WO2020235748A1 - 리튬 이차전지용 실리콘-흑연 복합 전극 활물질, 이를 포함하는 전극 및 리튬 이차전지, 이러한 실리콘-흑연 복합 전극 활물질의 제조방법 - Google Patents

리튬 이차전지용 실리콘-흑연 복합 전극 활물질, 이를 포함하는 전극 및 리튬 이차전지, 이러한 실리콘-흑연 복합 전극 활물질의 제조방법 Download PDF

Info

Publication number
WO2020235748A1
WO2020235748A1 PCT/KR2019/011870 KR2019011870W WO2020235748A1 WO 2020235748 A1 WO2020235748 A1 WO 2020235748A1 KR 2019011870 W KR2019011870 W KR 2019011870W WO 2020235748 A1 WO2020235748 A1 WO 2020235748A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
graphite
graphite composite
electrode active
active material
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.)
Ceased
Application number
PCT/KR2019/011870
Other languages
English (en)
French (fr)
Korean (ko)
Inventor
진홍수
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.)
Livenergy Co Ltd
Original Assignee
Livenergy Co Ltd
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
Application filed by Livenergy Co Ltd filed Critical Livenergy Co Ltd
Priority to JP2020552214A priority Critical patent/JP7540947B2/ja
Priority to CN201980001866.5A priority patent/CN112243540A/zh
Priority to US17/034,960 priority patent/US20210013499A1/en
Publication of WO2020235748A1 publication Critical patent/WO2020235748A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • 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
    • 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
    • H01M4/58—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode active material for a lithium secondary battery, an electrode and a secondary battery including the same, and a method of manufacturing such a silicon-graphite composite electrode active material, and more particularly, a combination of graphite and silicon provides high capacity and high efficiency charge and discharge characteristics It relates to an electrode active material capable of, an electrode and a secondary battery including the same, and a method of manufacturing such an electrode active material.
  • lithium secondary battery has been attracting attention as a power source for driving electronic devices, and such lithium secondary batteries are increasingly used in various fields from IT devices such as mobile phones to electric vehicles and energy storage devices.
  • lithium secondary batteries As the application fields and demands of lithium secondary batteries increase, the structure of lithium secondary batteries is also being developed in various ways, and various research and development are being actively carried out to improve the capacity, life, performance, and safety of the battery.
  • graphite-based materials have been mainly used as electrode active materials (cathode active materials) for lithium secondary batteries, but graphite has a capacity per unit mass of only 372 mAh/g, so there is a limit to high capacity. Since it is difficult to sufficiently improve the material, research to replace graphite-based materials with materials that form electrochemical alloys with lithium such as silicon (Si), tin (Sn), antimony (Sb), and aluminum (Al) has recently been conducted. Is being carried out.
  • these materials form an electrochemical alloy with lithium and have the property of expanding/contracting in volume during charging and discharging, and the volume change caused by such charging and discharging causes volume expansion of the electrode, thereby reducing the cycle characteristics of the secondary battery.
  • an electrode active material manufactured using these materials has not yet been actively commercialized.
  • silicon which is attracting the most attention as an electrode active material for secondary batteries that can replace graphite materials, can absorb up to 4.4 lithium per silicon and thus provide high capacity, but the volume is about 4 in the process of absorbing lithium ions.
  • graphite which has been widely used as an electrode active material in the past, exhibits an expansion rate of about 1.2 times when charging and discharging), and when charging and discharging of the secondary battery continues, the expansion of the electrode intensifies and the secondary battery There is a problem that the cycle characteristics rapidly deteriorate.
  • Patent Document 1 a technology for improving the performance of a secondary battery by forming a silicon layer on a carbon-based material such as graphite is disclosed.
  • Patent Document 1 discloses that a silicon coating layer is formed on the surface of a carbon-based material such as graphite to secure a higher capacity than a conventional electrode active material formed of graphite material, while at the same time reducing the cycle performance degradation of the secondary battery due to expansion/contraction of silicon. A method of doing this is disclosed.
  • the electrode active material disclosed in Patent Document 1 is formed in a structure in which a silicon layer is provided on the outer surface of a carbon-based material, the electrode active material is electrically shorted from the electrode while the outer silicon layer greatly expands/contracts during the charging and discharging process. There is still a problem in that the performance of the secondary battery is deteriorated due to problems such as an accelerated side reaction with the electrolyte due to the fine-differentiated surface of the electrode active material.
