WO2021066582A1 - 구형화된 카본계 음극활물질, 이의 제조방법, 이를 포함하는 음극 및 리튬 이차전지 - Google Patents

구형화된 카본계 음극활물질, 이의 제조방법, 이를 포함하는 음극 및 리튬 이차전지 Download PDF

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WO2021066582A1
WO2021066582A1 PCT/KR2020/013430 KR2020013430W WO2021066582A1 WO 2021066582 A1 WO2021066582 A1 WO 2021066582A1 KR 2020013430 W KR2020013430 W KR 2020013430W WO 2021066582 A1 WO2021066582 A1 WO 2021066582A1
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active material
carbon
negative electrode
spheroidized
electrode active
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French (fr)
Korean (ko)
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김현철
우상욱
정동섭
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LG Chem Ltd
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LG Chem Ltd
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Priority to CN202080064189.4A priority Critical patent/CN114402460B/zh
Priority to US17/641,322 priority patent/US12476251B2/en
Priority to EP20871902.1A priority patent/EP4024512A4/en
Priority to JP2022519323A priority patent/JP7498267B2/ja
Publication of WO2021066582A1 publication Critical patent/WO2021066582A1/ko
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    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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    • 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
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • 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
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    • H01M4/139—Processes of manufacture
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 spherical carbon-based negative electrode active material, a method for producing the same, a negative electrode and a lithium secondary battery including the same, and more particularly, a spherical carbon-based negative electrode active material with reduced internal pores and improved sphericity, It relates to a method for manufacturing the same, a negative electrode including the same, and a lithium secondary battery.
  • lithium secondary batteries having a high energy density and voltage, a long cycle life, and a low discharge rate have been commercialized and widely used.
  • the lithium secondary battery has a structure in which an electrolyte including a lithium salt is impregnated in an electrode assembly in which a porous separator is interposed between a positive electrode and a negative electrode, each of which an active material is applied on an electrode current collector, and the electrode is an active material and a binder. And a slurry in which a conductive material is dispersed in a solvent is applied to a current collector, dried and rolled.
  • lithium metal was used as the negative electrode of the conventional secondary battery, the battery short circuit due to the formation of dendrites and the risk of explosion due thereto are known, while maintaining structural and electrical properties, and reversible intercalation of lithium ions. ) And desorbable carbon-based compounds.
  • the carbon-based compound has a very low discharge potential of about -3 V with respect to the standard hydrogen electrode potential, and excellent electrode life characteristics due to very reversible charging and discharging behavior due to the uniaxial orientation of the graphene layer. Represents.
  • the electrode potential is 0V Li/Li+ when charging Li ions, it can exhibit a potential similar to that of pure lithium metal, so that higher energy can be obtained when constructing a battery with an oxide-based positive electrode.
  • carbon-based compound various types of carbon-based materials including artificial graphite, natural graphite, and hard carbon have been applied.
  • graphite is currently the most widely used.
  • natural graphite is used by changing the shape of the surface to a smooth shape through post-treatment processing such as spheronization to reduce irreversible reaction and improve the fairness of the electrode, and low crystalline carbon such as pitch is coated through heat treatment.
  • post-treatment processing such as spheronization to reduce irreversible reaction and improve the fairness of the electrode
  • low crystalline carbon such as pitch is coated through heat treatment.
  • the method of manufacturing an anode active material by coating spherical natural graphite with low crystalline carbon is a method used by most anode material manufacturing companies.
  • the negative electrode active material prepared by the above method is prepared by spheroidizing natural graphite having a scale-like particle shape, and contains a large amount of voids inside the spheroidized graphite particles. These voids lower the density of the negative electrode active material, making it difficult to manufacture a high-density negative electrode plate.
  • the low crystalline carbon coating layer was broken, and thus destruction by the electrolyte and irreversible reaction due to exposure of the graphite edge. The problem occurs.
  • natural graphite has a major disadvantage of electrode swelling compared to artificial graphite, and the internal pores generated in the spheroidization process of natural graphite are larger than that of artificial graphite, and the film layer formed by the many internal pores is gas due to side reactions at high temperatures. There may be a problem that the generation and high temperature storage performance is deteriorated.
