WO2017099456A1 - Matériau actif d'électrode négative pour batterie secondaire au lithium comprenant un cœur composé de carbone, son procédé de fabrication et batterie secondaire au lithium comprenant celui-ci - Google Patents

Matériau actif d'électrode négative pour batterie secondaire au lithium comprenant un cœur composé de carbone, son procédé de fabrication et batterie secondaire au lithium comprenant celui-ci Download PDF

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WO2017099456A1
WO2017099456A1 PCT/KR2016/014255 KR2016014255W WO2017099456A1 WO 2017099456 A1 WO2017099456 A1 WO 2017099456A1 KR 2016014255 W KR2016014255 W KR 2016014255W WO 2017099456 A1 WO2017099456 A1 WO 2017099456A1
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active material
negative electrode
electrode active
carbon
particles
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PCT/KR2016/014255
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English (en)
Korean (ko)
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이성만
신민선
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강원대학교산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • 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 disclosure provides a negative electrode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same.
  • lithium secondary batteries As the application of lithium secondary batteries to medium and large-sized lithium secondary batteries such as electric vehicles as well as portable electronic devices, high capacity and charge / discharge output characteristics are required to be improved.
  • silicon (Si) or its compound As a material which can replace graphite, silicon (Si) or its compound has been studied conventionally. Silicon reversibly occludes and releases lithium through compound formation reaction with lithium and is promising as a high capacity cathode material because its theoretical maximum capacity is about 4200 mAh / g (9800 mAh / cc, specific gravity 2.23), which is much larger than graphite.
  • One embodiment of the present invention is to provide a negative active material for a lithium secondary battery having a large charge and discharge capacity, excellent cycle life characteristics, excellent charge and discharge output characteristics at high current density and improved thermal stability.
  • Another embodiment of the present invention is to provide a method of manufacturing the negative electrode active material for the lithium secondary battery.
  • Another embodiment of the present invention is to provide a lithium secondary battery comprising the negative electrode active material for the lithium secondary battery.
  • One embodiment of the present invention includes a core particle including at least one selected from hard carbon, soft carbon, and spherical natural graphite, and a shell layer on the surface of the core particle,
  • the shell layer may comprise: i) a first shell layer comprising silicon (Si) / carbon black / carbon composite particles, and amorphous or semi-crystalline carbon; And ii) a structure in which amorphous or quasi-crystalline carbon is distributed between the flaky graphite fragment particles, and the flaky graphite fragment particles are stacked in a concentric manner and formed, and a second shell layer formed on the first shell layer.
  • a negative active material for a secondary battery is provided.
  • the average particle diameter (D50) of the core particles may be 2 to 20 ⁇ m.
  • the core particles may be included in 5 to 85% by weight based on the total amount of the negative electrode active material.
  • the average particle diameter (D50) of the composite particles included in the first shell layer may be 0.05 ⁇ m to 2 ⁇ m.
  • the composite particles included in the first shell layer may include silicon particles having an average particle diameter of 5 to 200 nm, and may include mesopores having an average size of 2.0 to 50 nm.
  • the composite particles included in the first shell layer may include silicon particles and carbon black particles in a weight ratio of 1: 9 to 9: 1.
  • the composite particles included in the first shell layer may include 0.1 to 70% by weight of amorphous or semicrystalline carbon.
  • the first shell layer may include the composite particles and amorphous or semicrystalline carbon in a weight ratio of 1: 9 to 9: 1.
  • the total weight of the first shell layer may be 10 to 94% by weight based on the total weight of the negative electrode active material.
  • An average thickness of the flaky graphite fragment particles included in the second shell layer may be 100 nm or less.
  • the flaky graphite fragment particles included in the second shell layer may be included in an amount of 1 to 40 wt% based on the total weight of the negative electrode active material.
  • the amorphous or semicrystalline carbon may be sucrose, phenol resin, naphthalene resin, polyvinyl alcohol, polyvinyl chloride, furfuryl alcohol, polyacrylonitrile, polyamide, furan resin, cellulose, styrene, polyyi It may be formed from a carbon precursor including at least one selected from the group consisting of mid, epoxy resin, vinyl chloride resin, coal-based pitch, petroleum-based pitch, mesoface pitch, tar and low molecular weight heavy oil.
  • the ratio of the average particle diameter (D50) of the core particles and the thickness of the shell layer may be 17 to 95: 5 to 83.
  • the ratio of the thickness of the first shell layer and the second shell layer may be 5 to 95:95 to 5.
  • the anode active material may further include a coating layer disposed on the surface of the shell layer and including the amorphous or semicrystalline carbon, and the thickness of the coating layer may be 0.01 to 5 ⁇ m.
  • the average particle diameter (D50) of the negative electrode active material may be 2 to 40 ⁇ m.