  • Patent Document 2 discloses a technology for improving the performance of an electrode active material by forming a silicon coating layer inside a carbon-based material such as graphite. Specifically, Patent Document 2 discloses that a carbon-based material is spheroidized to form a cavity therein, and then a silicon coating layer is deposited through a chemical vapor deposition (CVD) to form a silicon coating layer in the cavity inside the carbon-based material. The technology is disclosed.
  • CVD chemical vapor deposition
  • Patent Document 2 in the process of depositing a silicon coating layer by putting a carbon-based material with a spheroidization process and a cavity formed therein into a reaction chamber, raw material gas is injected, the carbon-based material as well as the cavity inside the carbon-based material
  • the silicon coating layer is naturally deposited on the outer surface of the material, and the silicon coating layer formed on the outer surface of the carbon-based material repeatedly expands/contracts during the charging and discharging process, deteriorating the cycle characteristics of the secondary battery, similar to Patent Document 1. Will act as.
  • Patent Document 1 and Patent Document 2 disclose a configuration in which a carbon or conductive coating layer is additionally formed on the surface of an electrode active material in which a silicon layer is formed on a carbon-based material.
  • silicon is exposed through the ruptured surface, and the silicon exposed to the outside accelerates side reactions with the electrolyte and acts as a cause of deteriorating the performance and life of the secondary battery. Is done.
  • Patent Document 1 Korean Patent No. 10-1628873 (Registration Date: 2016.06.02.)
  • Patent Document 2 Korean Patent No. 10-1866004 (Registration Date: 2018.06.01.)
  • the present invention is to solve the above-described problems of the conventional electrode active material for secondary batteries, an electrode active material for a secondary battery capable of improving the capacity of a secondary battery and providing excellent cycle characteristics at the same time, an electrode including the same, and a secondary battery, such an electrode It is an object of the present invention to provide a manufacturing method for manufacturing an active material.
  • a typical configuration of the present invention for achieving the above object is as follows.
  • a silicon-graphite composite electrode active material that can be used in a secondary battery.
  • the silicon-graphite composite electrode active material according to an embodiment of the present invention is formed by using a silicon-graphite composite in which silicon is mixed with a graphite material as a unit powder, and the silicon-graphite composite is formed in a form in which silicon is located inside the graphite material. , It may be formed so that silicon is not exposed on the outer surface of the graphite material.
  • silicon included in the silicon-graphite composite may be configured such that at least 90% of the total weight of silicon is located at a depth of 200 nm or more from the outer surface of the silicon-graphite composite.
  • all silicon included in the silicon-graphite composite may be configured to be located at a depth of 200 nm or more from the outer surface of the silicon-graphite composite.
  • silicon included in the silicon-graphite composite may be configured to be located at a depth of 1 ⁇ m or more from the outer surface of the silicon-graphite composite.
  • silicon included in the silicon-graphite composite may be configured to be located at a depth of 3 ⁇ m or more from the outer surface of the silicon-graphite composite.
  • the silicon included in the silicon-graphite composite may be configured to exceed 10wt% of the total weight of the silicon-graphite composite.
  • the silicon contained in the silicon-graphite composite may be configured to exceed 15wt% of the total weight of the silicon-graphite composite.
  • silicon is a raw material containing at least one of SiH 4 , Si 2 H 6 , Si 3 H 8 , SiCl 4 , SiHCl 3 , Si 2 Cl 6 , SiH 2 Cl 2 , SiH 3 Cl It can be deposited on a graphite material using a gas.
  • silicon may be deposited on a graphite material as a thin film layer having a thickness of 20 nm to 500 nm.
  • silicon is a raw material containing at least one of SiH 4 , Si 2 H 6 , Si 3 H 8 , SiCl 4 , SiHCl 3 , Si 2 Cl 6 , SiH 2 Cl 2 , SiH 3 Cl
  • the gas may be deposited on the graphite material while being supplied together with an auxiliary gas containing at least one of carbon, nitrogen, and germanium.
  • one or more elements of carbon, nitrogen, and germanium may be further included in silicon deposited on the graphite material.
