WO2026005404A1 - Matériau d'électrode de batterie secondaire et son procédé de fabrication - Google Patents

Matériau d'électrode de batterie secondaire et son procédé de fabrication

Info

Publication number
WO2026005404A1
WO2026005404A1 PCT/KR2025/008672 KR2025008672W WO2026005404A1 WO 2026005404 A1 WO2026005404 A1 WO 2026005404A1 KR 2025008672 W KR2025008672 W KR 2025008672W WO 2026005404 A1 WO2026005404 A1 WO 2026005404A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating layer
secondary battery
active material
electrode active
pitch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/KR2025/008672
Other languages
English (en)
Korean (ko)
Inventor
임장빈
장다원
임경원
전효진
최재원
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hanwha Solutions Corp
Original Assignee
Hanwha Solutions Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020250081947A external-priority patent/KR20250180159A/ko
Application filed by Hanwha Solutions Corp filed Critical Hanwha Solutions Corp
Publication of WO2026005404A1 publication Critical patent/WO2026005404A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—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
    • 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
    • H01M4/38—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
    • H01M4/58—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 invention relates to a secondary battery electrode material including petroleum pitch and a method for manufacturing the same.
  • Secondary batteries are a prime example of electrochemical devices that utilize this electrochemical energy, and their applications are expanding. With the recent technological development and increasing demand for portable devices such as laptops, mobile phones, and cameras, the demand for secondary batteries as an energy source has rapidly increased. Among these secondary batteries, lithium secondary batteries, which boast high energy density and high capacity, have been extensively studied and are now commercialized and widely used.
  • secondary batteries are composed of a positive electrode, a negative electrode, an electrolyte, and a separator.
  • the positive electrode material of a lithium secondary battery includes metal oxides such as LiCoO 2 , Li(NiCoMn)O 2 , Li(NiCoAl)O 2 , LiFePO 4 , LiMnO 2 , LiMn 2 O 4 or LiCrO 2
  • the negative electrode material includes metal lithium, carbon-based materials such as graphite or activated carbon, or silicon oxide (SiOx).
  • metal lithium was mainly used in the early days, but as the charge and discharge cycle progresses, lithium atoms grow on the surface of the metal lithium, damaging the separator and destroying the battery.
  • the present invention has been devised to overcome the above-described problems, and provides a secondary battery electrode material and a method for manufacturing the same, which can significantly improve the performance of a secondary battery to which the same is applied, by forming a coating layer containing petroleum pitch on the surface of an electrode active material, and then introducing an additional coating layer or performing an additional process to manufacture the secondary battery electrode material.
  • the secondary battery electrode material of the present invention may include an electrode active material including silicon (Si), a first coating layer coated on the surface of the electrode active material, and a second coating layer coated on the surface of the second coating layer.
  • the first coating layer may include carbonized petroleum pitch.
  • the carbonized petroleum pitch may be carbonized at a temperature of 500 to 900°C for 60 to 180 minutes.
  • the electrode active material includes a porous carbon support, and silicon can be disposed on the surface and inside the pores of the porous carbon support.
  • the electrode active material may include a nonporous carbon support including at least one of hard carbon and soft carbon.
  • the electrode active material may be a porous carbon support having an average particle size of 5 to 20 ⁇ m.
  • the first coating layer may have a thickness of 10 to 400 nm.
  • the second coating layer may include carbonized petroleum pitch or carbon.
  • the second coating layer may have a thickness of 10 to 400 nm.
  • the secondary battery electrode material of the present invention includes an electrode active material including silicon (Si) and a coating layer coated on the surface of the electrode active material, and the coating layer includes carbonized petroleum pitch and may have a thickness of 10 to 95 nm.
  • the secondary battery may be a lead (Pd) battery, a nickel-cadmium (NiCd) battery, a nickel-metal (Ni-metal) hydrogen battery, a lithium ion (Li-ion) battery, a solid-state battery, a soft carbon battery, a hard carbon battery, or a lithium ion polymer (Li-ion polymer) battery.
  • the electrode active material may be a negative electrode active material.
  • the electrode active material may be a spherical activated carbon powder having silicon (Si) coated on the surface.
  • the spherical activated carbon may contain 10 to 60 wt% of silicon based on the total wt%.
  • the secondary battery electrode material may be a secondary battery negative electrode material.
  • the method for manufacturing a secondary battery electrode material of the present invention may include a first step of forming a first coating layer on the surface of an electrode active material by coating petroleum pitch on the surface of the electrode active material, a second step of carbonizing the electrode active material having the first coating layer formed on the surface, a third step of forming a second coating layer on the surface of the carbonized first coating layer by coating petroleum pitch on the surface of the carbonized first coating layer, and a fourth step of carbonizing the negative electrode active material having the first coating layer and the second coating layer sequentially formed on the surface, thereby manufacturing a secondary battery negative electrode material.
  • the method for manufacturing a secondary battery electrode material of the present invention may include a first step of forming a first coating layer on the surface of an electrode active material by coating petroleum pitch on the surface of the electrode active material, a second step of carbonizing the electrode active material on the surface of which the first coating layer has been formed, and a third step of forming a second coating layer made of carbon on the surface of the carbonized first coating layer, thereby manufacturing a secondary battery negative electrode material.
  • the method for manufacturing a secondary battery electrode material of the present invention may include a first step of forming a coating layer on the surface of an electrode active material by coating petroleum pitch on the surface of the electrode active material, and a second step of carbonizing the electrode active material on the surface of which the coating layer has been formed, and then performing a CIP (Cold Isostatic Pressing) method to manufacture a secondary battery negative electrode material.
  • a CIP Cold Isostatic Pressing
  • the method for manufacturing a secondary battery electrode material of the present invention may include a first step of forming a first coating layer on the surface of an electrode active material by coating petroleum pitch on the surface of the electrode active material and then performing a CIP (Cold Isostatic Pressing) method, a second step of carbonizing the electrode active material having the first coating layer formed on the surface, a third step of forming a second coating layer on the surface of the carbonized first coating layer by coating petroleum pitch on the surface of the carbonized first coating layer, and a fourth step of carbonizing the negative electrode active material having the first coating layer and the second coating layer sequentially formed on the surface, thereby manufacturing a secondary battery negative electrode material.
  • a CIP Cold Isostatic Pressing
  • the first step coating can be performed by dry coating using the mechano-fusion method.
  • the second stage carbonization can be performed at a temperature of 500 to 900°C for 60 to 180 minutes.
  • the fourth stage carbonization can be performed at a temperature of 500 to 900°C for 60 to 180 minutes.
  • the third step may form a second coating layer made of carbon on the surface of the carbonized first coating layer using a CVD (Chemical Vapor Deposition) method.
  • CVD Chemical Vapor Deposition
  • the secondary battery electrode material of the present invention and its manufacturing method can significantly improve the performance of a secondary battery to which the secondary battery electrode material is applied by forming a coating layer containing petroleum pitch on the surface of an electrode active material and then introducing an additional coating layer or performing an additional process to manufacture the secondary battery electrode material.
  • the present invention can significantly improve the performance of a secondary battery using the electrode material by forming a coating layer containing petroleum pitch on the surface of an electrode active material and then introducing an additional coating layer or performing an additional process to manufacture a secondary battery electrode material.
