WO2025143761A1 - Composite carbone/silicium-polymère et son procédé de fabrication - Google Patents

Composite carbone/silicium-polymère et son procédé de fabrication Download PDF

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WO2025143761A1
WO2025143761A1 PCT/KR2024/021052 KR2024021052W WO2025143761A1 WO 2025143761 A1 WO2025143761 A1 WO 2025143761A1 KR 2024021052 W KR2024021052 W KR 2024021052W WO 2025143761 A1 WO2025143761 A1 WO 2025143761A1
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silicon
carbon
polymer composite
polymer
composite
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Korean (ko)
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김도흥
전효진
임경원
임장빈
강병찬
임성갑
강민정
장원태
최건우
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Korea Advanced Institute of Science and Technology KAIST
Hanwha Solutions Corp
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Korea Advanced Institute of Science and Technology KAIST
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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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

  • Secondary batteries such as lithium secondary batteries and all-solid-state batteries containing liquid electrolytes, are most widely used for this purpose because they have high energy density and a small degree of self-discharge when not in use.
  • Secondary batteries are generally composed of a positive electrode, a negative electrode, and an electrolyte (liquid or solid), and carbon-based materials such as graphite are widely used as the negative electrode material of secondary batteries.
  • Japanese Patent No. 4393610 discloses an anode material in which silicon is composited with carbon in a mechanical processing process and the surface of the silicon particles is covered with a carbon layer using a chemical vapor deposition (CVD) method.
  • CVD chemical vapor deposition
  • Patent Document 0001 Japanese Patent Publication No. 4393610
  • the porous carbon support may have a BET specific surface area of 300 to 3,000 m2/g, a tap density of 0.05 to 0.5 g/ml, and an average particle diameter of 1 to 20 ⁇ m.
  • the silicon may be 5 to 80 wt% of the total weight of the carbon/silicon-polymer composite.
  • the polymer thin film may be 1 to 30 wt% of the total weight of the carbon/silicon-polymer composite.
  • the polymer thin film may have a thickness of 1 to 450 nm.
  • the present invention provides a method for producing a carbon/silicon-polymer composite, including (1) a step of forming silicon on the surface and inside the pores of a porous carbon support to produce a carbon-silicon composite, and (2) a step of forming a polymer thin film on the surface of the porous carbon support, inside the pores, and the surface of the silicon of the carbon-silicon composite through an initiator-based chemical vapor deposition (iCVD) to produce a carbon/silicon-polymer composite.
  • iCVD initiator-based chemical vapor deposition
  • the monomer can be supplied at a flow rate of 0.1 sccm to 10 sccm, and the initiator can be supplied at a flow rate of 0.1 sccm to 5 sccm.
  • the initiator can be activated through a predetermined heat treatment, and the heat treatment can be performed at a temperature of 135 to 350°C.
  • step (2-3) can be performed in a vacuum state at a pressure of 50 to 1,000 mTorr for 10 minutes to 6 hours.
  • the present invention provides an anode material comprising the above-described carbon/silicon-polymer composite and a carbon-based anode material.
  • the present invention provides an all-solid-state battery including an SEI (Solid Electrolyte Interphase) film comprising the above-described carbon/silicon-polymer composite.
  • SEI Solid Electrolyte Interphase
  • the present invention provides a lithium ion battery including the above-described negative electrode material.
  • the carbon/silicon-polymer composite according to an embodiment of the present invention has excellent thickness uniformity of the polymer thin film, while the polymer thin film has little effect on electrical conductivity and lithium ion conductivity, so that when used as an anode material, it can act as a stable solid electrolyte interfacial layer while maintaining high specific power and coulombic efficiency, thereby suppressing degradation of battery performance and lifespan.
  • FIG. 1 schematically illustrates a process for forming a polymer thin film on a carbon-silicon composite using an initiator-based chemical vapor deposition (iCVD) method according to one embodiment of the present invention.
  • iCVD initiator-based chemical vapor deposition
  • Figure 2 is a schematic diagram of a carbon/silicon-polymer composite according to one embodiment of the present invention.
  • FIG. 3 shows the results of XPS (X-ray photoelectron spectroscopy) analysis of a carbon-silicon composite (FIG. 3a) according to Comparative Example 1 of the present invention and carbon/silicon-polymer composites (FIGS. 3b to 3e) according to Examples 1 to 4.
  • XPS X-ray photoelectron spectroscopy
  • one component is formed above/below another component or is connected or coupled to each other includes both the formation, connection or coupling between these components directly or indirectly through another component.
  • the silicon (12) above may be crystalline or amorphous, and preferably may be amorphous or a similar phase.
  • the silicon (12) 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. Meanwhile, when the silicon (12) is amorphous or a similar phase, the expansion or contraction during charge and discharge of the secondary battery is small, and the battery performance such as the capacity characteristics can be improved.
  • the silicon (12) may be 5 to 80 wt% of the total weight of the carbon/silicon-polymer composite (10) according to the present invention, and preferably 10 to 50 wt%. If the silicon is less than 5 wt% of the total weight of the carbon/silicon-polymer composite, the electric capacity may be reduced, and if the silicon exceeds 80 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 above silicon (12) 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 value when the x value is less than 0.5, expansion and contraction may increase and life characteristics may deteriorate during charging and discharging of the secondary battery, 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 polymer thin film is selected from the group consisting of 4-vinyl pyridine (4VP), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (PFDMA), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4D4), 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3), hexavinyldisiloxane (HVDS), glycidyl methacrylate (GMA), divinylbenzene (DVB), diethylene glycol divinyl ether, diethylene glycol diacrylate (DEGDA), ethylene glycol dimethacrylate, dimethylaminoeth
  • 4VP 4-vinyl
  • step (2-1) a carbon-silicon composite is supplied into the reactor.
  • the structure of the reactor used in the method for manufacturing a carbon/silicon-polymer composite according to one embodiment of the present invention is not particularly limited as long as it can form a polymer thin film on a carbon-silicon composite using the initiator-based chemical vapor deposition (iCVD) method described below.
  • iCVD initiator-based chemical vapor deposition
  • the reactor (1000) may include a chamber (100), a mounting portion (200), an inlet (300), an outlet (400), and a heating portion (500).
  • the above carbon-silicon composite may be placed on a mounting portion (200) provided at the bottom of a chamber (100) of a reactor (1000).