  • the silicon thin film layer formed on the silicon-graphite composite may be formed of amorphous or semi-crystalline silicon particles.
  • a surface coating layer may be additionally formed on the outer peripheral surface of the silicon-graphite composite.
  • a negative electrode for a lithium secondary battery including the above-described silicon-graphite composite electrode active material may be provided.
  • a secondary battery including a positive electrode, the aforementioned negative electrode, and an electrolyte positioned between the positive electrode and the negative electrode may be provided.
  • a method of manufacturing a silicon-graphite composite electrode active material that can be used in a secondary battery includes a graphite base material preparation step of preparing a graphite material as a base material, a silicon layer formation step of forming a silicon layer on the graphite base material, and a graphite formed with a silicon layer. It may include a reassembly step of mechanically assembling the silicon so that it is located only inside the graphite.
  • a silicon layer in the step of forming a silicon layer, may be deposited in the form of a thin film on a plate-like graphite through chemical vapor deposition.
  • the silicon layer forming step at least one of SiH 4 , Si 2 H 6 , Si 3 H 8 , SiCl 4 , SiHCl 3 , Si 2 Cl 6 , SiH 2 Cl 2 , SiH 3 Cl
  • the silicon layer can be formed using the raw material gas.
  • a silicon layer having a thickness of 20 nm to 500 nm may be formed on the base graphite.
  • a silicon layer may be deposited on the base graphite while the source gas is supplied together with the auxiliary gas.
  • the auxiliary gas may include one or more of carbon, nitrogen, and germanium.
  • the reassembly step may be configured to mechanically reassemble the silicon-graphite composite while injecting the base graphite on which the silicon layer is formed into the spheronization equipment and then rotating at high speed.
  • the silicon-graphite composite in the reassembly step, is mechanically reassembled by introducing the base graphite on which the silicon layer is formed into the spheronization equipment and rotating at high speed, and then adding additional graphite material to rotate at high speed. It can be configured to assemble.
  • a surface coating step of forming an outer coating layer on the surface may be further included.
  • a surface modification step of modifying the surface of the graphite base material may be further included between the step of preparing the graphite base material and the step of forming the silicon layer.
  • the base graphite prepared in the graphite base material preparation step may be natural or artificial plate-like graphite having a thickness of 2 ⁇ m to 20 ⁇ m.
  • the electrode active material according to the present invention including the same.
  • Other additional configurations may be further included in the manufacturing method of the electrode (cathode), the secondary battery, and the electrode active material within a range not impairing the technical idea of the present invention.
  • the electrode active material according to an embodiment of the present invention is formed in a silicon-graphite composite structure containing silicon in a graphite material, and silicon contained in the silicon-graphite composite is located only inside the graphite material and does not exist on the outer surface of the graphite material. Because it is configured, the capacity and performance of the secondary battery is improved by the silicon material contained in the electrode active material, while reducing the problem of volume expansion of the electrode due to the expansion/contraction of silicon, and the risk of electrical shorting of the electrode active material from the electrode. In addition, it is possible to provide an effect of greatly improving the life and cycle characteristics of a secondary battery by reducing the problem of accelerating side reactions with the electrolyte by silicon exposed to the surface of the electrode active material.
  • FIG. 1 exemplarily shows a scanning electron microscope (SEM) picture of an electrode active material for a secondary battery according to an embodiment of the present invention.
  • FIG. 2 exemplarily shows a scanning electron microscope (SEM) photograph of plate-shaped graphite that can be used to manufacture an electrode active material for a secondary battery according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 3 exemplarily shows a state in which a silicon coating layer is formed on the plate-shaped graphite shown in FIG. 2.
  • FIG. 4 exemplarily shows an electrode active material during a process of spheroidizing a plate-shaped graphite on which a silicon coating layer is formed.
  • 5 exemplarily shows changes in specific surface area properties of graphite before and after the surface modification process.
  • FIG. 6 exemplarily shows a silicon-graphite composite according to an embodiment of the present invention in which spheronization is completed.
  • FIG. 7 exemplarily shows a cross-sectional structure of a silicon-graphite composite (sphericalization completed) according to an embodiment of the present invention.
  • Figure 8 is a conventional silicon-graphite composite coated with a silicon layer on spherical graphite and then surface-coated with a petroleum pitch [Fig. The cross-sectional structure of the electrode plate after rolling in (b)] is illustrated as an example.