  • the secondary battery electrode material of the present invention may include an electrode active material including silicon (Si), a first coating layer coated on the surface of the electrode active material, and a second coating layer coated on the surface of the first coating layer.
  • the first coating layer may include carbonized pitch.
  • the second coating layer may include carbonized pitch and/or carbon.
  • the electrode active material containing silicon (Si) may be a porous carbon support containing silicon (Si), and preferably may be a spherical activated carbon powder having silicon (Si) coated on the surface.
  • the electrode active material may have an average particle size of 20 ⁇ m or less, preferably 5 to 20 ⁇ m.
  • the electrode active material is a porous carbon support containing silicon (Si)
  • the first coating layer is formed on the surface of the porous carbon support containing silicon (Si)
  • the surface of the porous carbon support containing silicon (Si) includes not only the surface exposed to the outside but also the surface located inside.
  • the porous carbon support containing silicon (Si) is a porous material having pores on the outer surface and/or the inner surface.
  • the petroleum pitch penetrates and coats not only the outer surface of the porous carbon support containing silicon (Si) but also the inner surface of the porous carbon support containing silicon (Si) through the pores, thereby partially or completely blocking the pores of the porous carbon support containing silicon (Si), and can be coated on the outer surface of the porous carbon support containing silicon (Si) with a certain thickness to form the first coating layer.
  • the second coating layer is formed on the surface of the first coating layer, and the surface of the first coating layer includes not only the surface exposed to the outside but also the surface located inside.
  • the porous carbon support including silicon (Si) having the first coating layer coated on the surface is a porous material having pores on the outer surface and/or the inner surface.
  • the petroleum pitch and/or carbon penetrate and coat not only the outer surface of the porous carbon support including silicon (Si) having the first coating layer coated on the surface, but also the inner surface of the porous carbon support including silicon (Si) having the first coating layer coated on the surface through the pores, thereby partially or completely blocking the pores of the porous carbon support including silicon (Si) having the first coating layer coated on the surface, and can form a second coating layer by coating the outer surface of the porous carbon support including silicon (Si) having the first coating layer coated on the surface with a certain thickness.
  • the spherical activated carbon powder coated with silicon (Si) on the surface means that silicon is formed on the surface of the spherical activated carbon powder, and the surface of the spherical activated carbon powder includes not only the surface exposed to the outside but also the surface located inside.
  • the spherical activated carbon powder is a porous material having pores on the outside and/or the inside.
  • the silicon penetrates and coats not only the outside surface of the spherical activated carbon powder but also the inside surface of the spherical activated carbon powder through the pores, thereby partially or completely blocking the pores of the spherical activated carbon powder and coating the outside surface of the spherical activated carbon powder with a certain thickness.
  • the spherical activated carbon may contain silicon in an amount of 10 wt% or more, preferably 10 to 60 wt%, based on the total weight.
  • the electrode active material may include a porous carbon support containing silicon (Si), and the silicon may be disposed on the surface and inside the pores of the porous carbon support.
  • the porous carbon support containing silicon (Si) means that silicon is formed on the surface of an activated carbon porous carbon support, and the surface of the porous carbon support includes not only the surface exposed to the outside but also the surface located inside.
  • the porous carbon support is a porous material having pores on the outer surface and/or the inner surface, and for example, when coating the surface of the porous carbon support using silicon, the silicon penetrates and coats not only the outer surface of the porous carbon support but also the inner surface of the porous carbon support through the pores, thereby partially or completely blocking the pores of the porous carbon support, and may be coated with a certain thickness on the outer surface of the porous carbon support.
  • the electrode active material is a porous carbon support containing silicon (Si)
  • the coating layer is formed on the surface of the porous carbon support containing silicon (Si)
  • the surface of the porous carbon powder containing silicon (Si) includes not only the surface exposed to the outside but also the surface located inside.
  • the porous carbon support containing silicon (Si) is a porous material having pores on the outer surface and/or the inner surface.
  • the petroleum pitch penetrates and coats not only the outer surface of the porous carbon support containing silicon (Si) but also the inner surface of the porous carbon support containing silicon (Si) through the pores, thereby not only blocking some or all of the pores of the porous carbon support containing silicon (Si), but also coating the outer surface of the porous carbon support containing silicon (Si) with a certain thickness to form a coating layer.
  • the electrode active material may include a nonporous carbon support including at least one of hard carbon and soft carbon.
  • the electrode active material may most preferably be a carbon-silicon composite.
  • a carbon-silicon composite comprises a carbon support including a surface portion and a core portion, and silicon (Si) disposed including a surface of the carbon support.
  • the core of the carbon support may mean an area within a distance of 1/2 the radius of the support from the center of the support, and the surface may mean the remaining area of the support excluding the core.
  • the porous carbon support may be any carbon support commonly used in the art without limitation, but preferably, at least one of a non-porous carbon support and a porous carbon support may be used, more preferably, at least one of graphite, hard carbon, soft carbon, and porous carbon support may be used, and even more preferably, using at least one of hard carbon, soft carbon, and porous carbon support may be more advantageous in achieving the purpose of the present invention.
  • the porous carbon support can be manufactured by a method including (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 a step of 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.
  • Step (1) of the method for manufacturing a porous carbon support according to the present invention may be a step of synthesizing pitch by thermal decomposition and polycondensation of petroleum-based raw materials.
  • the petroleum-based 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 (FCC-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
  • FCC-DO fluid catalytic cracking
  • RFCC-DO residue fluid catalytic cracking decant oil
  • heavy aromatic oil heavy aromatic oil.
  • the petroleum-based raw material may include pyrolysis fuel oil.
  • the petroleum-based raw material may contain an aromatic compound in an amount of 10 to 90 wt%.
  • the petroleum-based raw material may contain an aromatic compound in an amount of 20 to 80 wt%, more preferably 30 to 70 wt%.
  • the aromatic compound may be a compound having 1 to 4 aromatic rings.
  • the aromatic compound may include at least one selected from substituted or unsubstituted benzene, naphthalene, phenanthrene, indene, biphenyl, anthracene, tetralin, and fluorene.
  • the thermal decomposition and polycondensation of the petroleum-based raw material can be carried out at a temperature of 350 to 500°C. In a preferred specific embodiment of the present invention, the thermal decomposition and polycondensation of the petroleum-based raw material can be carried out at a temperature of 400 to 500°C. In a more preferred specific embodiment of the present invention, the thermal decomposition and polycondensation of the petroleum-based raw material can be carried out at a temperature of 430 to 470°C.
  • the temperature of the thermal decomposition and polycondensation of the petroleum-based raw material is 350 to 500°C, a pitch containing a large amount of relatively low molecular weight components can be produced, and in the activation process of step (5) described below, components having relatively small molecular weights are vaporized first, thereby sufficiently forming mesopores in the carbon support.
  • the thermal decomposition and polycondensation temperature of petroleum-based raw materials is less than 350°C, it is difficult to manufacture pitch that is solid at room temperature, and if this temperature exceeds 500°C, the pitch contains a large amount of relatively high molecular weight components, making it difficult to manufacture a carbon support having mesopores.
  • the thermal decomposition and polycondensation of the petroleum raw material may be performed under an atmosphere of an oxidizing gas, an inert gas, or a mixture thereof.
