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WO2025143677A1 - Composite carbone-silicium/carbone et son procédé de production - Google Patents

Composite carbone-silicium/carbone et son procédé de production Download PDF

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Publication number
WO2025143677A1
WO2025143677A1 PCT/KR2024/020556 KR2024020556W WO2025143677A1 WO 2025143677 A1 WO2025143677 A1 WO 2025143677A1 KR 2024020556 W KR2024020556 W KR 2024020556W WO 2025143677 A1 WO2025143677 A1 WO 2025143677A1
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Prior art keywords
carbon
silicon
carbon composite
pitch
composite
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Korean (ko)
Inventor
김도흥
전효진
채수종
이진수
박성수
윤기찬
고민성
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Pukyong National University
Hanwha Solutions Corp
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Pukyong National University
Hanwha Solutions Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/36—Reactivation or regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • 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
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • H—ELECTRICITY
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    • 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
    • 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 carbon-silicon/carbon composite, and more particularly, to a carbon-silicon/carbon composite and a method for producing the same.
  • pitch a viscoelastic solid polymer extracted from crude oil or plants, has the advantages of high yield when converted into carbon materials, low cost of raw materials, and its molecular structure is closer to the graphite structure than other raw materials, which can reduce energy required for heat treatment (U.S. Patent Nos. 4,242,196 and 4,340,464).
  • pyrolysis fuel oil PFO
  • naphtha cracking bottom oil NCB
  • vacuum residue VR
  • FCC-DO fluid catalytic cracking decant oil
  • Silicon theoretically has a very high energy density, and is attracting attention as a next-generation battery negative electrode active material to replace graphite.
  • it has the problem of very low mechanical stability, such as the volume increasing by up to 300% during charging and discharging, and the silicon, which is the negative electrode active material, is crushed as charging and discharging proceeds.
  • Patent Document 0001 Republic of Korea Patent Application Publication No. 10-2019-0093960
  • Patent Document 0002 U.S. Patent No. 4,242,196
  • Patent Document 0003 U.S. Patent No. 4,340,464
  • An object of the present invention is to provide a carbon-silicon/carbon composite in which a silicon/carbon composite matrix is formed in the pores and/or surface of a porous carbon support having controlled pore characteristics.
  • Another object of the present invention is to provide a negative electrode active material comprising the carbon-silicon/carbon composite.
  • the method may further include: (1) a step of synthesizing pitch by thermal decomposition and condensation polymerization of a petroleum-based raw material, (2) a step of solidifying and pelletizing the pitch to obtain a pellet-like pitch or solidifying, pelletizing, and pulverizing the pitch to obtain a powder-like pitch, (3) a step of stabilizing the pellet-like pitch or the powder-like pitch, (4) a step of carbonizing the stabilized pitch to obtain a carbonized body, and (5) a step of activating the carbonized body to obtain a porous carbon support.
  • the silicon/carbon composite matrix can be formed by composite CVD of a silicon source and a carbon source on the porous carbon support.
  • gas flow ratio of the silicon source and the carbon source can be 1:0.1 to 1:2.
  • the present invention provides a negative electrode active material comprising the carbon-silicon/carbon composite described above.
  • the present invention provides an all-solid-state battery including a solid electrolyte interphase (SEI) film including the carbon-silicon/carbon composite described above.
  • SEI solid electrolyte interphase
  • the carbon-silicon/carbon composite according to an embodiment of the present invention forms a silicon/carbon composite matrix in the pores and/or surface of a porous carbon support having a high ratio of mesopores among the total pores, thereby suppressing the overall silicon size when the carbon-silicon/carbon composite is used as an anode active material, and suppressing the formation of an intermediate phase Crystal-Li x Si y (e.g., Li 15 Si 4 or Li 3.75 Si) that affects battery performance deterioration, thereby alleviating battery performance deterioration during repeated charge/discharge.