  • Another embodiment of the present invention provides a surface of a core particle comprising at least one selected from hard carbon, soft carbon, and spherical natural graphite, a mixture of silicon / carbon black / carbon composite particles, and an amorphous or semicrystalline carbon precursor. Coating to form a first shell layer, and coating the surface of the first shell layer with a mixture of flaky graphite fragment particles and an amorphous or semi-crystalline carbon precursor to form a second shell layer to obtain anode active material precursor particles; And it provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of heat-treating the negative electrode active material precursor particles.
  • the method of manufacturing the negative active material may further include coating the surface of the negative electrode active material precursor particles with an amorphous or semi-crystalline carbon precursor before the heat treatment of the negative electrode active material precursor particles.
  • the heat treatment may be performed under an atmosphere containing nitrogen, argon, hydrogen or a mixed gas thereof, or under vacuum, and may be performed at a temperature of 700 to 1300 ° C.
  • the negative electrode including the negative electrode active material; anode; And it provides a lithium secondary battery comprising an electrolyte solution.
  • a lithium secondary battery having a large charge and discharge capacity, excellent cycle life characteristics, excellent charge and discharge output characteristics at a high current density, and greatly improved thermal stability can be implemented.
  • FIG. 1 is a schematic cross-sectional view of a negative electrode active material according to an embodiment.
  • FIG. 2 is a conceptual diagram of a cross section of a silicon (Si) / carbon black / carbon composite particle included in a core of a negative active material for a lithium secondary battery according to the present invention.
  • FIG. 3 is a schematic cross-sectional view of a negative electrode active material according to another embodiment.
  • FIG. 4 is a scanning electron microscope (SEM) photograph of the core particles used in Example 1 and Comparative Example 1.
  • SEM scanning electron microscope
  • Example 5 is a scanning electron microscope (SEM) photograph of the core particles used in Example 2 and Comparative Example 2.
  • FIG. 6 is a scanning electron microscope (SEM) photograph of the negative electrode active material prepared in Example 1.
  • SEM scanning electron microscope
  • FIG. 7 is a scanning electron microscope (SEM) photograph of the negative electrode active material prepared in Comparative Example 1.
  • SEM scanning electron microscope
  • FIG. 8 is a scanning electron microscope (SEM) photograph of the anode active material prepared in Example 2.
  • SEM scanning electron microscope
  • FIG. 9 is a scanning electron microscope (SEM) photograph of the negative electrode active material prepared in Comparative Example 2.
  • SEM scanning electron microscope
  • FIG. 10 is a particle size distribution of negative electrode active materials prepared in Example 1 and Comparative Example 1.
  • FIG. 10 is a particle size distribution of negative electrode active materials prepared in Example 1 and Comparative Example 1.
  • FIG. 11 is a particle size distribution of the negative electrode active materials prepared in Example 2 and Comparative Example 2.
  • Example 16 is a cycle curve for the lithium secondary battery prepared in Example 1 and Comparative Example 1.
  • Example 17 is a cycle curve for the lithium secondary battery prepared in Example 2 and Comparative Example 2.
  • FIG. 18 shows the results of differential scanning thermal analysis (DSC) of electrodes prepared using the negative electrode active materials of Example 1 and Comparative Example 1.
  • DSC differential scanning thermal analysis
  • FIG. 19 is a result of differential scanning thermal analysis (DSC) of electrodes prepared using the negative electrode active materials of Example 2 and Comparative Example 2.
  • DSC differential scanning thermal analysis
  • the negative electrode active material according to one embodiment may be described with reference to FIG. 1.
  • FIG. 1 is a schematic cross-sectional view of a negative electrode active material according to an embodiment.
  • the negative electrode active material 1 may include a core particle 11 and a shell layer located on the surface of the core particle 11.
  • the shell layer may have a shape surrounding the core particle 11.
  • the core particle 11 may include at least one selected from hard carbon, soft carbon, and spherical natural graphite.
  • the hard carbon may be amorphous hard carbon
  • the soft carbon may be specifically semicrystalline or low crystalline soft carbon.
  • the spherical natural graphite particles are formed by flakes of natural graphite fragments in the cabbage or random phase.
  • the shell layer comprises: i) a first shell layer comprising silicon (Si) / carbon black / carbon composite particles (12), and amorphous or semi-crystalline carbon (13); And ii) amorphous or quasi-crystalline carbon 15 is distributed between the flaky graphite fragment particles 14, and the flaky graphite fragment particles are laminated in a concentric direction and formed and formed on the first shell layer. It may comprise two shell layers.
  • Hard carbon or soft carbon used as the core particles has good output characteristics of the battery when used as a negative electrode material, but has low initial efficiency and low storage capacity of lithium ions.