  • the present invention is to solve the above problems, and one object of the present invention is a spheroidized carbon-based negative electrode active material with reduced internal pores and improved sphericity, a method for preparing the same, and a negative electrode and lithium including the same. It is to provide a secondary battery.
  • Another object of the present invention is to provide a negative electrode including the negative electrode active material and a lithium secondary battery having the same.
  • a negative electrode active material of the following embodiment a method for manufacturing the same, and a negative electrode and a secondary battery including the same are provided.
  • Preparing spheroidized granulated particles by mixing and spheronizing small-scale flaky graphite and opposing flaky graphite having an average particle diameter larger than that of the small-scale flaky graphite;
  • a method for producing a spheronized carbon-based negative active material comprising a step of disintegrating the carbon-coated spheroidized granulated particles.
  • the average particle diameter of the fine-grained flaky graphite may be 20 to 50 ⁇ m, and the average particle diameter of the large-grained flaky graphite may be 50 to 100 ⁇ m.
  • the weight ratio of the granular flaky graphite and the granular flaky graphite may be 70:30 to 40:60.
  • the specific surface area value of the negative active material is 1.5 to 2.8 m 2 /g
  • the total pore volume of the negative active material is 1.0e -2 to 1.8e -2 m 3 /g
  • a spheroidized carbon-based negative active material characterized in that the specific surface area of pores having a size of 24 nm or more in the negative active material is 0.1 to 0.8 m 2 /g.
  • the specific surface area value of the negative active material may be 1.8 to 2.5 m 2 /g.
  • the total pore volume of the negative active material may be 1.19e -2 to 1.57e -2 m 3 /g.
  • the specific surface area of pores having a size of 24 nm or more in the negative active material may be 0.3 to 0.7 m 2 /g.
  • the average particle diameter of the spheronized carbon-based negative active material may be 10 to 20 ⁇ m.
  • the degree of sphericity of the spheronized negative active material may be 0.82 to 0.98.
  • a negative electrode comprising a current collector and a negative electrode active material layer positioned on at least one surface of the current collector
  • a negative electrode is provided, wherein the negative electrode active material layer includes a spheroidized carbon-based negative electrode active material according to any one of the fourth to ninth embodiments.
  • a lithium secondary battery comprising the negative electrode according to the tenth embodiment is provided.
  • spheronization is not performed by applying the existing one type of flaky graphite, but spheronization is performed by mixing flaky graphite having a large average particle diameter and flaky graphite with a small scale. It is possible to provide a spheroidized carbon-based negative active material with improved and reduced internal pores. When such a negative electrode active material is applied to a negative electrode of a secondary battery, internal stress is reduced to improve swelling characteristics, and a secondary battery having excellent capacity retention during high-temperature storage can be provided.
  • FIG. 1 is a schematic diagram of a spheronization step in a method of manufacturing a spheroidized carbon-based negative electrode active material according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of a spheronization step in a method of manufacturing a conventional spheroidized carbon-based negative electrode active material.
  • Preparing spheroidized granulated particles by mixing and spheronizing small-scale flaky graphite and opposing flaky graphite having an average particle diameter larger than that of the small-scale flaky graphite;
  • It includes; disintegrating the carbon-coated spheroidized granulated particles.
  • the spheroidized carbon-based negative electrode reduces internal porosity, improves spheronization, suppresses swelling of the electrode when used as an electrode of a battery, and improves performance during high-temperature storage of the battery. To provide an active material.
  • granulated granulated particles are prepared by mixing and spheronizing small-scale flaky graphite and opposite-grain flaky graphite having an average particle diameter larger than that of the small-scale flaky graphite.
  • small-scale flake-like graphite and anti-granular flake-like graphite having an average particle diameter larger than that of the small-scale flake-like graphite are prepared in a predetermined weight ratio, then mixed and spheronized to produce spheronized granulated particles.
  • the small-scale scale-like graphites are inserted and filled in the empty space (void) created between the scale-like graphites, thereby reducing internal pores, and more compact spheroidized particles. Can provide.
  • a mixture of granular flaky graphite and opposing flaky graphite is used as a raw material to perform a spheronization method commonly known in the art, for example, a method of applying mechanical treatment such as impact compression, friction, or shearing force.