  • an intermediate phase Crystal-Li x Si y e.g., Li 15 Si 4 or Li 3.75 Si
  • Figure 3 is a dQ/dV measurement graph of Example 1, Example 2, and Comparative Example 1 of the present invention.
  • Figure 5 is an image of the XRD analysis results according to heat treatment temperature (Examples 1-1 to 1-3) of a carbon-silicon/carbon composite (Example 1) according to a comparative example and an embodiment of the present invention.
  • the present invention is not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the invention is not changed.
  • a carbon-silicon/carbon composite which includes a porous carbon support having a volume ratio of mesopores having a pore size of 2 to 50 nm based on a total pore volume of 5 to 80%, and a silicon/carbon composite matrix disposed on a surface and inside the pores of the porous carbon support.
  • a carbon-silicon/carbon composite according to an embodiment of the present invention comprises a porous carbon support.
  • the porous carbon support may have a tap density of 0.05 to 0.5 g/ml.
  • the porous carbon support may have a tap density of 0.05 to 0.3 g/ml, more preferably, a tap density of 0.1 to 0.3 g/ml.
  • the tap density of the porous carbon support is less than 0.05 g/ml, process control may be difficult during formation of a silicon/carbon composite matrix, which may result in a decrease in yield, and when the tap density of the porous carbon support exceeds 0.5 g/ml, it may be difficult to uniformly form a matrix during formation of a silicon/carbon composite matrix.
  • the silicon/carbon composite matrix may mean a continuous phase (Si x C y ) in which a silicon portion formed by a Si-Si bond and a silicon carbide portion formed by a Si-C bond are mixed.
  • a carbon-silicon/carbon composite can be obtained by performing composite CVD of a silicon source and a carbon source on a porous carbon support.
  • the silicon/carbon composite matrix may include crystalline silicon particles.
  • the size of the silicon crystals may be on the nano level.
  • the average size of the silicon crystals in the silicon/carbon composite matrix may be 10 nm or less.
  • the average size of the silicon crystals in the silicon/carbon composite matrix may be 8 nm or less, 5 nm or less, 3 nm or less, or 1 nm or less.
  • the silicon content in the total weight of the carbon-silicon/carbon composite may be 20 to 70 wt%, and preferably 25 to 65 wt%. If the silicon content in the total weight of the carbon-silicon/carbon composite is less than 20 wt%, the electric capacity may be reduced, and if it exceeds 70 wt%, the problem caused by the volume expansion of silicon during charge and discharge may not be solved, which may cause structural damage to the negative electrode material and deteriorate the cycle characteristics.
  • the silicon/carbon composite matrix may be 10 to 90 wt% of the total weight of the carbon-silicon/carbon composite, and preferably 15 to 85 wt%. If the silicon/carbon composite matrix is less than 10 wt% of the total weight of the carbon-silicon/carbon composite, the electric capacity may be reduced, and if it exceeds 90 wt%, a problem caused by volume expansion of silicon during charge and discharge may not be resolved, which may cause structural damage to the negative electrode material and deteriorate cycle characteristics.
  • the silicon may be crystalline or amorphous, and preferably may be amorphous or a similar phase.
  • the silicon is crystalline, the smaller the crystallite size, the more dense the composite can be obtained, so that the strength of the matrix is strengthened and cracks can be prevented. Accordingly, the initial efficiency or cycle life characteristics of the secondary battery can be improved.
  • the above silicon may further include a silicon oxide compound.
  • the silicon oxide compound may be represented by a general formula of SiO x (0.5 ⁇ x ⁇ 2).
  • x when the value of x is less than 0.5, expansion and contraction may increase during charge and discharge of the secondary battery, and the life characteristics may deteriorate, and when x exceeds 2, the initial efficiency of the secondary battery may decrease as the amount of inactive oxide increases.
  • the content of the silicon oxide compound in the silicon may be 50 wt% or less based on the total weight of the silicon. If the content of the silicon oxide compound in the silicon exceeds 50 wt%, the initial efficiency of the secondary battery may be reduced.