  • the spheronized natural graphite used as the core particles has a limit of theoretical capacity of 372 mAh / g of lithium ions, which has a need for increasing capacity.
  • the capacity of the battery is high, but the initial efficiency is low, and the volume change occurs, which causes micronization of the silicon active material powder and poor electrical contact between the silicon active material powder and the current collector. Can be.
  • the battery capacity is drastically reduced, which causes the cycle life to be shortened.
  • the thermal recognition property may be lowered by directly contacting and reacting with the electrolyte.
  • hard carbon, soft carbon, and spherical natural graphite are used as core particles, and the surface of the core particles is i) silicon (Si) / carbon black / carbon composite particles 12, and amorphous ( a first shell layer comprising amorphous or semi-crystalline carbon 13; And ii) amorphous or quasi-crystalline carbon 15 is distributed between the flaky graphite fragment particles 14, and the flaky graphite fragment particles are laminated in a concentric direction and formed and formed on the first shell layer. It has a structure of coating with 2 shell layers, which has a large lithium storage capacity, high capacity retention rate, improved initial efficiency, easy movement of lithium ions during charge and discharge, and excellent output characteristics and high charge and discharge efficiency. have.
  • the thermal stability of the negative electrode active material is greatly improved by preventing contact between the silicon (Si) / carbon black / carbon composite particles 12 and the electrolyte solution.
  • the average particle diameter (D50) of the core particles may be 2 to 20 ⁇ m, specifically 5 to 15 ⁇ m.
  • the coating for forming the shell layer with the carbon fine particles is well made, and thus can be usefully applied to a lithium secondary battery having a high capacity and excellent output characteristics.
  • the average particle diameter (D50) refers to the diameter of the particles corresponding to the cumulative volume 50% by volume in the particle size distribution.
  • the hard carbon may be sucrose, phenol resin, furan resin, furfuryl alcohol, polyacrylonitrile, polyimide, epoxy resin. ), Cellulose, styrene, citric acid, stearic acid, polyvinylidene fluoride, carboxymethyl cellulose (CMC), hydroxypropyl cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene At least one carbonaceous material selected from ethylene-propylene-diene monomer (EPDM), sulfonated ethylene-propylene-diene monomer (EPDM), starch, glucose, gelatin and saccharides may be used.
  • EPDM ethylene-propylene-diene monomer
  • EPDM sulfonated ethylene-propylene-diene monomer
  • starch glucose, gelatin and saccharides
  • the soft carbon may be formed by carbonizing at least one carbonaceous material selected from polyvinyl alcohol, polyvinyl chloride, coal-based pitch, petroleum-based pitch, mesoface pitch, and low molecular weight heavy oil.
  • the core particles may be included in 5 to 85% by weight, specifically, 20 to 80% by weight based on the total amount of the negative electrode active material.
  • the shell layer may be formed at an appropriate ratio around the core particles to exhibit excellent output characteristics and to improve capacity.
  • composite particles Silicon / carbon black / carbon composite particles (hereinafter referred to as “composite particles”) included in the first shell layer And amorphous or semicrystalline carbon in the core in a weight ratio of 1: 9 to 9: 1. If the weight ratio of the multiparticulates and amorphous or semicrystalline carbon is less than 1: 9, the effect of increasing the capacity may not be sufficient. If the weight ratio of the multiparticulates and the amorphous or semicrystalline carbon is less than 9: 1, it is difficult to uniformly mix and disperse the multiparticulates and the amorphous or semicrystalline carbon. Properties as the negative electrode active material may be lowered.
  • the total weight of the first shell layer including the composite particles and amorphous or semi-crystalline carbon is preferably included in 10 to 94% by weight based on the total weight of the negative electrode active material.
  • the composite particles 12 have a structure in which silicon particles 21 and carbon black particles 22 are uniformly mixed and bonded by amorphous or semi-crystalline carbon 23.
  • D 50 (0% volume cumulative particle diameter measured by laser diffraction scattering particle size distribution measurement) of the composite particles is preferably from 0.05 ⁇ m to 2 ⁇ m, which is dispersed during the preparation of the negative electrode active material when D 50 is less than 0.05 ⁇ m This may not be sufficient, and when it exceeds 2 ⁇ m, it may be difficult to form the first shell layer in the negative electrode active material.
  • the composite particle provides a negative active material for a lithium secondary battery, characterized in that the silicon particles and carbon black particles in a weight ratio of 1: 9 to 9: 1.
  • the weight ratio of the silicon particles and the carbon black particles is less than 1: 9, when the amount of the silicon particles is small, the high capacity effect by silicon may not be sufficient, and the weight ratio of the silicon particles and the carbon black particles is 9: 1.
  • the amount of the silicon particles is larger, the dispersion effect of the silicon particles by the carbon black may not be sufficient.