  • the mechanical treatment can be carried out using a spheronization apparatus commonly known in the art, for example, a counter jet mill (Hosokawa Micron, JP), an ACM palliator (Hosokawa Micron, JP), a current jet (Nissin, JP).
  • SARARA Kawasaki Heavy Indestries, Ltd, JP
  • GRANUREX Green Corporation, JP
  • New Gramasin Seishin, JP
  • Hosokawa Micron JP, etc.
  • a kneader such as two rolls, a mechano micro system, an extruder, a ball mill, a planetary mill, a mechano fusion system, a nobilta, hybridization, compression shear processing equipment such as a rotary ball mill, and the like.
  • the mixture is introduced into a spheronizing device to which the above-described mechanical shear force is applied to form a granulated particle core, and in a concentric direction 1 It is possible to form spheroidized granulated particles in which more than one layer is stacked to form a spherically bonded surface layer.
  • the granulated particle core and the surface layer are formed at the same time to form spheroidized granulated particles.
  • spheroidized granulated particles may be obtained by repeatedly processing a mixture of small-grained flaky graphite and opposing flaky graphite using a rotary processing machine.
  • small-grained flaky graphite and opposing flaky graphite were formed through crushing by collision between the inner surface of the processing machine and small-grained flaky graphite, friction processing between the graphites, and shearing by shear stress.
  • Granulation is performed, and finally, spheroidized granulated particles can be obtained.
  • the pulverization time and pulverization speed can be adjusted within an appropriate range according to the amount of graphite to be added.
  • the present step may further include isotropically pressing the prepared spheroidized granulated particles so as to improve the contact property between the granulated granulated graphite and the granulated granular graphite contained in the spheroidized granulated particles.
  • isotropic pressurization means three-dimensionally uniform pressurization of the spheroidized granulated particles, and water or argon is used as a medium at room temperature for isotropic pressurization of the spheroidized granulated particles, or isotropically pressurized at room temperature. It is possible to use a cold isotropic pressurization treatment or the like.
  • the pressure for isotropically pressing the spheronized granulated particles is not particularly limited, but is preferably 50 to 100 atm, and more preferably 100 to 200 atm.
  • the flake graphite refers to natural graphite having a scale shape, and may be prepared by pulverizing natural graphite such as scale, plate shape, crushed shape, and tablet shape to a desired particle size.
  • the average particle diameter of the granular flaky graphite may be 20 to 50 ⁇ m, or 25 to 45 ⁇ m, and the average particle diameter of the granular flaky graphite may be 50 to 100 ⁇ m, or 55 to 90 ⁇ m. have.
  • the average particle diameter of the granular flaky graphite and the granular flaky graphite satisfies this range, the internal pores are reduced, and the film layer formed by the internal pores generates gas and lowers the high-temperature storage performance due to side reactions at high temperature. Can be.
  • the weight ratio of the granular flaky graphite and the granular flaky graphite is 70:30 to 40:60, or 70:30 to 45:55, or 70:30 to 50:50, or 50: It may be 50 to 45:55.
  • the weight ratio of the granular flaky graphite and the granular flaky graphite satisfies this range, it may be advantageous in that internal pores can be adjusted.
  • the spheroidized granulated particles 100 are formed.
  • the spheroidized granulated particles 100 may be filled with small-scale flaky graphite 110 in the space created between the opposing flaky graphite 120, so that the internal void 130 may be greatly reduced.
  • the spheroidized granulated particles are coated with carbon.
  • a carbon coating material is attached to the surface of the spheroidized granulated particles by homogeneously mixing the surface of the previously prepared spheroidized granulated particles with the carbon coating material, and then carbonized to treat the carbon coating layer on the surface of the spheroidized granulated particles.
  • These carbon materials form a coating layer on the surface of the spheroidized granulated particles, further bonding the granular flaky graphite and the opposing flaky graphite constituting the spheroidized granulated particles to each other, resulting in spheronization that can occur by repetition of charging and discharging. It is possible to prevent the stability of the granulated particles from deteriorating.