  • the oxidizing gas may be oxygen, ozone, or a combination thereof
  • the inert gas may be nitrogen, helium, neon, argon, or a combination thereof
  • the mixture thereof may be air, but is not particularly limited thereto.
  • thermal decomposition and polycondensation can be performed at relatively high temperatures, thereby producing a pitch with a relatively high softening point.
  • the gas may be supplied at a flow rate of 10 to 800 ml/min during the thermal decomposition and polycondensation of a petroleum-based raw material. In a preferred specific embodiment of the present invention, the gas may be supplied at a flow rate of 100 to 500 ml/min during the thermal decomposition and polycondensation of a petroleum-based raw material.
  • the flow rate of the gas is less than 10 ml/min, the yield of the pitch increases, but the low molecular weight component increases too much, which is disadvantageous for subsequent processes (e.g., stabilization).
  • the flow rate of the gas exceeds 800 ml/min, the yield of the pitch may decrease.
  • the thermal decomposition and polycondensation of the petroleum-based raw material can be carried out for 1 to 10 hours. In a preferred embodiment of the present invention, the thermal decomposition and polycondensation of the petroleum-based raw material can be carried out for 2 to 8 hours. In a more preferred embodiment of the present invention, the thermal decomposition and polycondensation of the petroleum-based raw material can be carried out for 2 to 7 hours.
  • the thermal decomposition and polycondensation time of the petroleum-based raw material is less than 1 hour, it is difficult to produce a pitch having a high softening point, and if the thermal decomposition and polycondensation time of the petroleum-based raw material exceeds 10 hours, an excessive amount of quinoline-insoluble components may be produced.
  • the thermal decomposition and polycondensation of the petroleum-based raw material may be performed under stirring.
  • the stirring conditions for the petroleum-based raw material are not particularly limited, but, for example, a stirrer rotating at 10 to 500 rpm may 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 another specific embodiment of the present invention, the yield of the pitch may be 10 to 40 wt%. In yet another specific embodiment of the present invention, the yield of the pitch may be 20 to 30 wt%.
  • a step of pretreating the petroleum-based raw material may be performed prior to step (1) above.
  • a pitch having a higher softening point can be produced.
  • 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 time for thermal decomposition and polycondensation 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 above 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 liquid pitch obtained in step (1) is solidified, for example, by extrusion and cooling, and then 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 commercially available equipment. For example, this process can be performed using IPCO's Double Belt Cooler & Flaker, but is not particularly limited to this equipment.
  • 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 average particle size of the pitch pellets (pellet-shaped pitch) is within this range, a porous carbon support can be manufactured through stabilization, carbonization, and activation described below without separately pulverizing the pitch pellets (pellet-shaped pitch).
  • the pitch pellets (pellet-shaped pitch) can be further crushed or pulverized and classified.
  • 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.
  • classification can be performed by dry classification, wet classification, or classification using a sieve. Through crushing or pulverization and classification, a powdered pitch having a diameter 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.
  • step (3) may be a step of stabilizing the structure of the pitch by first oxidizing the pellet-shaped pitch or powder-shaped pitch.
  • the stabilization of the pitch may be performed at a temperature of 100 to 500°C, preferably 150 to 350°C.
  • the carbon structure within the pellet-shaped pitch or powder-shaped pitch changes from thermoplastic to thermosetting, so that the structure can be stably maintained during the subsequent carbonization process.
  • the heating rate may be 2 to 10°C/min. If the heating rate is too slow, productivity may be poor, and if the heating rate is excessively fast, uniform stabilization treatment may be difficult.
  • the stabilization may be performed at a pressure of 0.1 to 10 bar, preferably 0.5 to 5 bar.
  • the structure of the pellet-shaped pitch or the carbon inside the powder-shaped pitch can be sufficiently stabilized.
  • the stabilization can be performed under conditions of a flow rate of an oxidizing gas, preferably air or oxygen, of 0.1 to 500 ml/min, preferably 1 to 300 ml/min.
  • an oxidizing gas preferably air or oxygen
  • the structure of the carbon inside the pellet-shaped pitch or the powder-shaped pitch can be sufficiently stabilized.
  • the stabilization may be performed for 1 to 10 hours, preferably 2 to 8 hours. If the stabilization is performed for this period of time, the structure of the carbon within the pellet-shaped pitch or the powder-shaped pitch can be sufficiently stabilized.
  • the stabilized pitch can be carbonized to obtain a carbonized body.
  • other functional groups contained 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 of the pitch may be performed under a nitrogen or argon atmosphere, but is not particularly limited thereto.
  • the carbonization may be performed at a temperature of 700°C to 1,000°C, preferably 800°C to 1,000°C. If the temperature during the carbonization is lower than this range, carbonization may not be sufficiently performed, and if the temperature during the carbonization is higher than this range, the carbonization yield may decrease.
  • the carbonization may be performed under conditions of a flow rate 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.
  • the carbonization may be performed for 0.5 to 5 hours, preferably 1 to 3 hours. If the carbonization is performed for this period of time, the stabilized pitch can be sufficiently carbonized.
  • a porous carbon support can be obtained by activating the carbonized body (carbonized pitch).
  • carbonized body carbonized pitch
  • pores are formed in the pitch, thereby obtaining a porous carbon support.
  • the activation of the carbonized body may be performed under an oxidizing gas atmosphere.
  • the activation of the carbonized body may 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 700°C to 1,000°C or 800°C to 1,000°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 conditions of a flow rate of an oxidizing gas, preferably water vapor, of 0.1 to 100 ml/min, preferably 0.1 to 50 ml/min.
  • an oxidizing gas preferably water vapor
  • a porous carbon support in which micropores and mesopores are sufficiently formed can be obtained.
  • the activation of the carbonized body may 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 steps (3) to (5) above can each be performed in a heating furnace using microwaves.
  • the stabilization, carbonization, and activation of steps (3) to (5) above 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 stabilization, carbonization, and activation of steps (3) to (5) above can be performed continuously in a single device.
  • the stabilization, carbonization, and activation of steps (3) to (5) above can be performed continuously in a single rotary kiln, but this device is not particularly limited. Since the stabilization, carbonization, and activation are performed continuously in a single device, process optimization can be easily achieved.
  • the porous carbon support (or porous carbon support powder) obtained in step (5) may be further pulverized or ground and classified.
  • the porous carbon support powder can be further finely divided, and through classification, the particle size distribution of the porous carbon support can be made uniform.
  • classification may be dry classification, wet classification, or classification using a sieve.
  • a powdered porous carbon support having a diameter of 1 to 20 ⁇ m can be obtained.
  • the porous carbon support manufactured by performing the above steps (1) to (5) includes mesopores having a diameter of 2 nm to 50 nm, and the ratio of the volume of the mesopores of the surface layer to the volume of the entire mesopores may be 0.5 or more, preferably 0.5 to 0.76.
  • the ratio of the mesopores of the surface layer to the total mesopores of the porous carbon support is 0.5 or more, the mesopores formed in the surface layer may act as passages through which pores may be formed deep into the porous carbon support, so that silicon may be deposited into the interior of the support.
  • volume of the total mesopores of the porous carbon support may refer to the volume of the total mesopores arranged in the interior of the porous carbon support
  • volume of the mesopores of the surface layer may refer to the volume of the total mesopores arranged in the surface layer of the porous carbon support
  • volume of the mesopores of the surface layer may mean the volume of the area corresponding to the surface layer with respect to the entire mesopores arranged in the porous carbon support.