  • the composite particles may include 0.1 to 70% by weight of amorphous or semicrystalline carbon relative to the total weight of the composite particles for the purpose of bonding and coating the silicon particles and the carbon black particles.
  • amorphous or semi-crystalline carbon of the composite particles is less than 0.1% by weight, the effect of bonding and coating the silicon particles and the carbon black particles is not sufficient, and the capacity by silicon when the amorphous or semi-crystalline carbon is 70% by weight or more It is difficult to expect an increase effect.
  • Carbon black included in the composite particles may be exemplified by acetylene black, Caten black, channel black, furnace black, summer black, super P, but not limited thereto. Can be.
  • Carbon black particles generally have an average particle size of 10 nm to 100 nm, but several of these carbon black particles may be present in agglomerated particles such as grape clusters.
  • the carbon in the composite particles may be prepared using the same precursor as the precursor for forming amorphous or semicrystalline carbon, which will be described later as amorphous or semicrystalline carbon.
  • amorphous carbon refers to hard carbon that does not change into crystalline graphite even when the temperature is raised in a state in which carbon atoms are randomly arranged.
  • the semicrystalline carbon is crystalline graphite having low crystallinity when heated to a temperature of 2000 ° C. or less It means a low crystalline carbon is changed to.
  • the composite particles may include silicon particles having an average particle diameter of 5 to 200 nm, more preferably silicon particles having an average particle diameter of 20 to 100 nm.
  • the size of the silicon particles is less than 5 nm, it is easy to form a compound such as SiC during heat treatment at 1000 ° C. or higher during the preparation of the negative electrode active material, and thus it is difficult to expect a high capacity effect by silicon.
  • the size of the silicon particles exceeds 200 nm, it is difficult to control the volume expansion of the negative electrode active material particles due to the large volume expansion when forming a lithium compound by reacting with lithium.
  • the composite particles may comprise a mesopore (24) having an average size of 2.0 to 50 nm, thereby preventing the volume expansion by the reaction of the silicon particles in the composite particles with lithium during charge and discharge A buffering effect can be expected.
  • the amorphous or semi-crystalline carbon included in the first shell layer may be sucrose, phenol resin, naphthalene resin, polyvinyl alcohol, polyvinyl chloride, furfuryl alcohol, polyacrylonitrile, polyamide, furan resin And those formed from carbon precursors including at least one selected from cellulose, styrene, polyimide, epoxy resins, vinyl chloride resins, coal-based pitches, petroleum-based pitches, mesophase pitches, tars, and low molecular weight heavy oils.
  • the flaky graphite fragment particles 14 included in the second shell layer may be obtained by peeling flaky graphite to have an average thickness of 100 nm or less.
  • the flaky graphite fragment particles included in the second shell layer are preferably included in an amount of 1 to 40% by weight based on the total weight of the negative electrode active material, which is less than 1% by weight based on the total amount of the negative electrode active material. This is because the buffering effect on the volume expansion of the composite particles is not sufficient, and when the content exceeds 40% by weight, the charge / discharge output characteristics of the negative electrode active material may decrease and the capacity increase effect is insufficient.
  • the amorphous or quasicrystalline carbon 16 between the flaky graphite segments in the second shell layer may be made of the same material as the amorphous or quasicrystalline carbon of the first shell layer, and may exist in the form of the particles or the matrix.
  • pores may be included between the flaky graphite fragments.
  • the thickness of the shell layer including the first shell layer and the second shell layer is preferably 1 to 15 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the thickness of the shell layer is less than 1 ⁇ m, the capacity increase and structural stability improvement effect of the negative electrode active material by the shell layer are insufficient, and when the thickness of the shell layer exceeds 15 ⁇ m, the reaction of the composite particles with lithium during charge and discharge may occur. It is suppressed, so it is difficult to expect high capacity at high rate charge and discharge.
  • the ratio of the average particle diameter (D50) of the core particles and the thickness of the shell layer may be 17 to 95: 5 to 83, specifically 30 to 90: 70 to 10.
  • the negative electrode active material having a ratio in the above range may have a high capacity and exhibit excellent high rate output characteristics.
  • the ratio of the thickness of a said 1st shell layer and a said 2nd shell layer is 5-95: 95-5.
  • the negative electrode active material 1 may be manufactured according to the following two methods, but is not necessarily limited thereto, and any method capable of finally obtaining the negative electrode active material according to the present invention may be used without limitation.
  • the surface of the core particles is coated with a mixture of silicon / carbon black / carbon composite particles and an amorphous or semicrystalline carbon precursor to form a first shell layer, and the surface of the first shell layer is flaky graphite fragment particles and amorphous particles.
  • the negative electrode active material may be prepared by coating a mixture of semi-crystalline carbon precursors to form a second shell layer to prepare negative electrode active material precursor particles and heat treating the same.