  • Such carbon coating materials include sucrose, phenol resin, naphthalene resin, polyvinyl alcohol resin, furfuryl alcohol resin, polyacrylonitrile resin, Polyamide resin, furan resin, cellulose resin, styrene resin, polyimide resin, epoxy resin or vinyl chloride resin, coal-based pitch, petroleum It may be prepared from a carbon precursor including a system pitch, polyvinyl chloride, mesophase pitch, tar, a block-copolymer, a low molecular weight heavy oil, or a mixture thereof.
  • the carbon coating material may be used in 1 to 10 parts by weight, or 3 to 6 parts by weight based on 100 parts by weight of the spheronized granulated particles.
  • the content of the carbon coating layer satisfies this range, a problem in that the capacity per weight decreases due to the formation of a coating layer that is too thick and the initial efficiency decreases due to irreversibility, or the specific surface area of the active material increases due to the formation of an excessively thin coating layer to increase side reactions.
  • the method of homogeneously mixing the surface of the spheroidized granulated particles with the carbon coating material is not particularly limited and may be performed by a method commonly known in the art.
  • a mechanical and chemical method such as a kneader such as two rolls, a blade, a mechano micro system, an extruder, a ball mill, a planetary mill, a mechano fusion system, a nobilta, a hydration, a rotary ball mill, etc. It can be carried out using a spray drying method, an emulsion method, or the like.
  • carbonization treatment is performed at a temperature of 900 to 1,300°C for 12 to 48 hours, thereby forming a carbon coating layer on the spheroidized granulated particles.
  • the formed carbon coating layer may be made of amorphous or crystalline carbon.
  • the spheroidized granulated particles obtained through carbonization treatment in the step of carbon coating the spheroidized granulated particles may exist in agglomerated form with each other.
  • the agglomerated particles are subjected to a disintegration process to separate them from each other.
  • the molded article can be easily crushed by simply applying a slight shearing force to the resulting molded article.
  • the crushing step is not particularly limited, for example, it can be carried out using a stirrer having a stirring blade, and a known pulverizer such as a conventional jet mill, vibrating mill, pin mill, hammer mill, etc. Can be implemented.
  • the specific surface area value of the negative active material is 1.5 to 2.8 m 2 /g
  • the total pore volume of the negative active material is 1.0e -2 to 1.8e -2 m 3 /g
  • the specific surface area of pores having a size of 24 nm or more in the negative active material is 0.1 to 0.8 m 2 /g.
  • the spheronized carbon-based negative active material may be prepared by the above-described method for preparing the spheroidized carbon-based negative active material.
  • the specific surface area value of the negative active material may be 1.5 to 2.8 m 2 /g, and according to an embodiment of the present invention, it may be 1.8 to 2.5 m 2 /g.
  • the specific surface area value of the negative electrode active material satisfies this range, it is advantageous in terms of high-temperature storage performance by reducing side reactions with the electrolyte.
  • the “specific surface area” is measured by the BET method, and can be specifically calculated from the amount of nitrogen gas adsorption under liquid nitrogen temperature (77K) using BELSORP-mino II of BEL Japan.
  • the total pore volume of the negative active material may be 1.0e -2 to 1.8e -2 m 3 /g, and according to an embodiment of the present invention, it may be 1.19e -2 to 1.57e -2 m 3 /g.
  • the total pore volume of the negative electrode active material satisfies this range, it is advantageous in terms of high-temperature storage performance by reducing side reactions with the electrolyte.
  • the total pore volume of the negative active material may be measured by the BET method in the same manner as the specific surface area measurement described above, and may be measured using the same equipment as the specific surface area measurement.
  • the specific surface area of the pores having a size of 24 nm or more in the negative active material may be 0.1 to 0.8 m 2 /g, and according to an embodiment of the present invention, it may be 0.3 to 0.7 m 2 /g.
  • the specific surface area of the pores having a size of 24 nm or more in the negative electrode active material satisfies this range, it is advantageous in that side reactions with the electrolyte are reduced.
  • the specific surface area of the pores having a size of 24 nm or more in the negative electrode active material can be measured by the BET method in the same manner as the specific surface area measurement described above, and can be measured using the same equipment as the specific surface area measurement.