  • the shape, size, and material of the mounting portion are not particularly limited as long as it can accommodate the carbon-silicon composite.
  • the mounting portion may be a flat plate on which the carbon-silicon composites may be placed while spreading out so as not to overlap each other as much as possible.
  • a silicon substrate (wafer) may be used as a mounting portion that accommodates the carbon-silicon composite, but is not particularly limited thereto.
  • the above mounting portion may be connected to a position-changing means (not shown) capable of changing the position of the carbon-silicon composite.
  • the position-changing means may, for example, vibrate or move the mounting portion, which is a silicon substrate, to change or rotate the position of the carbon-silicon composite placed on the silicon substrate, thereby allowing a polymer film to be evenly formed on the carbon-silicon composite in step (2-3) described below, but is not particularly limited thereto.
  • step (2-2) monomers and initiator are fed into the reactor.
  • the monomer (M) and the initiator (I) can be vaporized and supplied to the chamber (100) through the inlet (300) of the reactor (1000).
  • the above monomer (M) is a volatile substance that can be activated by an initiator (I) to form a polymer.
  • the details of the above monomer are as described in the carbon/silicon-polymer complex section above.
  • the initiator (I) supplied into the chamber (100) of the reactor (1000) in a vaporized state is activated by contacting the heating unit (500) to form free radicals (I * ).
  • the heating unit may be, for example, a plurality of filaments heated by electricity, but is not particularly limited thereto.
  • the temperature of the heating unit is not limited as long as it can decompose and activate the initiator, but is preferably in the range of 135 to 350° C., more preferably in the range of 140 to 340° C., which may be advantageous in terms of preventing changes in the properties of the reactants.
  • the initiator and monomer remaining in the gas phase used in the reaction of the above step (2-3) can be discharged out of the reactor through the outlet (400).
  • the properties of the polymer thin film formed in the above steps (2-3) can be easily controlled by controlling the process variables of iCVD. That is, by controlling the pressure and temperature inside the chamber, reaction time, flow rates of initiator and monomer, heating section, and temperature on the surface and inside the pores of the carbon-silicon composite, the molecular weight, thickness, composition, deposition rate, etc. of the polymer thin film can be easily controlled.
  • the method for manufacturing the carbon/silicon-polymer composite may further include, before step (1), (a) a step of synthesizing pitch by thermal decomposition and condensation polymerization of a petroleum-based raw material, (b) 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, (c) a step of stabilizing the pellet-like pitch or the powder-like pitch, (d) a step of carbonizing the stabilized pitch to obtain a carbonized body, and (e) a step of activating the carbonized body to obtain 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 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 the group consisting of substituted or unsubstituted benzene, naphthalene, phenanthrene, indene, biphenyl, anthracene, tetralin, and fluorene.
  • the solid pitch pellets described below are stabilized, carbonized, and activated without separately pulverizing, a porous carbon support having controlled pore characteristics can be obtained.
  • the thermal decomposition and polycondensation of the petroleum raw material can be performed 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 raw material can be performed 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 raw material can be performed at a temperature of 430 to 470°C.
  • step (e) When the temperature of the thermal decomposition and polycondensation of the petroleum raw material is 350 to 500°C, a pitch containing a large amount of relatively low molecular weight components can be manufactured, and in the activation process of step (e) described below, components having relatively small molecular weights are vaporized first, thereby sufficiently forming mesopores in the carbon support. If the thermal decomposition and polycondensation temperature of the petroleum-based raw material 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 lot 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 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 gas may be supplied at a flow rate of 10 to 800 ml/min during the thermal decomposition and polycondensation of the petroleum 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 the petroleum 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 the subsequent process (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 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 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 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 solid pitch pellets obtained above were pulverized to manufacture pitch particles having an average particle size of 200 ⁇ m, and then placed in a rotary kiln having three zones to sequentially perform stabilization, carbonization, and activation.
  • 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.
  • a pulverizer NETZSCH, air jet mill
  • 15 g of the fine powder of the porous carbon support was placed into a rotary rotary kiln, and silane (SiH 4 ) gas was injected to form a silicon layer on the porous carbon support, thereby producing a carbon-silicon composite.
  • SiH 4 silane
  • step Standard example Silicon layer formation conditions Batch (g) 15 enter Normal pressure Temperature (°C) 475 Time (minutes) 120 Properties of carbon-silicon composites after silicon layer formation Average particle size ( ⁇ m) 8.9 Specific surface area (m2/g) 10.4 Tap density (g/ml) 0.6
  • a carbon/silicon-polymer composite was manufactured in the same manner as in Example 1, but the following changes were made so that a polymer thin film (pGMA) was formed on the surface of the porous carbon support, inside the pores, and on the surface of the silicon of the carbon/silicon-polymer composite, thereby manufacturing a carbon/silicon-polymer composite.
  • the average thickness of the formed polymer thin film was 10 nm.
  • a carbon/silicon-polymer composite was manufactured in the same manner as in Example 1, but the following changes were made so that a polymer thin film (pDVB) was formed on the surface of the porous carbon support, inside the pores, and on the surface of the silicon of the carbon/silicon-polymer composite, thereby manufacturing a carbon/silicon-polymer composite.
  • the average thickness of the formed polymer thin film was 500 nm.
  • the iCVD process reaction time was controlled to 6 hours.
  • a carbon-silicon composite was prepared according to the preparation example.
  • Half coin cells were manufactured using the composites of Examples 1 to 6 and Comparative Example 1, and then electrochemical evaluation was performed.
  • the conditions for manufacturing the half coin cells are shown in Table 3, and the evaluation results are shown in Table 4 and FIG. 5.
  • 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)
  • Examples 1 to 5 showed a reversible capacity of 1500 mAh/g or more, and it was confirmed that the ICE and cycle maintenance rate were excellent.
  • Example 6 it was confirmed that the reversible capacity was lower and the cycle retention rate was also lowered as the average thickness of the polymer thin film was relatively thicker compared to Examples 1 to 5.