  • the carbon-silicon/carbon composite may have a c/a peak ratio of 0 to 1.5, preferably 0 to 1.3, more preferably 0 to 1.2, even more preferably 0 to 1.18, and even more preferably 0 to 1.15.
  • the c/a peak ratio of the carbon-silicon/carbon composite satisfies the above range, it may be more advantageous in achieving the purpose of the present invention, such as having an effect of maintaining stable electrochemical performance during a life evaluation.
  • the c/a peak ratio represents the peak ratio of crystal (c) and amorphous (a).
  • a carbon-silicon/carbon composite according to one embodiment of the present invention is manufactured by a manufacturing method including a step of manufacturing a carbon-silicon/carbon composite by forming a silicon/carbon composite matrix on the surface and inside the pores of a porous carbon support.
  • pitch can be synthesized by thermal decomposition and polycondensation of petroleum-based raw materials.
  • the petroleum raw material may include at least one selected from the group consisting of pyrolysis fuel oil (PFO), naphtha cracking residue (NCB), ethylene cracker bottom oil (EBO), vacuum residue (VR), de-asphalted oil (DAO), atmospheric residue (AR), fluid catalytic cracking (RFCC-DO) oil, residue fluid catalytic cracking decant oil (RFCC-DO), and heavy aromatic oil.
  • PFO pyrolysis fuel oil
  • NBB naphtha cracking residue
  • EBO ethylene cracker bottom oil
  • VR vacuum residue
  • DAO de-asphalted oil
  • AR atmospheric residue
  • RFCC-DO fluid catalytic cracking
  • RFCC-DO residue fluid catalytic cracking decant oil
  • heavy aromatic oil heavy aromatic oil.
  • the petroleum raw material may include pyrolysis fuel oil.
  • the thermal decomposition and polycondensation of the petroleum raw material can be performed under an atmosphere of an oxidizing gas, an inert gas, or a mixture thereof.
  • the oxidizing gas can be oxygen, ozone, or a combination thereof
  • the inert gas can be nitrogen, helium, neon, argon, or a combination thereof
  • the mixture thereof can be air, but is not particularly limited thereto.
  • the thermal decomposition and polycondensation of the petroleum-based raw material can be performed under stirring.
  • the stirring conditions of the petroleum-based raw material are not particularly limited, but, for example, a stirrer rotating at 10 to 500 rpm can be used.
  • the pitch synthesized in step (1) may have a softening point of 200 to 350°C.
  • the pitch may have a softening point of 200 to 330°C.
  • the pitch may have a softening point of 200 to 300°C. Since the pitch manufactured according to the present invention has a high softening point, when used as a precursor for manufacturing a carbon support, the stabilization process is easy, and a high yield can be obtained after carbonization and activation.
  • the yield of the pitch synthesized in step (1) may be 10 to 50 wt%. In a preferred specific embodiment of the present invention, the yield of the pitch may be 10 to 40 wt%. In a more preferred specific embodiment of the present invention, the yield of the pitch may be 20 to 30 wt%.
  • a step of pretreating a petroleum-based raw material may be performed before step (1) above.
  • a pitch having a higher softening point can be manufactured.
  • the pretreatment step may be performed at a temperature equal to or lower than the thermal decomposition and polycondensation temperature of the petroleum-based raw material in step (1), but is not particularly limited to this condition.
  • the pretreatment step may be performed at 250 to 450°C, preferably 250 to 400°C, and more preferably 300 to 400°C.
  • the pretreatment step may be performed for a time equal to or shorter than the thermal decomposition and polycondensation time of the petroleum-based raw material in step (1), but is not particularly limited to this condition. Specifically, the pretreatment step may be performed for 1 to 8 hours, preferably 1 to 6 hours, and more preferably 1 to 5 hours.