  • the charge/discharge capacity may decrease and the cycle characteristics may deteriorate.
  • the porous carbon support of the carbon-silicon composite according to the present invention may have a ratio of the volume of mesopores to the total pore volume of 0.1 or more.
  • the pores of the porous carbon support can be classified into micropores with a diameter of less than 2 nm, mesopores with a diameter of 2 nm to 50 nm, and macropores with a diameter of more than 50 nm, depending on their size.
  • Such porous supports have been studied in the direction of increasing the ratio of micropores to increase the specific surface area or increasing the ratio of macropores to increase the amount of material supported inside the pores.
  • silicon can be sufficiently deposited deep within the pores during deposition.
  • the carbon-silicon composite particles according to the present invention can deposit a sufficient amount of silicon within the pores of the porous support by including mesopores within a predetermined range.
  • porous carbon support may have a higher porosity in the surface layer than in the deep layer, and thus may be more advantageous in achieving the purpose of the present invention.
  • the ratio of the volume of the mesopores to the volume of the entire pores of the porous carbon support may be, but is not limited to, 0.10 or more, 0.12 or more, 0.14 or more, or 0.15 or more.
  • the upper limit of the ratio of the volume of the mesopores to the volume of the entire pores of the porous carbon support is not particularly limited, but may be, for example, 0.7 or less.
  • the tap density of the porous carbon support may be 0.7 g/ml or less.
  • the tap density of the porous carbon support may be a value measured using PT-TD200 (Pharma Test). Specifically, 40 ml of the porous carbon support is loaded into a cylinder, tapped 1,000 times, and the primary volume is observed. After the observation, the process of performing another 1,000 taps and observing the volume is repeated three times until there is no difference from the previous volume, and then the tap density can be calculated using the final volume.
  • the tap density of the porous carbon support may be 0.70 g/ml or less, 0.65 g/ml or less, or 0.60 g/ml or less, and may be 0.05 g/ml or more, 0.10 g/ml or more, 0.15 g/ml or more, 0.20 g/ml or more, or 0.22 g/ml or more, but is not limited thereto. If the tap density of the porous carbon support is too low, process control may be difficult during silane gas deposition, resulting in a decrease in yield. In addition, if the tap density of the porous carbon support is too high, uniform coating may be difficult during silane gas deposition.
  • the BET (Brunauer-Emmett-Teller) specific surface area of the porous carbon support according to the present invention may be in the range of 200 m 2 /g to 3,000 m 2 /g.
  • the BET specific surface area of the porous carbon support may be a value measured using ASAP 2420 (Micromeritics instrument (USA)). Specifically, analysis was performed after vacuum drying at 300°C for 5 hours, and the N2/77K Isotherm adsorption results according to ISO9277 can be calculated using the BET equation and the BJH equation.
  • the BET specific surface area of the porous carbon support may be 200 m2/g or more, 400 m2/g or more, or 500 m2/g or more, and may be 3,000 m2/g or less, 2,800 m2/g or less, 2,600 m2/g or less, 2,000 m2/g or less, or 1,900 m2/g or less, but is not limited thereto. If the BET specific surface area of the porous carbon support is excessively low, the proportion of macropores may increase, which may lower the mechanical strength of the negative electrode material and may result in a lack of effective pores. In addition, if the BET specific surface area of the porous carbon support is too high, the proportion of micropores may increase, and silicon may not be sufficiently deposited deep into the porous carbon support.
  • the diameter of the porous carbon support may be 20 ⁇ m or less.
  • the diameter may refer to the D 50 diameter and may be a value measured using MICROTRAC S3500 equipment. Specifically, it may refer to an average value obtained by dispersing the porous carbon support in ethanol and then performing particle size analysis three times.
  • the diameter of the porous carbon support may be 20 ⁇ m or less, 18 ⁇ m or less, 16 ⁇ m or less, 14 ⁇ m or less, 12 ⁇ m or less, or 10 ⁇ m or less, and may be 1 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, or 4.5 ⁇ m or more, but is not limited thereto.
  • the diameter of the porous carbon support is too small, when performing coating, silicon may be quickly filled inside and then additional coating may be performed on the surface, so that the surface coating layer may be formed thickly. In this case, deterioration may be accelerated during charge and discharge, and agglomeration of materials with small particle sizes may occur during electrode manufacturing, and deterioration of the agglomerated portion may be significant.
  • the diameter of the porous carbon support is too large, it may be difficult for silane gas to diffuse into the interior of the porous carbon support, making it difficult to form a uniform silicon coating layer inside the support.
  • the diameter of the porous carbon support is too large, it may be difficult to uniformly coat the slurry on the current collector during electrode manufacturing, which may result in a decrease in capacity uniformity.
  • the porous carbon support of the carbon-silicon composite according to the present invention may include macropores having a diameter exceeding 50 nm.
  • the ratio of the volume of the macropores to the total pore volume of the porous carbon support may be 0.4 or less.
  • the ratio of the volume of the macropores to the total pore volume of the porous carbon support may be 0.40 or less, 0.35 or less, 0.30 or less, 0.25 or less, 0.20 or less, or 0.15 or less, but is not limited thereto.
  • the lower limit of the ratio of the volume of the macropores to the total pore volume of the porous carbon support is not particularly limited, but may be, for example, 0 or more or greater than 0.
  • the ratio of the macropores of the porous carbon support of the carbon-silicon composite is too high, the mechanical strength of the negative electrode material manufactured from the carbon-silicon composite may be reduced.
  • local agglomeration of silicon occurs inside the negative electrode material, which can cause stress due to volume expansion during repeated charge and discharge processes, thereby causing damage to the negative electrode material.
  • the hard carbon when the carbon support is hard carbon, the hard carbon can be manufactured by a method including the steps of (1') synthesizing pitch by thermal decomposition and condensation polymerization of petroleum-based raw materials, (2') solidifying and pelletizing the pitch to obtain pellet-like pitch, or solidifying, pelletizing, and pulverizing the pitch to obtain powder-like pitch, (3') stabilizing the pellet-like pitch or powder-like pitch, and (4') carbonizing the stabilized pitch to obtain hard carbon.
  • the pitch for manufacturing the hard carbon may be at least one of an isotropic pitch and an anisotropic pitch, and it is more advantageous to achieve the purpose of the present invention to be an isotropic pitch.
  • the soft carbon when the carbon support is soft carbon, the soft carbon can be manufactured by a method including the steps of (1") synthesizing pitch by thermal decomposition and condensation polymerization of petroleum-based raw materials, (2") solidifying and pelletizing the pitch to obtain pellet-like pitch, or solidifying, pelletizing, and pulverizing the pitch to obtain powder-like pitch, (3") stabilizing the pellet-like pitch or powder-like pitch, and (4") carbonizing the stabilized pitch to obtain soft carbon.
  • step (3") and the step (4") described below may be performed as a series of steps in a rotary kiln, as in the above-described steps (3) and (4), or may be performed as a series of steps by placing the material in a crucible and placing it in an oven.
  • step (4" is a step of carbonizing the stabilized pitch to obtain soft carbon, and through carbonization of the stabilized pitch, other functional groups included in the pitch are removed, and soft carbon composed of substantially pure carbon can be obtained.