  • 9 and 10 exemplarily show electrochemical performance test results of a conventional silicon-graphite composite and a silicon-graphite composite according to an embodiment of the present invention.
  • Electrode active material according to the present invention and electrode and secondary battery comprising the same
  • a silicon-graphite composite electrode active material in which silicon is mixed with a graphite material may be provided.
  • the graphite material which was conventionally used as an electrode active material for secondary batteries, has problems such as capacity limitation and output characteristics deterioration during high-speed charging.
  • Silicone material has low conductivity and causes significant volume expansion during charging and discharging. There is a problem of greatly deteriorating the cycle characteristics of a secondary battery by causing serious damage to the active material and the electrode plate.
  • the electrode active material according to an embodiment of the present invention is formed in a composite structure in which silicon is mixed with a graphite material, so that the battery capacity can be greatly improved compared to a conventional electrode active material made of graphite.
  • the silicon contained in the active material is not exposed to the outer surface of the graphite material, and all of it is configured to be located inside the graphite material (more preferably, it is located considerably deeper into the graphite material). It is configured to prevent the problem of side reaction caused by exposure of silicon to the electrolyte in the process of forming and to suppress the problem of deteriorating the life and performance of the secondary battery due to the volume expansion of silicon due to expansion/contraction of silicon only inside the graphite material. Has been.
  • the electrode active material according to an embodiment of the present invention may be configured to be formed using a silicon-graphite composite in which a silicon material is mixed with a graphite material (a powder mass shown enlarged in FIG. 1).
  • Such a silicon-graphite composite functions as a unit powder forming an electrode active material of a secondary battery, and may be configured such that silicon is formed as a thin film layer, etc. on a graphite material. Are gathered to form an electrode active material.
  • silicon may be configured to be deposited and formed on a graphite material by a method such as chemical vapor deposition (CVD), and silicon is not exposed to the outer surface of the graphite material. It may be configured to be located inside the graphite material.
  • CVD chemical vapor deposition
  • the silicon-graphite composite functioning as a unit powder forming the electrode active material is configured to be located inside the graphite material so that silicon is not exposed to the outer surface of the silicon-graphite composite, It is possible to suppress damage to the electrode plate due to the expansion/contraction of the exposed silicon, and to prevent side reactions from accelerating due to contact of the silicon exposed to the electrolyte, thereby greatly improving the performance and life of the secondary battery. .
  • the silicon included in the silicon-graphite composite constituting the electrode active material may be configured to exceed 10wt%, more preferably to exceed 15wt% with respect to the total weight of the silicon-graphite composite. have. Since silicon can provide a larger capacity than graphite, the more silicon the electrode active material contains, the higher the secondary battery capacity can be, but the silicon contained in the electrode active material is the cycle characteristics of the secondary battery due to expansion that occurs during charging and discharging. There may be a limit to increasing the amount of silicon added to the electrode active material because it can greatly decrease the.
  • conventionally known silicon-graphite composite electrode active materials have been configured to contain only a small amount of silicon in the electrode active material due to the problem of deteriorating the cycle characteristics of the secondary battery due to the expansion/contraction of silicon.
  • the electrode active material according to an embodiment of the present invention is configured so that all silicon is located inside the graphite material and is not exposed to the outside of the graphite, silicon exceeding 10 wt% (more preferably exceeding 15 wt%) is used as the electrode active material. Even if included in, since it is possible to suppress surface cracking caused by expansion/contraction of silicon, more silicon can be mixed with the silicon-graphite composite to further improve the capacity of the secondary battery.
  • silicon included in a silicon-graphite composite constituting an electrode active material may be formed to have amorphous or semi-crystalline silicon particles.
  • amorphous or semi-crystalline silicon does not have a direction in which lithium is absorbed, so it can expand in volume uniformly, and it has a high moving speed of lithium and has a stable structure due to less stress or strain in absorption or desorption of lithium compared to crystalline silicon. It has the advantage of being able to maintain. Therefore, when silicon is formed into amorphous or semi-crystalline particles, it is possible to prevent a problem in which the secondary battery is damaged due to expansion of silicon even if a larger amount of silicon is contained in the electrode active material.