  • the surface of the first shell layer is flake graphite fragment particles and amorphous particles.
  • the negative electrode active material may be prepared by coating a mixture of semi-crystalline carbon precursors to form a second shell layer to prepare negative electrode active material precursor particles, and to perform a second heat treatment.
  • the amorphous or semi-crystalline carbon precursor may be sucrose, phenol resin, naphthalene resin, polyvinyl alcohol, polyvinyl chloride, furfuryl alcohol, polyacrylonitrile, polyamide, furan resin, cellulose, styrene, At least one selected from polyimide, epoxy resin, vinyl chloride resin, coal pitch, petroleum pitch, mesoface pitch, tar and low molecular weight heavy oil can be used.
  • a mechanochemical method such as a blade, mechano-fusion, etc., which can give a shear force
  • a spray dry method or an emulsion method may also be used. (emulsion) may be used, but is not limited thereto.
  • the core particles, the silicon / carbon black / carbon composite particles, and the amorphous or semi-crystalline carbon precursor are introduced into a rotor blade mill, and thus, at a temperature higher than the softening point of the amorphous or semi-crystalline carbon precursor.
  • the first shell layer may be coated by imparting a strong mechanical shear force.
  • the composite particle including the first shell layer, the flaky graphite fragment particles, and the amorphous or quasi-crystalline carbon precursor are introduced into a rotor blade mill, whereby the temperature above the softening point of the amorphous or quasi-crystalline carbon precursor. In order to give a strong mechanical shear force in the second shell layer can be coated.
  • All heat treatments including the first heat treatment and the second heat treatment may be performed under an atmosphere containing nitrogen, argon, hydrogen, or a mixed gas thereof, or under vacuum.
  • the heat treatment may be performed at a temperature of 700 to 1300 °C, more preferably may be carried out at a temperature of 800 to 1200 °C.
  • the silicon of the silicon / carbon black / carbon composite particles is suppressed from forming a silicon compound (eg, SiC), so that the capacity increase effect is excellent, and the amorphous or quasi-crystalline carbon precursor Carbonization can take place sufficiently.
  • the negative electrode active material according to another embodiment may be described with reference to FIG. 3.
  • FIG. 3 is a schematic cross-sectional view of a negative electrode active material according to another embodiment.
  • the negative electrode active material 2 may further include a coating layer 16 positioned on the shell layer of the negative electrode active material particles having the structure shown in FIG. 1.
  • the shell layer may be in the form of surrounding the core particles
  • the coating layer may be in the form of surrounding the shell layer.
  • the coating layer 16 may include amorphous or semicrystalline carbon, and the amorphous or semicrystalline carbon is as described above.
  • the exposure of the graphite edge surface may be reduced, thereby improving initial charge and discharge efficiency, and appropriately buffering the volume expansion of silicon in the composite particles to provide cycle life characteristics and thermal properties. Stability can be further improved.
  • the thickness of the coating layer may be 0.01 to 5 ⁇ m, specifically 0.1 to 3 ⁇ m.
  • the thickness of the coating layer is formed in the above range, the exposure of the graphite edge surface is reduced, thereby increasing the initial charge and discharge efficiency, excellent output characteristics, and can implement a lithium secondary battery having improved high capacity and thermal stability.
  • the negative electrode active material 1 may be manufactured according to the following two methods, but is not necessarily limited thereto, and any method capable of finally obtaining the negative electrode active material according to the present invention may be used without limitation. .
  • the surface of the core particles is coated with a mixture of silicon / carbon black / carbon composite particles and an amorphous or semicrystalline carbon precursor to form a first shell layer, and the surface of the first shell layer is flaky graphite fragment particles and amorphous particles.
  • the coated negative electrode active material precursor may be prepared by heat treating the particles.
  • the surface of the first shell layer is flake graphite fragment particles and amorphous particles.
  • the coated negative electrode active material precursor may be prepared by subjecting the particles to a second heat treatment.
  • the silicon / carbon black / carbon composite particles, flaky graphite fragment particles, and amorphous or semicrystalline carbon precursors are as described above, and the atmosphere and temperature of the heat treatment are also as described above.
  • the shape of the negative active material according to the exemplary embodiment illustrated through FIGS. 1 and 3 may be spherical, but is not limited thereto.
  • the average particle diameter (D50) of the negative electrode active material may be 2 to 40 ⁇ m, specifically, may be 5 to 30 ⁇ m.
  • the negative electrode active material has an average particle diameter (D50) in the above range it can be obtained an excellent electrode manufacturing process efficiency and electrode density.
  • a cathode including a cathode active material capable of intercalating and deintercalating lithium ions, a cathode including the anode active material, and a lithium secondary battery including an electrolyte is provided. .