  • the carbonization in step (4") may be performed under an inert gas atmosphere.
  • the carbonization in step (4") may be performed under a nitrogen or argon atmosphere, but is not particularly limited thereto.
  • the carbonization in step (4") may be performed at a temperature of 1,000°C to 2,700°C, preferably 1,200°C to 2,200°C. If the temperature during the carbonization in step (4") is lower than this range, the crystal structure of carbon may not develop sufficiently, and if the temperature during the carbonization is higher than this range, the carbonization yield may decrease.
  • the carbonization in step (4") can be performed under a flow rate condition of an inert gas, preferably argon, of 0.1 to 30 ml/min, preferably 0.1 to 10 ml/min.
  • an inert gas preferably argon
  • the stabilized pitch can be sufficiently carbonized.
  • the carbonization in step (4") can be performed for 0.5 to 5 hours, preferably 1 to 3 hours.
  • the stabilized pitch can be sufficiently carbonized.
  • the pitch for manufacturing the soft carbon may be at least one of an isotropic pitch and an anisotropic pitch, and preferably, an anisotropic pitch may be more advantageous in achieving the purpose of the present invention.
  • Pitch which may be included in the first coating layer and/or the second coating layer, is a solid organic material at room temperature or a residue resulting from the thermal decomposition of tar distillation, and is composed of a complex mixture of numerous highly aromatic hydrocarbons and heterocyclic compounds. Pitch is not a substance with a constant melting point, but rather has a wide softening range, with a softening temperature ranging from approximately 320 K to 570 K, depending on the molecular weight and component composition.
  • the pitch of the present invention may include at least one selected from petroleum pitch, coal tar pitch, and mesogenic pitch, and preferably may include petroleum pitch.
  • the secondary battery of the present invention may be a lead (Pd) battery, a nickel-cadmium (NiCd) battery, a nickel-metal (Ni-metal) hydrogen battery, a lithium ion (Li-ion) battery, a solid-state battery, a soft carbon battery, a hard carbon battery, or a lithium ion polymer (Li-ion) battery, and preferably a lithium ion (Li-ion) battery.
  • a lead (Pd) battery a nickel-cadmium (NiCd) battery, a nickel-metal (Ni-metal) hydrogen battery, a lithium ion (Li-ion) battery, a solid-state battery, a soft carbon battery, a hard carbon battery, or a lithium ion polymer (Li-ion) battery, and preferably a lithium ion (Li-ion) battery.
  • the electrode active material of the present invention may be a negative electrode active material, and the negative electrode active material may include silicon (Si).
  • the first coating layer can be formed by coating petroleum pitch on the surface of an electrode active material including silicon and then carbonizing it.
  • the carbonized petroleum pitch may be carbonized at a temperature of 500 to 900°C, preferably 600 to 800°C, and even more preferably 650 to 750°C for 60 to 180 minutes, and preferably 90 to 150 minutes.
  • the carbonization temperature is less than 500°C, there may be a problem of incomplete carbonization, and if it exceeds 900°C, there may be a problem of excessive reaction with silicon.
  • the carbonization time is less than 60 minutes, there may be a problem of incomplete carbonization, and if it exceeds 180 minutes, there may be a problem of excessive reaction with silicon.
  • the first coating layer may have a thickness of 10 to 400 nm, preferably 20 to 300 nm, more preferably 30 to 200 nm, and even more preferably 30 to 150 nm. If the thickness is less than 10 nm, the effect of suppressing the increase in expansion rate may be insignificant, and if it exceeds 400 nm, it is advantageous in terms of low expansion rate and suppression of side reaction layer formation, but the effect of increasing the electrical efficiency of the secondary battery may be reduced.
  • the second coating layer may be formed by coating petroleum pitch on the surface of the electrode active material including silicon coated with the first coating layer and then carbonizing it, or may be formed on the surface of the electrode active material including silicon coated with the first coating layer using a CVD (Chemical Vapor Deposition) method.
  • CVD Chemical Vapor Deposition
  • the second coating layer may have a thickness of 10 to 400 nm, preferably 20 to 300 nm, more preferably 20 to 200 nm, and even more preferably 20 to 150 nm. If the thickness is less than 10 nm, the effect of suppressing the increase in expansion rate may be insignificant, and if it exceeds 400 nm, it is advantageous in terms of low expansion rate and suppression of side reaction layer formation, but the effect of increasing the electrical efficiency of the secondary battery may be reduced.
  • the secondary battery electrode material of the present invention may be a secondary battery negative electrode material.
  • another secondary battery electrode material of the present invention includes an electrode active material including silicon (Si) and a coating layer coated on the surface of the electrode active material, and the coating layer includes carbonized petroleum pitch and may have a thickness of 10 to 95 nm.
  • another secondary battery electrode material of the present invention has a single coating layer and may have a thinner thickness through the CIP (Cold Isostatic Pressing) method.
  • the method for manufacturing a secondary battery electrode material of the present invention includes steps 1 to 4.
  • a first coating layer can be formed on the surface of the electrode active material by coating the surface of the electrode active material with petroleum pitch.
  • the electrode active material and/or the petroleum pitch are each as described above.
  • the first stage coating can be performed by dry coating using the mechano-fusion method.
  • dry coating can be performed at a speed of 500 to 5,000 rpm, preferably 900 to 4,500 rpm, for 5 to 30 minutes, preferably 10 to 20 minutes. If the speed is less than 500 rpm, there may be a problem of coating detachment, and if it exceeds 5,000 rpm, there may be a problem of particle damage. In addition, if the time is less than 10 minutes, there may be a problem of incomplete coating, and if it exceeds 30 minutes, there may be a problem of particle damage.
  • the second step of the method for manufacturing a secondary battery electrode material of the present invention can carbonize an electrode active material having a first coating layer formed on the surface.
  • carbonization can be performed at a temperature of 500 to 900°C, preferably 600 to 800°C, more preferably 650 to 750°C, for 60 to 180 minutes, preferably 90 to 150 minutes.
  • the carbonized first coating layer may have a thickness of 10 to 400 nm, preferably 30 to 300 nm, more preferably 50 to 200 nm, and even more preferably 80 to 150 nm.
  • a second coating layer can be formed on the surface of the carbonized first coating layer by coating petroleum pitch on the surface of the carbonized first coating layer.
  • the petroleum pitch is as described above.
  • the third-stage coating can be performed by dry coating using the mechano-fusion method.
  • dry coating can be performed at a speed of 500 to 5,000 rpm, preferably 900 to 4,500 rpm, for 5 to 30 minutes, preferably 10 to 20 minutes. If the speed is less than 500 rpm, there may be a problem of coating detachment, and if it exceeds 5,000 rpm, there may be a problem of particle damage. In addition, if the time is less than 5 minutes, there may be a problem of incomplete coating, and if it exceeds 30 minutes, there may be a problem of particle damage.
  • a secondary battery negative electrode material can be manufactured by carbonizing a negative electrode active material on the surface of which a first coating layer and a second coating layer are sequentially formed.
  • carbonization can be performed at a temperature of 500 to 900°C, preferably 600 to 800°C, more preferably 650 to 750°C, for 60 to 180 minutes, preferably 90 to 150 minutes.
