-01-28 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP3084256B2 (ja) * 1997-07-03 2000-09-04 日本カーボン株式会社 Ｌｉイオン二次電池の負極用材
KR101283962B1 (ko) * 2011-06-16 2013-07-09 (주)포스코켐텍 비수계 리튬이차전지용 음극 활물질 및 그의 제조 방법
JP2013030355A (ja) * 2011-07-28 2013-02-07 Hitachi Vehicle Energy Ltd リチウムイオン二次電池用負極電極及び該負極電極を用いたリチウムイオン二次電池
KR20140147240A (ko) * 2013-06-19 2014-12-30 주식회사 엘지화학 탄소계 음극 활물질, 이를 채용한 음극 및 전기화학소자

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11335909B2 (en) 2017-10-30 2022-05-17 Lg Energy Solution, Ltd. Negative electrode active material for electrochemical device, negative electrode including the negative electrode active material and electrochemical device including the same
EP3641029A4 (fr) * 2017-10-30 2020-07-22 LG Chem, Ltd. Matériau actif d'anode destiné à un dispositif électrochimique, anode comportant ledit matériau actif d'anode et dispositif électrochimique comportant ladite anode
US11217783B2 (en) * 2017-12-22 2022-01-04 Samsung Sdi Co., Ltd. Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode
US20190198857A1 (en) * 2017-12-22 2019-06-27 Samsung Sdi Co., Ltd. Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode
CN110400906A (zh) * 2018-04-24 2019-11-01 三星Sdi株式会社 用于可再充电锂电池的负电极和包括其的可再充电锂电池
CN117832499A (zh) * 2018-04-24 2024-04-05 三星Sdi株式会社 用于可再充电锂电池的负电极和包括其的可再充电锂电池
US12126013B2 (en) 2018-06-15 2024-10-22 Panasonic Energy Co., Ltd. Non-aqueous electrolyte secondary cell
EP4576273A3 (fr) * 2018-06-15 2025-10-08 Panasonic Energy Co., Ltd. Pile secondaire à électrolyte non aqueux
EP3809494A4 (fr) * 2018-06-15 2021-07-14 Panasonic Intellectual Property Management Co., Ltd. Batterie secondaire à électrolyte non aqueux
JPWO2019239948A1 (ja) * 2018-06-15 2021-06-24 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
JP7233013B2 (ja) 2018-06-15 2023-03-06 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
WO2019239652A1 (fr) * 2018-06-15 2019-12-19 三洋電機株式会社 Accumulateur à électrolyte non aqueux
WO2020013718A1 (fr) * 2018-07-13 2020-01-16 Uniwersytet Warszawski Procédé de fabrication d'une matière carbonée pour constituer une masse anodique d'une pile au lithium-ion ainsi que la matière obtenue à l'aide de ce procédé, procédé de fabrication d'anode de pile au lithium-ion utilisant ladite matière et anode ainsi obtenue
US12381203B2 (en) 2018-11-22 2025-08-05 Sk On Co., Ltd. Method for manufacturing anode, and secondary battery with improved rapid charging performance, having anode according thereto
WO2020106106A1 (fr) * 2018-11-22 2020-05-28 에스케이이노베이션 주식회사 Procédé de fabrication d'anode, et batterie rechargeable à performance de charge rapide améliorée, ayant une anode ainsi fabriquée
US11876215B2 (en) 2018-11-22 2024-01-16 Sk On Co., Ltd. Method for manufacturing anode, and secondary battery with improved rapid charging performance, having anode according thereto
CN113728460A (zh) * 2019-04-24 2021-11-30 三洋电机株式会社 非水电解质二次电池
EP4037014A4 (fr) * 2019-09-27 2023-08-09 Panasonic Intellectual Property Management Co., Ltd. Électrode négative pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion
US12322802B2 (en) 2019-09-27 2025-06-03 Panasonic Intellectual Property Management Co., Ltd. Negative electrode for lithium ion secondary battery, and lithium ion secondary battery
CN114430864A (zh) * 2019-09-27 2022-05-03 松下知识产权经营株式会社 锂离子二次电池用负极和锂离子二次电池
EP4071849A4 (fr) * 2019-12-06 2023-06-07 SANYO Electric Co., Ltd. Batterie secondaire à électrolyte non aqueux
EP4071850A4 (fr) * 2019-12-06 2023-06-07 SANYO Electric Co., Ltd. Batterie secondaire à électrolyte non aqueux
CN114788048A (zh) * 2019-12-06 2022-07-22 三洋电机株式会社 非水电解液二次电池
CN113097445A (zh) * 2019-12-23 2021-07-09 松下电器产业株式会社 非水电解质二次电池用负极及非水电解质二次电池
CN113097445B (zh) * 2019-12-23 2024-05-17 松下控股株式会社 非水电解质二次电池用负极及非水电解质二次电池
CN115336040A (zh) * 2020-07-07 2022-11-11 株式会社Lg新能源 负极和包含所述负极的二次电池
CN115380407A (zh) * 2020-10-30 2022-11-22 株式会社Lg新能源 锂二次电池用负极活性材料、负极和锂二次电池
CN113659107A (zh) * 2021-07-15 2021-11-16 恒大新能源技术(深圳)有限公司 电池极片及其制备方法、二次电池
CN114142028A (zh) * 2021-11-30 2022-03-04 蜂巢能源科技有限公司 负极材料、负极片及其制备方法和应用
WO2025112768A1 (fr) * 2023-11-30 2025-06-05 宁德时代新能源科技股份有限公司 Matériau actif d'électrode négative, feuille d'électrode négative, batterie et dispositif électrique
CN120545348A (zh) * 2025-06-03 2025-08-26 青岛龙迪碳材料科技有限公司 锂电池石墨负极材料及其制备方法

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