  • the silicon located in the graphite material is such that 90% or more of the total weight of the silicon is located at a depth of at least 200 nm or more from the outer surface of the silicon-graphite composite.
  • all silicon may be configured to be located at a depth of at least 200 nm or more from the outer surface.
  • the performance of the secondary battery and the performance of the secondary battery are effectively prevented by effectively preventing the silicon from being exposed to the outer surface and causing side reactions in contact with the electrolyte.
  • the lifespan can be further improved.
  • the silicon-graphite composite according to an embodiment of the present invention may be configured to be located at a depth of 1 ⁇ m, more preferably 3 ⁇ m or more from the surface of the silicon-graphite composite.
  • the electrode active material according to an embodiment of the present invention is such that the thickness or distance between the outermost silicon and the outer surface of the silicon-graphite composite is formed larger than the thickness or distance from the center of the silicon-graphite composite to the outermost silicon. It can also be configured. According to this structure, the electrode active material according to an embodiment of the present invention may be formed in a core-shell structure in which the graphite material surrounds a core in which the electrode active material is mixed with silicon and graphite, Silicon can function by being stably located deep inside the graphite.
  • a surface coating layer may be further included on the outer peripheral surface of the silicon-graphite composite constituting the electrode active material.
  • the surface coating layer formed on the outer circumferential surface of the silicon-graphite composite provides an electron transfer path to improve electrical conductivity, and suppresses volume change of silicon during charging and discharging, thereby improving electrode plate stability.
  • the surface coating layer formed on the outer circumferential surface of the silicon-graphite composite is a carbon material different from the graphite constituting the silicon-graphite composite (e.g., coal tar pitch, petroleum pitch, epoxy resin, panel Resin, polyvinyl alcohol, polyvinyl chloride, ethylene, acetylene, and one or more carbon materials of methane).
  • a carbon material different from the graphite constituting the silicon-graphite composite e.g., coal tar pitch, petroleum pitch, epoxy resin, panel Resin, polyvinyl alcohol, polyvinyl chloride, ethylene, acetylene, and one or more carbon materials of methane.
  • the surface coating layer is not necessarily provided, and it is possible to omit the surface coating layer and form an electrode active material, and it is also possible to form an additional coating layer (conductive coating layer, etc.) in addition to the surface coating layer of the above-described carbon material.
  • an electrode (cathode) and a secondary battery including the above-described electrode active material may be provided.
  • the electrode and secondary battery according to an embodiment of the present invention may include the electrode active material formed of the above-described silicon-graphite composite, and the silicon-graphite composite forming the electrode active material is inside the graphite material as described above. It may be formed in a structure in which silicon is mixed.
  • a silicon-graphite composite can be formed in a structure in which silicon is located inside the graphite material, so that the electrode and secondary battery due to volume expansion of silicon and contact with the electrolyte, while promoting the increase in battery capacity by silicon. It is possible to effectively suppress the problem of performance/lifetime degradation.
  • the electrode active material according to an embodiment of the present invention can be used to form an electrode of a secondary battery alone, and is mixed with a conventional electrode active material (for example, an electrode active material formed of a graphite-based material) to form an electrode for a secondary battery. It may be configured to form an active material.
  • a conventional electrode active material for example, an electrode active material formed of a graphite-based material
  • the electrode active material according to an embodiment of the present invention can stably control problems such as damage to the electrode due to volume expansion of silicon as described above, it is sufficient to include a larger amount of silicon in the electrode active material than in the prior art. Since the capacity can be expanded, a sufficiently improved capacity improvement effect can be provided compared to the conventional even if it is used in combination with a conventional electrode active material. Rather, silicon is mixed with a conventional electrode active material such as an electrode active material formed of a graphite-based material. Due to the volume expansion problem can be more effectively controlled.
  • a method of manufacturing a silicon-graphite composite electrode active material in which silicon is added to a graphite material is provided.
  • the electrode active material (silicon-graphite composite constituting the electrode active material) is (i) a base graphite preparation step of preparing a graphite material (eg, plate-like graphite), (ii) the prepared base graphite A silicon layer forming step of forming silicon, (iii) a re-assembly step of mechanically assembling the silicon layer so that the silicon layer is formed only inside the graphite by spheronizing the graphite formed thereon may be included.