  • the specific surface area value of the anode active material is 1.5 to 2.8 m 2 /g
  • the total pore volume of the anode active material is 1.0e -2 to 1.8e -2 m 3 /g
  • the anode active material has a size of 24 nm or more.
  • the average particle diameter of the spheroidized carbon-based negative active material may be 10 to 20 ⁇ m, or 11 to 18 ⁇ m.
  • the average particle diameter D50 means a particle diameter at 50% of the cumulative distribution of the number of particles according to the particle diameter.
  • D90 is the particle diameter at 90% of the cumulative distribution of the number of particles according to the particle diameter
  • D10 is the particle diameter at 10% of the cumulative distribution of the number of particles according to the particle diameter.
  • the average particle diameter can be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in a dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (for example, Microtrac S3500) to measure the difference in the diffraction pattern according to the particle size when the particles pass through the laser beam. Can be calculated. D10, D50, and D90 can be measured by calculating the particle diameter at a point at 10%, 50%, and 90% of the cumulative distribution of the number of particles according to the particle diameter in the measuring device.
  • a laser diffraction particle size measuring device for example, Microtrac S3500
  • the sphericity of the spheronized carbon-based negative active material may be 0.82 to 0.98, or 0.88 to 0.92.
  • the sphericity degree may be a value obtained by dividing the circumference of a circle having the same area as the projected image by the circumference of the projected image when the anode active material is projected, and can be specifically expressed by Equation 1 below.
  • the degree of sphericity can be measured using a particle shape analyzer, for example, a particle shape analyzer such as sysmex FPIA3000 manufactured by Malvern.
  • Sphericity Circumference of a circle with the same area as the projected image of the active material/Circumference of the projected image
  • a negative electrode including the negative electrode active material is provided.
  • a negative electrode according to an embodiment of the present invention includes a current collector and a negative electrode active material layer including the negative electrode active material according to the present invention on at least one surface of the current collector.
  • the electrode layer may be prepared by coating a slurry for a negative electrode active material layer obtained by dispersing the negative electrode active material, a binder, and a conductive material according to the present invention on at least one surface of a current collector, followed by drying and rolling.
  • the current collector is not particularly limited as long as it has conductivity without causing chemical changes to the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, carbon, nickel on the surface of copper or stainless steel , Titanium, silver, etc. surface-treated, aluminum-cadmium alloy, etc. may be used.
  • the thickness of the current collector is not particularly limited, but may have a thickness of 3 to 500 ⁇ m, which is generally applied.
  • the negative electrode active material may be included in an amount of 80% to 99% by weight based on the total weight of the negative electrode slurry composition.
  • the binder is a component that aids in bonding between a conductive material, an active material, or a current collector, and is typically included in an amount of 0.1 to 20% by weight based on the total weight of the negative electrode slurry composition.
  • a binder include polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidenefluoride, polyacrylonitrile, and polymethylmethacrylate.
  • Polyvinyl alcohol Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, styrene butyrene rubber (SBR), lithium -And substituted polyacrylate (lithium polyacrylate, Li-PAA).
  • CMC carboxymethyl cellulose
  • SBR styrene butyrene rubber
  • Li-PAA lithium -And substituted polyacrylate
  • lithium-substituted polyacrylate can provide excellent adhesion compared to other binders, such as SBS/CMC, when used for a negative electrode having a silicon content of about 80% in the active material, Due to this feature, it is advantageous in that it is applied to a Si-based negative electrode to achieve a high capacity retention rate during charge and discharge.
  • the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
  • carbon such as carbon black, acetylene black, Ketjen black, channel black, Parnes black, lamp black, thermal black, etc. black
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as fluorocarbon, aluminum, and nickel powder
  • Conductive whiskers such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives may be used.
  • the conductive material may be added in an amount of 0.1 to 20% by weight based on the total weight of the negative electrode slurry composition.
  • the dispersion medium may contain water or an organic solvent such as NMP (N-methyl-2-pyrrolidone), and when the negative electrode slurry contains a negative electrode active material, and optionally a binder and a conductive material, it is in an amount that becomes a desirable viscosity. Can be used.
  • NMP N-methyl-2-pyrrolidone
  • the method of coating the negative electrode slurry is not particularly limited as long as it is a method commonly used in the art.