  • the pitch in the step (2), can be solidified and pelletized to obtain a pellet-like pitch, or the pitch can be solidified, pelletized, and pulverized to obtain a powder-like pitch.
  • the pitch (liquid) obtained in the step (1) is solidified, for example, by extrusion and cooling, and is pelletized into a desired size to obtain a solid pitch pellet (pellet-shaped pitch).
  • the process of extruding, cooling, and pelletizing the liquid pitch to obtain a solid pitch pellet can be performed using a commercialized device.
  • this process can be performed using a double belt cooler & flaker of IPCO, but is not particularly limited to this device.
  • the pitch pellets (pellet-shaped pitch) obtained in step (2) have an average particle size of 1 to 30 mm, preferably 5 to 25 mm.
  • the pitch pellets (pellet-shaped pitch) can be used to manufacture a porous carbon support through stabilization, carbonization, and activation, which will be described later, without separately pulverizing them.
  • the pitch pellets (pellet-shaped pitch) can be further crushed or pulverized and classified. Through crushing or pulverization, the pitch pellets (pellet-shaped pitch) can be further finely divided, and through classification, the particle size distribution of the pitch pellets (pellet-shaped pitch) can be made uniform.
  • the classification can be dry classification, wet classification, classification using a sieve, etc. By crushing or pulverizing and classification, a powdered pitch having an average particle size of 50 to 500 ⁇ m can be obtained.
  • step (3) a step of stabilizing the pellet-shaped pitch or powder-shaped pitch can be performed.
  • the pellet-shaped pitch or powder-shaped pitch obtained in step (2) is first oxidized to stabilize the carbon structure of the pitch.
  • the stabilization can be performed under conditions of a flow rate of an oxidizing gas, preferably air, of 0.1 to 500 ml/min, preferably 1 to 300 ml/min.
  • an oxidizing gas preferably air
  • the structure of the carbon inside the pellet-shaped pitch or the powder-shaped pitch can be sufficiently stabilized.
  • the stabilization can be performed for a period of 1 to 10 hours, preferably 2 to 8 hours.
  • the structure of the carbon inside the pellet-shaped pitch or the powder-shaped pitch can be sufficiently stabilized.
  • step (4) the stabilized pitch is carbonized to obtain a carbonized body.
  • the stabilized pitch is carbonized to obtain a carbonized body.
  • other functional groups included in the pitch are removed, and a carbonized body composed of substantially pure carbon can be obtained.
  • the carbonization may be performed under an inert gas atmosphere.
  • the carbonization may be performed under a nitrogen or argon atmosphere, but is not particularly limited thereto.
  • the carbonization may be performed at a temperature of more than 700°C and less than or equal to 1,000°C, preferably 800 to 900°C. If the temperature during carbonization is lower than this range, carbonization may not be sufficiently performed, and if the temperature during carbonization is higher than this range, the carbonization yield may decrease.
  • the carbonization can be performed under a flow rate condition of an inert gas, preferably nitrogen, of 0.1 to 30 ml/min, preferably 0.1 to 10 ml/min.
  • an inert gas preferably nitrogen
  • the stabilized pitch can be sufficiently carbonized.
  • step (5) the carbonized body is activated to obtain a porous carbon support.
  • pores are formed in the carbonized body, thereby obtaining a porous carbon support.
  • the activation of the carbonized body can be performed under an oxidizing gas atmosphere.
  • the activation of the carbonized body can be performed under a steam atmosphere, but is not particularly limited thereto.
  • the activation of the carbonized body can be performed at a temperature of more than 700°C and less than or equal to 1,000°C, preferably 800 to 900°C.
  • a porous carbon support in which micropores and mesopores are sufficiently formed can be obtained.
  • the activation of the carbonized body can be performed at a pressure of 0.1 to 10 bar, preferably 0.1 to 5 bar.
  • a porous carbon support in which micropores and mesopores are sufficiently formed can be obtained.