  • a base graphite preparation step of preparing a graphite material (eg, plate-like graphite)
  • the prepared base graphite A silicon layer forming step of forming silicon
  • a re-assembly step of mechanically assembling the silicon layer so that the silicon layer is formed only inside the graphite by spheronizing the graphite formed thereon may be included.
  • Preparing the base graphite is a step of preparing a graphite base material that is a basic material of the silicon-graphite composite according to an embodiment of the present invention, and the base material may be natural or artificial graphite having a plate-like structure, for example, from 2 ⁇ m to It can be formed of a material having a particle size of 20 ⁇ m.
  • the silicon layer forming step is a step of coating a silicon material on a plate-shaped graphite base material to increase the capacity of the electrode active material, and the silicon layer may be formed through chemical vapor deposition or the like.
  • the silicon layer may be performed by injecting a raw material gas containing silicon into a high-temperature reaction chamber and depositing it on the base graphite, and the reaction chamber heated to a temperature of 400°C to 700°C is SiH 4 , Si 2 H 6. , Si 3 H 8 , SiCl 4 , SiHCl 3 , Si 2 Cl 6 , SiH 2 Cl 2 , SiH 3 Cl, etc., by injecting raw material gas to deposit a silicon coating layer on the plate-shaped graphite material.
  • the silicon layer can be formed on the graphite material at a relatively low temperature (a temperature range of 400°C to 700°C), the silicon coating layer can be formed of amorphous or semi-crystalline silicon particles rather than crystalline.
  • the formation of the silicon coating layer may be performed by injecting an auxiliary gas containing carbon, nitrogen, germanium, etc. together with the above-described source gas.
  • an auxiliary gas containing materials such as carbon, nitrogen, germanium, etc.
  • materials such as carbon, nitrogen and germanium are contained in the silicon layer formed on the graphite material.
  • the silicon included in the silicon-graphite composite forming the electrode active material may be formed to exceed 10wt%, more preferably to exceed 15wt% with respect to the total weight of the silicon-graphite composite. And, it may be formed in the form of a thin film layer having a thickness in the range of 20nm to 500nm.
  • the reassembly step is a step of spheroidizing the graphite on which the silicon layer is formed.Since the silicon layer deposited on the base graphite through the reassembly step moves to a position inside the graphite and is mechanically reassembled, the silicon layer is not exposed to the outside surface. -A graphite complex can be formed.
  • the reassembly step is (i) injecting the base graphite on which the silicon layer is formed into the spheronization equipment, and then rotating at high speed to form a silicon-graphite composite, or (ii) first, a silicon layer is formed. It can be carried out in a manner in which the base graphite is injected into the spheronization equipment, rotated at high speed, and then spheronized together by adding additional graphite material after a predetermined period of time has elapsed, and the silicon layer is formed through this process. It may be configured to form a silicon-graphite composite located only inside the graphite material and not exposed to the external surface.
  • a surface modification step of preparing the base graphite and then modifying the surface of the base graphite material before forming a silicon coating layer on the base graphite may be further included.
  • Surface modification is a step in which the micropores formed in the base graphite are filled to prevent the inflow of silicon into the micropores where it is difficult to secure a space for the expansion of the silicon.
  • Micropores are filled with heterogeneous amorphous or crystalline carbon, so that the specific surface area of the base graphite material can be reduced [When the surface modification process is performed, the micropores inside the base graphite are filled with heterogeneous amorphous or crystalline carbon.
  • the specific surface area can be reduced from 2 to 10 m 2 /g to 1 to 5 m 2 /g], whereby the silicon layer will be formed only outside the graphite and the large cavity that exists inside the base graphite. You will be able to.
  • the silicon coating layer formed in the micropores may not provide enough space for the expansion of silicon and may cause cracks in the base graphite. If the surface modification process is performed, the formation of the silicon coating layer in these micropores is prevented and Damage can be suppressed.
  • the surface modification process may be performed by coating a precursor such as petroleum pitch, coal pitch, resin, asphalt, methane, ethylene, and acetylene on the surface of the base graphite.
  • precursors such as petroleum-based pitch, coal-based pitch, resin, and asphalt can be coated on the base graphite using a rotary furnace or an atmosphere furnace, and the temperature range of 600°C to 1,000°C in an inert gas atmosphere such as N 2 and Ar. Coating can proceed by holding the furnace material for 2 hours or longer.