  • the lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of separator and electrolyte used, and may be classified into a cylindrical shape, a square shape, a coin type, a pouch type, etc., Depending on the size, it can be divided into bulk type and thin film type. Since the structure and manufacturing method of these batteries are well known in the art, detailed description thereof will be omitted.
  • the negative electrode may be prepared by mixing the above-described negative electrode active material, a binder, and optionally a conductive material to prepare a composition for forming a negative electrode active material layer, and then coating the negative electrode current collector.
  • the binder may be polyvinyl alcohol, carboxymethyl cellulose / styrene-butadiene rubber, hydroxypropylene cellulose, diacetylene cellulose, polyvinylchloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene or Polypropylene may be used, but is not limited thereto.
  • the binder may be mixed in an amount of 1 to 30 wt% based on the total amount of the composition for forming the negative electrode active material layer.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical changes to the battery.
  • graphite such as natural graphite and artificial graphite
  • Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and summer black
  • Conductive fibers such as carbon fiber and metal fiber
  • 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.
  • the conductive material may be mixed in an amount of 0.1 to 30 wt% based on the total amount of the composition for forming the negative electrode active material layer.
  • the negative electrode current collector may have a thickness of 3 to 500 ⁇ m.
  • Examples of the negative electrode current collector may include stainless steel, aluminum, nickel, titanium, calcined carbon, or a surface treated with carbon, nickel, titanium, silver, or the like on the surface of aluminum or stainless steel.
  • the negative electrode current collector may increase the adhesion of the negative electrode active material by forming fine irregularities on its surface, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the positive electrode includes a positive electrode active material, and as the positive electrode active material, a compound capable of reversible intercalation and deintercalation of lithium (lithiated intercalation compound) may be used. Specifically, at least one selected from cobalt, manganese and nickel and at least one of complex oxides of lithium can be used.
  • the positive electrode may also be prepared by mixing the positive electrode active material, a binder, and optionally a conductive material to prepare a composition for forming a positive electrode active material layer, and then applying the composition to a positive electrode current collector such as aluminum.
  • the electrolyte solution is a lithium salt; And non-aqueous organic solvents, organic solid electrolytes, inorganic solid electrolytes, and the like.
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, lithium chloroborane, lower aliphatic lithium carbonate, lithium tetraphenylborate, imide and the like can be used.
  • the non-aqueous organic solvent is N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimethoxyethane, tetrahydrate Roxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile, nitromethane, methyl formate, methyl acetate, triphosphate Esters, trimethoxy methane, dioxoron derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl pyrionate, ethyl propionate And the like can be used.
  • the organic solid electrolyte may include a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, a poly etchation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, and an ionic dissociation group.
  • a polyethylene derivative a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, a poly etchation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, and an ionic dissociation group.
  • To the polymer can be used.
  • the inorganic solid electrolyte may be Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Li 4 SiO 4 ⁇ Nitrides, halides, sulfates, and the like of Li, such as LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 , may be used.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexa phosphate triamide, nitrobenzene Derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like can be added.
  • halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included to impart nonflammability
  • carbon dioxide gas may be further included to improve high temperature storage characteristics.
  • the separator may exist between the positive electrode and the negative electrode according to the type of the lithium secondary battery.
  • As the separator an insulating thin film having high ion permeability and mechanical strength may be used.
  • the separator may have a pore diameter of 0.01 to 10 ⁇ m and a thickness of 5 to 300 ⁇ m.
  • the separator may include an olefin polymer such as polypropylene having chemical resistance and hydrophobicity; Sheets or nonwovens made of glass fibers, polyethylene, and the like can be used.
  • an olefin polymer such as polypropylene having chemical resistance and hydrophobicity
  • Sheets or nonwovens made of glass fibers, polyethylene, and the like can be used.
  • the electrolyte may also serve as a separator.
  • a graphite fragment having an average particle diameter (D50) of 200 ⁇ m was added to an ethyl alcohol solution, mixed using a magnetic stirrer, and then a flaky graphite fragment having an average thickness of 30 nm using a high shear mixer. Particles were prepared.
  • the obtained composite particle powder was mixed with flaky graphite fragment particles having a thickness of 30 nm and a petroleum pitch and introduced into a rotor blade mill, and the surface of the composite particle was coated with a shell layer composed of flaky graphite fragments and a petroleum pitch. Obtained composite particles.
  • the obtained composite particle powder was heat-treated at 1000 ° C. for 1 hour at an elevated temperature rate of 5 ° C./min in argon atmosphere, and then cooled to prepare a negative electrode active material having an average particle diameter (D50) of 15 ⁇ m.
  • a graphite fragment having an average particle diameter (D50) of 200 ⁇ m was added to an ethyl alcohol solution, mixed using a magnetic stirrer, and then a flaky graphite fragment having an average thickness of 30 nm using a high shear mixer. Particles were prepared.