  • the activation of the carbonized body can be performed under a flow rate condition of an oxidizing gas, preferably steam, of 0.1 to 100 ml/min, preferably 0.1 to 50 ml/min.
  • an oxidizing gas preferably steam
  • a porous carbon support in which micropores and mesopores are sufficiently formed can be obtained.
  • the activation of the carbonized body can be performed for 0.5 to 5 hours, preferably 1 to 3 hours.
  • a porous carbon support in which micropores and mesopores are sufficiently formed can be obtained.
  • the stabilization, carbonization and activation of the above steps (3) to (5) can each be performed in a heating furnace using microwaves.
  • the stabilization, carbonization and activation of the above steps (3) to (5) can all be performed in a heating furnace using microwaves.
  • a heating furnace using microwaves is preferred because it can increase the temperature of the pitch itself without increasing the external temperature of the pitch, but is not particularly limited thereto.
  • the above steps (3) to (5) can be performed continuously in one device.
  • the above steps (3) to (5) can be performed continuously in one rotary kiln, but are not particularly limited to this device. By performing the above steps (3) to (5) continuously in one device, optimization of the process can be achieved.
  • the porous carbon support obtained in step (5) can be further disintegrated or pulverized and classified.
  • the porous carbon support can be further finely divided through disintegration or pulverization, and the particle size distribution of the porous carbon support can be made uniform through classification.
  • the classification can be dry classification, wet classification, classification using a sieve, etc.
  • a porous carbon support powder having an average particle size of 1 to 20 ⁇ m, a BET specific surface area of 300 to 3,000 m2/g, and a tap density of 0.05 to 0.5 g/ml can be obtained.
  • the porous carbon support powder has a volume ratio of mesopores having a pore size of 2 to 50 nm based on the total pore volume of 5 to 80%.
  • SiCx may be formed relatively in large quantities, which may result in a decrease in electric capacity and a deterioration in cycle characteristics.
  • the weight ratio is less than 1:0.1 (silicon source more than 1 and carbon source less than 0.1)
  • SiCx may be formed relatively in small quantities and Si may be formed relatively in large quantities, which may not resolve the problem caused by volume expansion of silicon during charge and discharge, which may result in structural damage to the negative electrode material.
  • the negative electrode active material according to an embodiment of the present invention may additionally include a carbon-based negative electrode material, specifically a graphite-based negative electrode material, in addition to the carbon-silicon/carbon composite.
  • the negative electrode active material may be obtained by mixing the carbon-silicon/carbon composite according to an embodiment of the present invention and a carbon-based negative electrode material, for example, a graphite-based negative electrode material.
  • the carbon-based negative electrode material may include at least one selected from the group consisting of, for example, natural graphite, artificial graphite, soft carbon, hard carbon, mesocarbon, carbon fibers, carbon nanotubes, pyrolytic carbons, cokes, organic polymer compound sintered bodies, and carbon black, but is not particularly limited thereto.
  • the negative active material according to an embodiment of the present invention can be effectively used in manufacturing a secondary battery, specifically, a negative electrode of a lithium secondary battery and a negative electrode of an all-solid-state battery.
  • the above-described all-solid-state battery may be an all-solid-state battery including a cathode, an anode, and a solid electrolyte between the cathode and the anode, and the anode may include a cathode active material layer, and may include a solid electrolyte interphase (SEI) film including the carbon-silicon/carbon composite described above on at least a portion of cathode active material particles of the cathode active material layer.
  • SEI solid electrolyte interphase
  • the above-described negative electrode active material particles may be carbon-based negative electrode materials, in which case the description may be similar to that described in the above-described negative electrode active material, and therefore, the related description will be omitted.
  • the negative electrode configuration, positive electrode configuration, and solid electrolyte configuration can be applied to known configurations of all-solid-state batteries, and therefore the present invention does not specifically limit them.