  • precursors such as methane, ethylene, and acetylene may be coated on the base graphite using a vapor deposition device or a rotary furnace, and the precursors for the plate-shaped graphite at a temperature of 800°C to 1,000°C at a flow rate of 3L to 8L per minute. It can be coated on the surface by spilling it.
  • the silicon-graphite electrode active material according to an embodiment of the present invention manufactured in this way is formed in a state where silicon is stably located inside the graphite material (more preferably, it is located deep inside the graphite material), It is possible to reduce the risk of causing side reactions in contact with the electrolyte, and to further improve the performance and life of electrodes and secondary batteries.
  • the structure of the active material is greatly broken and ruptured in the process of forming an electrode by rolling the electrode active material as shown in Fig. 8(a).
  • the silicon-graphite composite according to an embodiment of the present invention maintains a solid structure even after the rolling process as shown in FIG. 8(b), so that the silicon is not exposed to the outside and is maintained inside the graphite material. can confirm.
  • the silicon-graphite composite mechanically reassembled by performing heat treatment in an inert atmosphere may be further integrated into one structure.
  • heat treatment may be performed by creating a vacuum environment in the reaction chamber and then heating the inside of the chamber to a high temperature of 800° C. or higher while injecting an inert gas such as Ar or N2, and then cooling it by air cooling. .
  • a surface coating step of forming an outer coating layer on the surface of the silicon-graphite composite completed through the above-described process may be additionally performed.
  • Such surface coating may improve electrical conductivity, thereby improving the performance and life of the electrode active material and the electrode/secondary battery having the same according to an exemplary embodiment of the present invention.
  • the surface coating is a carbon material on the surface of the silicon-graphite composite forming the electrode active material (eg, a carbon material different from the plate-shaped graphite used as the basic material of the silicon-graphite composite; coal tar pitch) , Petroleum pitch, epoxy resin, phenol resin, polyvinyl alcohol, polyvinyl chloride, ethylene, acetylene, methane, etc.).
  • the surface coating layer is not necessarily provided, and it is possible to omit the surface coating layer and form an electrode active material, and it is also possible to form an additional coating layer (conductive coating layer, etc.) in addition to the surface coating layer of the above-described carbon material.
  • a plate-shaped graphite material having an average particle size of 4 ⁇ m is prepared.
  • 10g of graphite is put into the rotary furnace and the inside of the rotary furnace is vacuum-replaced with a nitrogen atmosphere, and the temperature is raised to 580°C while flowing nitrogen of 99.999% purity.
  • SiH 4 having a purity of 99.999% is poured for about 17 minutes, and nitrogen of 99.999% of purity is flowed through air-cooling to apply a silicon coating layer on the plate-like graphite.
  • the plate-shaped graphite on which the silicon coating layer has been deposited is put into a spheroidizing equipment and reassembled.
  • the plate-like graphite on which the silicon coating layer is deposited is put into the spheronization equipment, mechanically polished for 10 minutes at a rotational speed of 16,000RPM, and then additional graphite material is added to the equipment and rotated at a rotational speed of 7,000rpm.
  • the silicon-graphite composite is mechanically reassembled so that the coating layer is moved and placed inside the graphite material.
  • the reassembled silicon-graphite composite is put into a reaction chamber, and the chamber is heated to 900°C in a vacuum and inert gas environment to perform heat treatment and air cooling.
  • a plate-shaped graphite material having an average particle size of 4 ⁇ m is prepared.
  • 10g of graphite is put into the rotary furnace and the inside of the rotary furnace is vacuum-replaced with a nitrogen atmosphere, and the temperature is raised to 580°C while flowing nitrogen of 99.999% purity.
  • SiH 4 with a purity of 99.999% is poured for about 20 minutes, and nitrogen with a purity of 99.999% is air-cooled to apply a silicon coating layer on the plate-like graphite.
  • the plate-shaped graphite on which the silicon coating layer has been deposited is put into a spheroidizing equipment and reassembled.
  • the plate-like graphite on which the silicon coating layer is deposited is put into the spheronization equipment, mechanically polished for 10 minutes at a rotational speed of 16,000RPM, and then additional graphite material is added to the equipment and rotated at a rotational speed of 7,000rpm.