  • D50 average particle diameter
  • Si silicon
  • D50 average particle diameter
  • the surface of the hard carbon is coated with a mixture of the silicon (Si) / carbon black / carbon composite particles and the petroleum pitch Composite particle powder was obtained.
  • the obtained composite particle powder was mixed with flaky graphite fragment particles having a thickness of 30 nm and a petroleum pitch and introduced into a rotor blade mill, and the surface of the composite particle was coated with a shell layer composed of flaky graphite fragments and a petroleum pitch. Obtained composite particles.
  • the obtained composite particle powder was heat-treated at 1000 ° C. for 1 hour at an elevated temperature rate of 5 ° C./min in argon atmosphere, and then cooled to prepare a negative electrode active material having an average particle diameter (D50) of 15 ⁇ m.
  • a negative electrode active material was prepared in the same manner as in Comparative Example 1 except that the average particle diameter (D50) of 10 ⁇ m population type natural graphite was used in Comparative Example 1.
  • FIG. 4 is a scanning electron microscope (SEM) photograph of hard carbon particles as core particles used in Example 1 and Comparative Example 1
  • FIG. 5 is spherical natural graphite particles as core particles used in Example 2 and Comparative Example 2.
  • the hard carbon particles which are the core particles used in Example 1 and Comparative Example 1
  • the hard carbon particles have a sharp shape, and are spherical natural particles of the core particles used in Examples 2 and Comparative Example 2.
  • graphite it can be confirmed that spherical natural graphite fragments are spherical.
  • FIG. 6 is a scanning electron microscope (SEM) photograph of the negative electrode active material according to Comparative Example 1
  • FIG. 7 is a scanning electron microscope (SEM) photograph of the negative electrode active material according to Example 1.
  • Example 1 a semi-crystalline material obtained by carbonizing carbon fine particles, silicon (Si) / carbon black / carbon composite particles, and petroleum pitch on the surface of core particles that are hard carbon or soft carbon It can be confirmed that the core particles made of carbon have a core-shell structure forming a shell layer, and in Comparative Example 1, only core particles were present without the coated shell layer.
  • FIG. 8 is a scanning electron microscope (SEM) picture of the negative electrode active material according to Comparative Example 2
  • Figure 9 is a scanning electron microscope (SEM) picture of the negative electrode active material according to Example 2.
  • Example 2 carbon particles, silicon (Si) / carbon black / carbon composite particles, and semicrystalline carbon obtained by carbonizing petroleum pitch on the surface of spherical natural graphite core particles It can be confirmed that the core particles have a core-shell structure forming a shell layer, and in Comparative Example 2, only core particles were present without the coated shell layer.
  • Figure 11 is a particle size distribution of the negative electrode active material according to Example 2 and Comparative Example 2.
  • the particle size distribution of the negative electrode active material of Example 1 increases as compared with the case of the negative electrode active material of Comparative Example 1. This is due to the fact that the negative electrode active material prepared in Example 1 had a shell layer composed of flaky graphite and semi-crystalline carbon on the surface of the negative electrode active material particles of Comparative Example 1.
  • the negative electrode active material, carbon black, and CMC / SBR (carboxymethyl cellulose / styrene-butadiene rubber) prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were mixed in distilled water at a weight ratio of 80: 5: 15.
  • a negative electrode slurry was prepared.
  • the negative electrode slurry was coated on a copper foil, followed by drying and pressing to prepare a negative electrode.
  • DEC diethyl carbonate
  • EC ethylene carbonate
  • charging was performed in CC / CV mode, the termination voltage was maintained at 0.02V, and charging was terminated when the current was 0.02mA. Discharge was performed in CC mode, and the termination voltage was kept at 2.0V. Charging was performed in CC mode from three cycles thereafter, and the termination voltage was maintained at 0.02V. Discharge was performed in CC mode, and the termination voltage was kept at 2.0V.
  • 12 and 13 are charge and discharge curves of one (1st) and two (2nd) cycles of the lithium secondary battery manufactured using the negative electrode active materials prepared in Example 1 and Comparative Example 1, respectively.
  • 15 is a charge and discharge curve of one and two cycles for the lithium secondary battery prepared using the negative electrode active material prepared in Example 2 and Comparative Example 2, respectively, from which the lithium secondary including the negative electrode active material according to the present invention It was found that the battery can obtain better initial efficiency characteristics.
  • 16 and 17 are cycle curves for the lithium secondary battery manufactured by using the negative electrode active materials prepared in Example 1, Comparative Example 1, Example 2, and Comparative Example 2, respectively. It was found that the included lithium secondary battery can obtain better life characteristics.