  • a coating method using a slot die may be used, and in addition, a Mayer bar coating method, a gravure coating method, an immersion coating method, a spray coating method, and the like may be used.
  • the lithium secondary battery may be manufactured by injecting a lithium salt-containing electrolyte into an electrode assembly including a positive electrode, a negative electrode as described above, and a separator interposed therebetween.
  • a slurry is prepared by mixing a positive electrode active material, a conductive material, a binder, and a solvent, and then directly coated on a metal current collector, or cast on a separate support and a positive electrode active material film peeled from the support is laminated on the metal current collector.
  • a positive electrode can be manufactured.
  • Active materials used for the positive electrode include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCoPO 4 , LiFePO 4 and LiNi 1-xyz Co x M1 y M2 z O 2 (M1 and M2 are independently of each other Al, Ni, Co, Any one selected from the group consisting of Fe, Mn, V, Cr, Ti, W, Ta, Mg, and Mo, and x, y and z are independently of each other as atomic fractions of the oxide composition elements, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, 0 ⁇ x+y+z ⁇ 1), or a mixture of two or more of them.
  • the conductive material, the binder, and the solvent may be used in the same manner as those used in manufacturing the negative electrode.
  • the separator is a conventional porous polymer film used as a conventional separator, for example, a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer.
  • the prepared porous polymer film may be used alone or by laminating them.
  • an insulating thin film having high ion permeability and mechanical strength may be used.
  • the separator may include a safety reinforced separator (SRS) in which a ceramic material is thinly coated on the surface of the separator.
  • a conventional porous nonwoven fabric for example, a nonwoven fabric made of a high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used, but is not limited thereto.
  • the electrolyte solution includes a lithium salt and an organic solvent for dissolving the lithium salt as an electrolyte.
  • the lithium salt may be used without limitation, if the ones commonly used in the secondary battery, the electrolytic solution, for example, is in the lithium salt anion F -, Cl -, I - , NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3 ) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, ( CF 3 SO 2) 2 CH - , (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, One selected from the group consisting of SCN
  • the organic solvent contained in the electrolyte may be used without limitation as long as it is commonly used, and typically propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, dipropyl carbonate, dimethyl sulfoxide At least one selected from the group consisting of side, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, sulfolane, gamma-butyrolactone, propylene sulfite, and tetrahydrofuran may be used.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates
  • cyclic carbonates are highly viscous organic solvents and can be preferably used because they dissociate lithium salts in the electrolyte well due to their high dielectric constant.
  • These cyclic carbonates include dimethyl carbonate and diethyl
  • an electrolyte solution having a high electrical conductivity can be prepared, and thus it can be more preferably used.
  • the electrolyte stored according to the present invention may further include an additive such as an overcharge preventing agent included in a conventional electrolyte.
  • an additive such as an overcharge preventing agent included in a conventional electrolyte.
  • a separator is disposed between a positive electrode and a negative electrode to form an electrode assembly, and the electrode assembly is placed in, for example, a pouch, a cylindrical battery case, or a prismatic battery case, and then an electrolyte is added.
  • the secondary battery can be completed.
  • a lithium secondary battery may be completed by laminating the electrode assembly, impregnating the electrode assembly with an electrolyte, and sealing the obtained resultant in a battery case.
  • the lithium secondary battery may be a stack type, a wound type, a stack and folding type, or a cable type.
  • the lithium secondary battery according to the present invention can be used not only as a battery cell used as a power source for a small device, but also can be preferably used as a unit cell in a medium or large battery module including a plurality of battery cells.
  • Preferred examples of the medium and large-sized devices include electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage systems, and are particularly useful for hybrid electric vehicles and batteries for storing renewable energy in areas requiring high output. Can be used.
  • Confronting flaky graphite with an average particle diameter of 75 ⁇ m and small flaky graphite with an average particle diameter of 35 ⁇ m were prepared in a weight ratio of 70:30, mixed using a ball mill, and a counter jet mill (Hosokawa Micron, JP). Then, it spheroidized to obtain spheroidized granulated particles. 100 parts by weight of the obtained spheroidized granulated particles and 5 parts by weight of pitch (solid pitch) as a carbon coating material were mixed and carbonized by carbonization at 1,500°C for 24 hours, followed by carbon-coated spheroidized granulated particles. Disintegration treatment was performed to prepare a spherical carbon-based negative electrode active material.