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Abstract

La présente invention concerne un composite carbone/silicium-polymère et son procédé de fabrication. Un composite carbone/silicium-polymère selon un mode de réalisation de la présente invention présente une excellente uniformité d'épaisseur d'une couche mince polymère, tandis que la couche mince polymère affecte peu la conductivité électrique et la conductivité lithium-ion. Par conséquent, lorsqu'il est utilisé en tant que matériau d'électrode négative, le composite carbone/silicium-polymère peut servir de couche d'interface d'électrolyte solide stable tout en maintenant une capacité spécifique et un rendement en quantité élevés, et peut ainsi supprimer la dégradation des performances de la batterie et de la durée de vie.
PCT/KR2024/021052 2023-12-29 2024-12-24 Composite carbone/silicium-polymère et son procédé de fabrication Pending WO2025143761A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160033637A (ko) * 2014-09-18 2016-03-28 주식회사 엘지화학 실리콘-탄소나노튜브 복합체, 이의 제조방법, 이를 포함하는 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지
KR20180039925A (ko) * 2016-10-11 2018-04-19 울산과학기술원 리튬 이차 전지용 음극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
KR20190116818A (ko) * 2018-04-05 2019-10-15 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지
KR20230113900A (ko) * 2022-01-24 2023-08-01 한국화학연구원 다공성 벌집 구조를 갖는 실리콘/탄소복합체의 제조 방법 및 이를 이용하여 제조된 실리콘/탄소복합 음극재

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4393610B2 (ja) 1999-01-26 2010-01-06 日本コークス工業株式会社 リチウム二次電池用負極材料、リチウム二次電池、及び同二次電池の充電方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160033637A (ko) * 2014-09-18 2016-03-28 주식회사 엘지화학 실리콘-탄소나노튜브 복합체, 이의 제조방법, 이를 포함하는 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지
KR20180039925A (ko) * 2016-10-11 2018-04-19 울산과학기술원 리튬 이차 전지용 음극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
KR20190116818A (ko) * 2018-04-05 2019-10-15 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지
KR20230113900A (ko) * 2022-01-24 2023-08-01 한국화학연구원 다공성 벌집 구조를 갖는 실리콘/탄소복합체의 제조 방법 및 이를 이용하여 제조된 실리콘/탄소복합 음극재

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CARTER RACHEL, JOSEPH F. PARKER, MEGAN B. SASSIN, EMILY J. KLEIN, MASON A. WOLAK, COREY T. LOVE, JEFFREY W. LONG: "Initiated Chemical Vapor Deposition of Ultrathin Polymer Coatings at Graphite Electrodes for Enhanced Performance in Li-Ion Batteries", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, ELECTROCHEMICAL SOCIETY, vol. 170, 1 January 2023 (2023-01-01), XP093330030, ISSN: 0013-4651, DOI: 10.1149/1945-7111 *

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