  • Examples 18 and 19 show the results of differential scanning sequence analysis of the electrodes prepared using the negative electrode active materials of Example 1, Comparative Example 1, Example 2, and Comparative Example 2, respectively. It can be seen that the calorific values of Examples 1 and 2 are lower than those of Comparative Examples 1 and 2 in the low temperature (250 ° C. or lower) range, and the exothermic peaks of Examples 1 and 2 in the high temperature (250 ° C. or higher) range. It turned out that was higher than the comparative example 1 and the comparative example 2.

Abstract

La présente invention concerne un matériau actif d'électrode négative pour batterie secondaire au lithium, son procédé de fabrication et une batterie secondaire au lithium comprenant celui-ci, ledit matériau actif d'électrode négative comprenant : des particules de cœur qui comprennent un ou plusieurs éléments choisis parmi le carbone dur, le carbone doux et le graphite naturel sphérique ; et des couches d'écorce disposées sur les surfaces des particules de cœur, ladite couche d'écorce comprenant i) une première couche d'écorce qui comprend des particules composites de silicium (Si)/noir de carbone/carbone, et du carbone amorphe ou semi-cristallin, et ii) une seconde couche d'écorce qui présente une structure dans laquelle le carbone amorphe ou semi-cristallin est dispersé entre les particules de fragments de graphite lamellaire, et les particules de fragments de graphite lamellaire sont empilées et structurées dans une direction de cercle concentrique, et qui est formée sur la première couche d'écorce.
PCT/KR2016/014255 2015-12-07 2016-12-06 Matériau actif d'électrode négative pour batterie secondaire au lithium comprenant un cœur composé de carbone, son procédé de fabrication et batterie secondaire au lithium comprenant celui-ci WO2017099456A1 (fr)

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CN109524635A (zh) * 2018-09-16 2019-03-26 北京化工大学 一种用于锂离子电池负极的硅炭复合材料的制备方法及其应用
US10468674B2 (en) 2018-01-09 2019-11-05 South Dakota Board Of Regents Layered high capacity electrodes
US20200243846A1 (en) * 2017-09-30 2020-07-30 Btr New Material Group Co., Ltd. Carbon matrix composite material, preparation method therefor and lithium ion battery comprising same
CN113380998A (zh) * 2021-06-02 2021-09-10 夏秀明 一种硅碳负极材料及其制备方法和应用
CN113889593A (zh) * 2020-07-02 2022-01-04 洛阳月星新能源科技有限公司 一种硬碳包覆软碳复合材料的制备方法
CN115275191A (zh) * 2022-09-26 2022-11-01 江苏正力新能电池技术有限公司 一种负极材料、负极片及钠离子电池
US11489160B2 (en) * 2020-12-10 2022-11-01 The Industry & Academic Cooperation In Chungnam National University (Iac) Anode active material including carbon composite for lithium secondary battery and method of manufacturing the same
US11626584B2 (en) 2014-04-25 2023-04-11 South Dakota Board Of Regents High capacity electrodes
US11682757B2 (en) 2017-09-26 2023-06-20 Unist (Ulsan National Institute Of Science And Technology) Composite anode active material, method of preparing the composite anode material, and lithium secondary battery comprising the composite anode active material

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KR20190067474A (ko) * 2017-12-07 2019-06-17 에스케이이노베이션 주식회사 리튬 이차 전지용 음극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 이차 전지
KR102051072B1 (ko) * 2018-01-10 2019-12-02 울산과학기술원 복합음극활물질, 이의 제조 방법 및 이를 포함하는 음극을 구비한 리튬이차전지
CN110085856A (zh) 2018-01-26 2019-08-02 三星电子株式会社 含硅结构体、其制备方法、使用其的碳复合物及各自包括其的电极、锂电池和设备
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US11626584B2 (en) 2014-04-25 2023-04-11 South Dakota Board Of Regents High capacity electrodes
US11682757B2 (en) 2017-09-26 2023-06-20 Unist (Ulsan National Institute Of Science And Technology) Composite anode active material, method of preparing the composite anode material, and lithium secondary battery comprising the composite anode active material
US20200243846A1 (en) * 2017-09-30 2020-07-30 Btr New Material Group Co., Ltd. Carbon matrix composite material, preparation method therefor and lithium ion battery comprising same
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CN113889593B (zh) * 2020-07-02 2023-04-07 洛阳月星新能源科技有限公司 一种硬碳包覆软碳复合材料的制备方法
US11489160B2 (en) * 2020-12-10 2022-11-01 The Industry & Academic Cooperation In Chungnam National University (Iac) Anode active material including carbon composite for lithium secondary battery and method of manufacturing the same
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CN115275191A (zh) * 2022-09-26 2022-11-01 江苏正力新能电池技术有限公司 一种负极材料、负极片及钠离子电池

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