  • the carbonized second coating layer may have a thickness of 10 to 400 nm, preferably 30 to 300 nm, more preferably 50 to 200 nm, and even more preferably 80 to 150 nm.
  • first coating layer and the second coating layer manufactured by the method for manufacturing a secondary battery electrode material of the present invention may have a thickness ratio of 1:0.8 to 1.2, preferably a thickness ratio of 1:0.9 to 1.1, and by satisfying such a thickness ratio, a secondary battery electrode material having the desired performance can be manufactured.
  • Another method for manufacturing a secondary battery electrode material of the present invention includes steps 1 to 3.
  • a first coating layer can be formed on the surface of the electrode active material by coating the surface of the electrode active material with petroleum pitch.
  • the electrode active material and/or the petroleum pitch are as described above, respectively.
  • the first stage coating can be performed by dry coating using the mechano-fusion method.
  • dry coating can be performed at a speed of 500 to 5,000 rpm, preferably 900 to 4,500 rpm, for 5 to 30 minutes, preferably 10 to 20 minutes. If the speed is less than 500 rpm, there may be a problem of coating detachment, and if it exceeds 5,000 rpm, there may be a problem of particle damage. In addition, if the time is less than 5 minutes, there may be a problem of incomplete coating, and if it exceeds 30 minutes, there may be a problem of particle damage.
  • the second step of another method for manufacturing a secondary battery electrode material of the present invention can carbonize an electrode active material having a first coating layer formed on the surface.
  • carbonization can be performed at a temperature of 500 to 900°C, preferably 600 to 800°C, more preferably 650 to 750°C, for 60 to 180 minutes, preferably 90 to 150 minutes.
  • the carbonized first coating layer may have a thickness of 10 to 400 nm, preferably 30 to 300 nm, more preferably 50 to 200 nm, and even more preferably 80 to 150 nm.
  • a second coating layer made of carbon can be formed on the surface of the carbonized first coating layer, thereby manufacturing a secondary battery negative electrode material.
  • a second coating layer made of carbon can be formed on the surface of the carbonized first coating layer using a CVD (Chemical Vapor Deposition) method, and as a precursor for performing the CVD (Chemical Vapor Deposition) method, any precursor used in the art to enable carbon to be coated and/or deposited during coating and/or deposition can be used, and preferably, ethylene can be used.
  • the CVD method can be performed at a reaction temperature of 375 to 575°C, preferably 400 to 550°C, more preferably 425 to 525°C, and even more preferably 450 to 500°C, an ethylene flow rate of 800 to 1200 sccm, preferably 900 to 1100 sccm, and even more preferably 950 to 1050 sccm, and a reaction time of 10 to 60 minutes, preferably 20 to 50 minutes, and even more preferably 20 to 40 minutes, and by satisfying these conditions, a secondary battery electrode material having the desired performance can be manufactured.
  • the formed second coating layer may have a thickness of 10 to 400 nm, preferably 10 to 100 nm, more preferably 10 to 50 nm, and even more preferably 15 to 30 nm.
  • the first coating layer and the second coating layer manufactured by another method for manufacturing a secondary battery electrode material of the present invention may have a thickness ratio of 1:0.05 to 0.5, preferably a thickness ratio of 1:0.1 to 0.3, and more preferably a thickness ratio of 1:0.15 to 0.25, and by satisfying such a thickness ratio, a secondary battery electrode material having the desired performance can be manufactured.
  • another method for manufacturing a secondary battery electrode material of the present invention includes a first step and a second step.
  • the first step of another method for manufacturing a secondary battery electrode material of the present invention can form a coating layer on the surface of the electrode active material by coating the surface of the electrode active material with petroleum pitch.
  • the electrode active material and/or the petroleum pitch are as described above, respectively.
  • the first stage coating can be performed by dry coating using the mechano-fusion method.
  • dry coating can be performed at a speed of 500 to 5,000 rpm, preferably 900 to 4,500 rpm, for 5 to 30 minutes, preferably 10 to 20 minutes. If the speed is less than 500 rpm, there may be a problem of coating detachment, and if it exceeds 5,000 rpm, there may be a problem of particle damage. In addition, if the time is less than 5 minutes, there may be a problem of incomplete coating, and if it exceeds 30 minutes, there may be a problem of particle damage.
  • a secondary battery negative electrode material can be manufactured by carbonizing an electrode active material having a coating layer formed on its surface and then performing a CIP (Cold Isostatic Pressing) method. At this time, the carbonization can be performed at a temperature of 500 to 900°C, preferably 600 to 800°C, and more preferably 650 to 750°C for 60 to 240 minutes, and preferably 150 to 210 minutes.
  • CIP Cold Isostatic Pressing
  • the CIP method can use water as a compressed fluid, and can be performed under conditions of a temperature of 15 to 30°C, preferably 20 to 28°C, more preferably 23 to 27°C, and a pressure of 15,000 to 25,000 psi, preferably 17,000 to 23,000 psi, more preferably 19,000 to 21,000 psi, and by satisfying these conditions, a secondary battery electrode material having the desired performance can be manufactured.
  • the coating layer manufactured by another method for manufacturing a secondary battery electrode material of the present invention can have a thickness of 10 to 95 nm, preferably a thickness of 20 to 70 nm, more preferably a thickness of 40 to 60 nm, which can have an advantage of having a thinner thickness and better performance than when the coating layer is formed using the mechano-fusion method.
  • Another method for manufacturing a secondary battery electrode material of the present invention includes steps 1 to 4.
  • the first stage coating can be performed by dry coating using the mechano-fusion method.
  • dry coating can be performed at a speed of 500 to 5,000 rpm, preferably 900 to 4,500 rpm, for 5 to 30 minutes, preferably 10 to 20 minutes. If the speed is less than 500 rpm, there may be a problem of coating detachment, and if it exceeds 5,000 rpm, there may be a problem of particle damage. In addition, if the time is less than 5 minutes, there may be a problem of incomplete coating, and if it exceeds 30 minutes, there may be a problem of particle damage.
  • the CIP method can use water as a compressed fluid, and can be performed at a temperature of 15 to 30°C, preferably 20 to 28°C, more preferably 23 to 27°C, and a pressure of 15,000 to 25,000 psi, preferably 17,000 to 23,000 psi, more preferably 19,000 to 21,000 psi, and by satisfying these conditions, a secondary battery electrode material having the desired performance can be manufactured.
  • the second step of another method for manufacturing a secondary battery electrode material of the present invention can carbonize an electrode active material having a first coating layer formed on the surface.
  • carbonization can be performed at a temperature of 500 to 900°C, preferably 600 to 800°C, more preferably 650 to 750°C, for 60 to 180 minutes, preferably 90 to 150 minutes.
  • the carbonized first coating layer may have a thickness of 10 to 400 nm, preferably 20 to 300 nm, more preferably 30 to 100 nm, and even more preferably 40 to 70 nm.
  • a second coating layer can be formed on the surface of the carbonized first coating layer by coating petroleum pitch on the surface of the carbonized first coating layer.
  • the petroleum pitch is as described above.
  • the third-stage coating can be performed by dry coating using the mechano-fusion method.