  • step (2) The solid pitch pellets obtained above were pulverized to manufacture pitch particles having an average particle size of 200 ⁇ m (step (2)), and then placed in a rotary kiln having three zones to sequentially perform stabilization (step (3)), carbonization (step (4)), and activation (step (5)).
  • step (3) stabilization
  • step (4) carbonization
  • step (5) activation
  • Table 1 The conditions for stabilization, carbonization, and activation are as shown in Table 1 below.
  • the specific surface area of the carbon support was measured using Belsorp mini II according to ASTM D4820-93.
  • the tap density of the carbon support was measured using a tap density analyzer (Electrolab, ETD-1020x) according to ASTM B527.
  • the average particle size of the carbon support was measured using a particle size analyzer (Horiba, laser particle analyzer, LA-960V2) according to ASTM E112. The results are shown in Table 1.
  • step condition Standard example stabilization Temperature (°C) 300 Time (hr) 3 atmosphere air carbonization Temperature (°C) 900 Time (hr) 1 atmosphere nitrogen activate Temperature (°C) 900 Time (hr) 3 Water vapor flow rate (ml/min) 200 Support properties Average particle size ( ⁇ m) 200 Specific surface area (m2/g) 1409.1 Tap density (g/ml) 0.44
  • the porous carbon support of the reference example was pulverized with a pulverizer (NETZSCH, air jet mill) to obtain a fine powder of the porous carbon support having an average particle size of 7 ⁇ m.
  • the carbon-silicon/carbon composite manufactured according to Example 1 was observed using a scanning electron microscope (SEM). The results of the SEM analysis are shown in Fig. 1.
  • Half coin cells were manufactured using the composites of Examples 1, 2, 3, and Comparative Examples, and then electrochemical evaluations were performed.
  • the conditions for manufacturing the half coin cells are shown in Table 2, and the evaluation results are shown in Tables 3 to 4 and FIG. 2.
  • AM, CM, and BM represent active material (carbon-silicon/carbon composite), conductor (Super P carbon black), and binder (styrene-butadiene rubber/carboxymethyl cellulose 5:5), respectively
  • EC, EMC, DMC, FEC, VC, and PS represent ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, fluoroethylene carbonate, vinylene carbonate, and propane sultone, respectively.
  • Composition (AM:CM:BM) 8:1:1 Area capacity (mAh/cm2) 1 Electrolyte 1.3 M LiPF 6 EC/EMC/DMC 3:5:2, FEC 10%, LiBF 4 0.2%, 0.5% VC, 1% PS Cut-off voltage (V) Formation: 0.005-1.5, Cycle test: 0.005-1.2 C-rate (C) Formation: 0.1-0.1, 0.005 V at 0.01 C cut-off (CV)
  • Example 1 The composite according to Example 1 was heat treated at temperatures of 600°C (Example 1-1), 700°C (Example 1-2), and 900°C (Example 1-3), respectively.
  • XRD analysis was performed on the composite according to Example 1, the heat-treated composite according to Examples 1-1 to 1-3, and the comparative composite under the following conditions. This is shown in Fig. 5.

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Abstract

La présente invention concerne : un composite carbone-silicium/carbone dans lequel une matrice composite silicium/carbone est formée sur la surface et à l'intérieur des pores d'un support de carbone poreux ayant des propriétés de pore contrôlées ; et son procédé de production. Lorsque le composite carbone-silicium/carbone selon un mode de réalisation de la présente invention est utilisé en tant que matériau actif d'électrode négative, la taille globale du silicium peut être supprimée, et la formation de cristal-LixSiy (par exemple Li15Si4 ou Li3,75Si), qui est une phase intermédiaire affectant la dégradation des performances de la batterie, peut être supprimée pour atténuer la dégradation des performances de la batterie au cours de charges et décharges répétées.
PCT/KR2024/020556 2023-12-29 2024-12-18 Composite carbone-silicium/carbone et son procédé de production Pending WO2025143677A1 (fr)

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