  • the previously prepared carbon-based negative electrode active material, Super C65 as a conductive material, styrene butadiene rubber (SBR) as a binder, and carboxymethylcellulose (CMC) as a thickener were mixed in a weight ratio of 96.6:1:1.3:1.1, respectively, and water was added to prepare a slurry.
  • the slurry prepared above was applied to a copper foil and vacuum-dried at about 130° C. for 10 hours to prepare a 1.4875 cm 2 negative electrode. At this time, the loading of the negative electrode was prepared to be 3.61mAh/cm 2.
  • An electrode assembly was manufactured by using the prepared negative electrode as a working electrode and 1.7671 cm 2 Li-metal as a counter electrode, and a polyethylene separator interposed between the working electrode and the counter electrode. Ethylene carbonate (EC) and diethylene carbonate (EMC) are mixed in a volume ratio of 1:4, and vinylene carbonate (VC) 0.5wt% and 1M LiPF 6 are added as a nonaqueous electrolyte additive to the mixed solvent to prepare a nonaqueous electrolyte. I did.
  • the electrode assembly was embedded in a coin-type case, and the prepared non-aqueous electrolyte was injected to prepare a coin-type half-cell secondary battery.
  • Sphericalized carbon-based negative electrode active material was prepared in the same manner as in Example 1, except that an average particle diameter of 75 ⁇ m was prepared in an average particle diameter of 35 ⁇ m in a weight ratio of 50:50. I did.
  • a secondary battery was manufactured in the same manner as in Example 1, except that the negative active material thus prepared was used.
  • Sphericalized carbon-based negative electrode active material was prepared in the same manner as in Example 1, except that an average particle diameter of 75 ⁇ m of granular flaky graphite and an average particle diameter of 35 ⁇ m of granular flaky graphite were prepared in a weight ratio of 45:55. I did.
  • a secondary battery was manufactured in the same manner as in Example 1, except that the negative active material thus prepared was used.
  • a spheroidized carbon-based negative electrode active material was prepared in the same manner as in Example 1, except that only granular flaky graphite having an average particle diameter of 75 ⁇ m was used and small-grained flaky graphite having an average particle diameter of 35 ⁇ m was not used. .
  • a secondary battery was manufactured in the same manner as in Example 1, except that the negative active material thus prepared was used.
  • a spheroidized carbon-based negative electrode active material was prepared in the same manner as in Example 1, except that only fine-grained flaky graphite having an average particle diameter of 75 ⁇ m was not used, and only small-grained flaky graphite having an average particle diameter of 35 ⁇ m was used.
  • a secondary battery was manufactured in the same manner as in Example 1, except that the negative active material thus prepared was used.
  • the specific surface area of the negative electrode active material of Examples 1 to 3, Comparative Example 1, and Comparative Example 2, the total pore volume of the negative electrode active material, and the specific surface area of pores having a size of 24 nm or more in the negative electrode active material were measured by the BET method, Specifically, it was calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77 K) using BELSORP-mino II from BEL Japan.
  • the sphericity of the negative electrode active material of Examples 1 to 3, Comparative Example 1, and Comparative Example 2 is defined by the following Equation 1, and the sphericity was measured using a particle analyzer, Malvern's sysmex FPIA3000.
  • Sphericity Circumference of a circle with the same area as the projected image of the active material/Circumference of the projected image
  • the swelling ratio of the secondary batteries of Examples 1 to 3, Comparative Examples 1, and 2 was measured after 30 cycles of charging and discharging under the conditions of 0.1C charging/discharging current and 5mV to 1.5V charging/discharging voltage, and the following table It is shown in 1.
  • the swelling ratio (%) is defined by the following equation.
  • Swelling ratio (%) [(electrode thickness after charging/discharging-initial electrode thickness)/(initial electrode thickness)] X 100
  • the capacity retention rate (%) is defined by the following equation.
  • Capacity retention rate (%) [(Capacity after high temperature storage)/(Initial capacity)] X 100

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