  • dry coating can be performed at a speed of 500 to 5,000 rpm, preferably 900 to 4,500 rpm, for 5 to 30 minutes, preferably 10 to 20 minutes. If the speed is less than 500 rpm, there may be a problem of coating detachment, and if it exceeds 5,000 rpm, there may be a problem of particle damage. In addition, if the time is less than 5 minutes, there may be a problem of incomplete coating, and if it exceeds 30 minutes, there may be a problem of particle damage.
  • a secondary battery negative electrode material can be manufactured by carbonizing a negative electrode active material on which a first coating layer and a second coating layer are sequentially formed on the surface.
  • carbonization can be performed at a temperature of 500 to 900°C, preferably 600 to 800°C, more preferably 650 to 750°C, for 60 to 180 minutes, preferably 90 to 150 minutes.
  • the carbonized second coating layer may have a thickness of 10 to 400 nm, preferably 30 to 300 nm, more preferably 50 to 200 nm, and even more preferably 80 to 150 nm.
  • first coating layer and the second coating layer manufactured by another method for manufacturing a secondary battery electrode material of the present invention may have a thickness ratio of 1:1 to 3, preferably a thickness ratio of 1:1.5 to 2.5, and more preferably a thickness ratio of 1:1.8 to 2.2, and by satisfying such thickness ratios, a secondary battery electrode material having the desired performance can be manufactured.
  • the negative active material having a first coating layer formed on the surface was carbonized at a temperature of 700°C for 120 minutes.
  • a secondary battery negative electrode material was manufactured by forming a second coating layer made of carbon on the surface of a carbonized first coating layer using a CVD (Chemical Vapor Deposition) method using ethylene as a precursor. Meanwhile, the CVD method was performed at a reaction temperature of 475°C, an ethylene flow rate of 1000 sccm, and a reaction time of 30 minutes, and the first coating layer of the manufactured secondary battery negative electrode material was formed to a thickness of 100 nm, and the second coating layer was formed to a thickness of 20 nm.
  • CVD Chemical Vapor Deposition
  • the negative active material having a first coating layer formed on the surface was carbonized at a temperature of 700°C for 120 minutes.
  • a negative electrode active material having a first coating layer and a second coating layer sequentially formed on the surface was carbonized at a temperature of 700°C for 120 minutes to manufacture a secondary battery negative electrode material. Meanwhile, the first coating layer of the manufactured secondary battery negative electrode material was formed to a thickness of 100 nm, and the second coating layer was formed to a thickness of 100 nm.
  • the negative electrode active material having a coating layer formed on the surface was carbonized at a temperature of 700°C for 180 minutes, and then the CIP (Cold Isostatic Pressing) method was performed to manufacture a secondary battery negative electrode material. Meanwhile, the CIP method was performed using water as a compressed fluid, at a temperature of 25°C, and a pressure of 20,000 psi, and the coating layer of the manufactured secondary battery negative electrode material was formed with a thickness of 50 nm.
  • the negative active material having a first coating layer formed on the surface was carbonized at a temperature of 700°C for 120 minutes.
  • a negative electrode active material having a first coating layer and a second coating layer sequentially formed on the surface was carbonized at a temperature of 700°C for 120 minutes to manufacture a secondary battery negative electrode material. Meanwhile, the first coating layer of the manufactured secondary battery negative electrode material was formed to a thickness of 50 nm, and the second coating layer was formed to a thickness of 100 nm.
  • a secondary battery negative electrode material was manufactured by carbonizing a negative electrode active material having a coating layer formed on its surface at a temperature of 700°C for 120 minutes. Meanwhile, the coating layer of the manufactured secondary battery negative electrode material was formed to a thickness of 100 nm.
  • the secondary battery negative electrode material, conductive material, and binder manufactured in Example 1 were mixed to manufacture a negative electrode material slurry.
  • the negative electrode material slurry was mixed with 80 wt% of the secondary battery negative electrode material manufactured in Example 1, 10 wt% of the conductive material, and 10 wt% of the binder based on 100 wt% of the total.
  • Super-P which is a conductive carbon black, was used as the conductive material, and styrene butadiene rubber (SBR) and sodium carboxymethyl cellulose (CMC) were mixed in a weight ratio of 5:5 as the binder.
  • Lithium foil was prepared, and the prepared lithium foil and the negative electrode plate were used as counter electrodes, and a porous polyethylene film was used as a separator, and a secondary battery half coin cell was manufactured by punching to have a diameter of 20 mm and a thickness of 3.2 mm.
  • the manufactured secondary battery half coin cell was filled with an electrolyte, and a 1.3 M LiPF 6 solution containing 10 wt% fluoro-ethylene carbonate (FEC), 0.2 wt% lithium tetrafluoroborate (LiBF 4 ), 0.5 wt% vinylene carbonate (VC), and 1 wt% propane sulton (PS) additive was dissolved in a mixed solution, and the mixed solution was a mixture of 30 vol% ethylene carbonate (EC), 50 vol% ethyl methyl carbonate (EMC), and 20 vol% dimethyl carbonate (DMC) with respect to the total 100 vol%.
  • FEC fluoro-ethylene carbonate
  • LiBF 4 lithium tetrafluoroborate
  • VC 0.5 wt% vinylene carbonate
  • PS propane sulton
  • a secondary battery half-coil cell was manufactured using the same method as Manufacturing Example 1. However, unlike Manufacturing Example 1, the secondary battery negative electrode material manufactured in Example 2 was used instead of the secondary battery negative electrode material manufactured in Example 1, and a secondary battery half-coil cell was finally manufactured.
  • a secondary battery half-coil cell was manufactured using the same method as Manufacturing Example 1. However, unlike Manufacturing Example 1, the secondary battery negative electrode material manufactured in Example 3 was used instead of the secondary battery negative electrode material manufactured in Example 1, and a secondary battery half-coil cell was finally manufactured.
  • a secondary battery half-coil cell was manufactured using the same method as Manufacturing Example 1. However, unlike Manufacturing Example 1, the secondary battery negative electrode material manufactured in Example 4 was used instead of the secondary battery negative electrode material manufactured in Example 1, and a secondary battery half-coil cell was finally manufactured.
  • a secondary battery half-coil cell was manufactured using the same method as Manufacturing Example 1. However, unlike Manufacturing Example 1, the secondary battery negative electrode material manufactured in Comparative Example 1 was used instead of the secondary battery negative electrode material manufactured in Example 1, and a secondary battery half-coil cell was finally manufactured.
  • a secondary battery half-coil cell was manufactured using the same method as Manufacturing Example 1. However, unlike Manufacturing Example 1, instead of the secondary battery negative electrode material manufactured in Example 1, a spherical activated carbon powder with silicon (Si) coated on the surface was used to manufacture a secondary battery half-coil cell.
  • Si silicon
  • A represents the volume expansion rate of each of the secondary battery coin cells manufactured in Manufacturing Examples 1 to 4 and Comparative Manufacturing Example 1 after 50 cycles of charging and discharging
  • B represents the volume expansion rate of the secondary battery half coin cell manufactured in Reference Example 1 after 50 cycles of charging and discharging.
  • the secondary battery coin cells manufactured in Manufacturing Examples 1 to 4 not only had superior electric capacity and initial charge/discharge efficiency compared to the secondary battery coin cells manufactured in Comparative Manufacturing Example 1, but also had superior volume expansion reduction rate after 50 charge/discharge cycles and retention rate compared to the initial electric capacity after 50 charge/discharge cycles.
  • the secondary battery coin cell manufactured in Manufacturing Example 1 not only had the best electric capacity and initial charge/discharge efficiency, but also had the best volume expansion reduction rate after 50 charge/discharge cycles and the best retention rate compared to the initial electric capacity after 50 charge/discharge cycles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un matériau d'électrode de batterie secondaire comprenant du brai de pétrole et son procédé de fabrication. Le matériau d'électrode de batterie secondaire est fabriqué par la formation d'une couche de revêtement comprenant du brai de pétrole sur la surface d'un matériau actif d'électrode, puis par l'introduction d'une couche de revêtement supplémentaire ou par la réalisation d'un processus supplémentaire, ce qui permet d'améliorer significativement les performances d'une batterie secondaire sur laquelle le matériau d'électrode de batterie secondaire est appliqué.
PCT/KR2025/008672 2024-06-24 2025-06-23 Matériau d'électrode de batterie secondaire et son procédé de fabrication Pending WO2026005404A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20240082015 2024-06-24
KR10-2024-0082015 2024-06-24
KR10-2025-0081947 2025-06-20
KR1020250081947A KR20250180159A (ko) 2024-06-24 2025-06-20 이차전지 전극재 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2026005404A1 true WO2026005404A1 (fr) 2026-01-02

Family

ID=98222288

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2025/008672 Pending WO2026005404A1 (fr) 2024-06-24 2025-06-23 Matériau d'électrode de batterie secondaire et son procédé de fabrication

Country Status (1)

Country Link
WO (1) WO2026005404A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140101640A (ko) * 2013-02-12 2014-08-20 (주)포스코켐텍 리튬 이차 전지용 음극 활물질 및 이의 제조 방법
KR20180052683A (ko) * 2015-12-31 2018-05-18 썬쩐 비티아르 뉴 에너지 머티어리얼스 아이엔씨이 복합 실리콘 음극 재료, 제조 방법 및 용도
KR20200023241A (ko) * 2018-08-23 2020-03-04 주식회사 엘지화학 음극 활물질, 이를 포함하는 음극, 및 리튬 이차전지
KR20220091672A (ko) * 2020-12-23 2022-07-01 대주전자재료 주식회사 다공성 규소 구조체, 이를 포함하는 다공성 규소-탄소 복합체 및 음극 활물질
KR20230015077A (ko) * 2021-07-22 2023-01-31 충북대학교 산학협력단 건식 스피드 믹서를 이용한 이차전지 음극활물질 복합소재의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140101640A (ko) * 2013-02-12 2014-08-20 (주)포스코켐텍 리튬 이차 전지용 음극 활물질 및 이의 제조 방법
KR20180052683A (ko) * 2015-12-31 2018-05-18 썬쩐 비티아르 뉴 에너지 머티어리얼스 아이엔씨이 복합 실리콘 음극 재료, 제조 방법 및 용도
KR20200023241A (ko) * 2018-08-23 2020-03-04 주식회사 엘지화학 음극 활물질, 이를 포함하는 음극, 및 리튬 이차전지
KR20220091672A (ko) * 2020-12-23 2022-07-01 대주전자재료 주식회사 다공성 규소 구조체, 이를 포함하는 다공성 규소-탄소 복합체 및 음극 활물질
KR20230015077A (ko) * 2021-07-22 2023-01-31 충북대학교 산학협력단 건식 스피드 믹서를 이용한 이차전지 음극활물질 복합소재의 제조 방법

Similar Documents

Publication Publication Date Title
WO2020130443A1 (fr) Méthode de production de matériau actif d'électrode négative pour batterie secondaire au lithium
WO2020256395A2 (fr) Composite d'oxyde composite carbone-silicium pour matériau d'anode de batterie secondaire au lithium, et son procédé de préparation
WO2020111446A1 (fr) Matériau actif d'anode pour batterie secondaire au lithium, son procédé de préparation, et batterie secondaire au lithium le comprenant
WO2021034109A1 (fr) Complexe siliciumㆍoxyde de silicium-carbone, son procédé de préparation et matériau actif d'électrode négative le comprenant pour batterie rechargeable au lithium
WO2019093681A2 (fr) Carbone poreux, et électrode positive et batterie secondaire au lithium le comprenant
WO2017099456A1 (fr) 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
WO2022131695A1 (fr) Matériau d'anode destiné à une batterie secondaire au lithium-ion, son procédé de préparation, et batterie secondaire au lithium-ion le comprenant
WO2015065047A1 (fr) Matériau actif d'électrode négative et procédé pour fabriquer ce dernier
WO2010041907A2 (fr) Matière active négative destinée à une batterie lithium rechargeable, procédé de préparation de ladite matière, et batterie lithium rechargeable contenant ladite matière
WO2022139243A1 (fr) Structure de silicium poreux, composite carbone-silicium poreux comprenant celle-ci, et matériau actif d'électrode négative
WO2018034553A1 (fr) Matériau d'électrode négative comprenant des paillettes de silicium et procédé de préparation de paillettes de silicium
WO2023033370A1 (fr) Matériau actif d'électrode négative, électrode négative comprenant un matériau actif d'électrode négative, batterie secondaire comprenant une électrode négative et procédé de préparation de matériau actif d'électrode négative
WO2023224177A1 (fr) Nouvelle méthode de préparation de graphite sphérique granulé, graphite sphérique granulé ainsi préparé, et batterie secondaire le comprenant en tant que matériau actif d'anode
WO2024136052A1 (fr) Matériau actif négatif pour batterie rechargeable au lithium, procédé de fabrication associé et batterie rechargeable au lithium le comprenant
WO2022270967A1 (fr) Matériau actif d'anode, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2021034097A1 (fr) Batterie secondaire et son procédé de fabrication
WO2023018258A1 (fr) Matériau actif d'électrode négative, électrode négative le comprenant, batterie secondaire comprenant cette électrode et procédé de fabrication du matériau actif d'électrode négative
WO2025143677A1 (fr) Composite carbone-silicium/carbone et son procédé de production
WO2026005404A1 (fr) Matériau d'électrode de batterie secondaire et son procédé de fabrication
WO2024123064A1 (fr) Structure carbonée poreuse dopée à l'azote, hautement graphitée, batterie lithium-soufre la comprenant, et son procédé de fabrication
WO2024128541A1 (fr) Procédé de préparation de matériau actif d'électrode négative, matériau actif d'électrode négative, électrode négative et batterie secondaire
WO2026005423A1 (fr) Composition de revêtement pour revêtement de surface de matériau actif d'électrode de batterie secondaire, et matériau d'électrode de batterie secondaire la comprenant
WO2026005390A1 (fr) Matériau d'électrode de batterie secondaire et son procédé de fabrication
WO2026005426A1 (fr) Composite silicium-carbone à faible expansion, son procédé de fabrication, matériau d'électrode négative le comprenant, et batterie au lithium-ion et batterie entièrement solide le comprenant
WO2026005439A1 (fr) Composite silicium-carbone à faible expansion à conductivité électrique améliorée, son procédé de fabrication, matériau d'électrode négative le comprenant, et batterie au lithium-ion et batterie tout solide le comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25827369

Country of ref document: EP

Kind code of ref document: A1