  • the silicon-graphite composite is mechanically reassembled so that the coating layer is moved and placed inside the graphite material.
  • the reassembled silicon-graphite composite is put into a reaction chamber, and the chamber is heated to 900°C in a vacuum and inert gas environment to perform heat treatment and air cooling.
  • a plate-shaped graphite material having an average particle size of 4 ⁇ m is prepared.
  • 10g of graphite is put into the rotary furnace and the inside of the rotary furnace is vacuum-replaced with a nitrogen atmosphere, and the temperature is raised to 580°C while flowing nitrogen of 99.999% purity.
  • SiH 4 with a purity of 99.999% is poured for about 25 minutes, and nitrogen with a purity of 99.999% is air-cooled to apply a silicon coating layer on the plate-like graphite.
  • the plate-shaped graphite on which the silicon coating layer has been deposited is put into a spheroidizing equipment and reassembled.
  • the plate-like graphite on which the silicon coating layer is deposited is put into the spheronization equipment, mechanically polished for 10 minutes at a rotational speed of 16,000RPM, and then additional graphite material is added to the equipment and rotated at a rotational speed of 7,000rpm.
  • the silicon-graphite composite is mechanically reassembled so that the coating layer is moved and placed inside the graphite material.
  • the reassembled silicon-graphite composite is put into a reaction chamber, and the chamber is heated to 900°C in a vacuum and inert gas environment to perform heat treatment and air cooling.
  • the comparative example is a silicon-graphite composite manufactured according to the process conditions of the example disclosed in Patent Document 1, using spherical graphite as a raw material and decomposing SiH 4 thereon to deposit a silicon coating layer, and then coating a petroleum pitch on the surface. A silicon-graphite composite was formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
PCT/KR2019/011870 2019-05-17 2019-09-11 리튬 이차전지용 실리콘-흑연 복합 전극 활물질, 이를 포함하는 전극 및 리튬 이차전지, 이러한 실리콘-흑연 복합 전극 활물질의 제조방법 Ceased WO2020235748A1 (ko)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020552214A JP7540947B2 (ja) 2019-05-17 2019-09-11 リチウム二次電池用シリコン－黒鉛複合電極活物質、これを含む電極およびリチウム二次電池、ならびにシリコン－黒鉛複合電極活物質の製造方法
CN201980001866.5A CN112243540A (zh) 2019-05-17 2019-09-11 锂二次电池用硅-石墨复合电极活性材料、包括其的电极和锂二次电池以及该硅-石墨复合电极活性材料的制备方法
US17/034,960 US20210013499A1 (en) 2019-05-17 2020-09-28 Silicon-graphite composite electrode active material for lithium secondary battery, electrode and secondary battery provided therewith, and manufacturing method for such a silicon-graphite composite electrode active material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2019-0058161 2019-05-17
KR1020190058161 2019-05-17

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/034,960 Continuation US20210013499A1 (en) 2019-05-17 2020-09-28 Silicon-graphite composite electrode active material for lithium secondary battery, electrode and secondary battery provided therewith, and manufacturing method for such a silicon-graphite composite electrode active material

Publications (1)

Publication Number Publication Date
WO2020235748A1 true WO2020235748A1 (ko) 2020-11-26

Family

ID=73458903

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/011870 Ceased WO2020235748A1 (ko) 2019-05-17 2019-09-11 리튬 이차전지용 실리콘-흑연 복합 전극 활물질, 이를 포함하는 전극 및 리튬 이차전지, 이러한 실리콘-흑연 복합 전극 활물질의 제조방법

Country Status (4)

Country Link
US (1) US20210013499A1 (enExample)
JP (1) JP7540947B2 (enExample)
CN (1) CN112243540A (enExample)
WO (1) WO2020235748A1 (enExample)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240347728A1 (en) * 2021-02-24 2024-10-17 Focus Graphite Inc. Advanced anode materials comprising spheroidal additive-enhanced graphite particles and process for making same
JP2024534889A (ja) 2021-09-03 2024-09-26 アンワイヤー シリコン－カーボン複合材料の製造方法
CN115832267B (zh) * 2021-09-16 2024-10-11 南宁宸宇新能源科技有限公司 非晶硅/硬碳复合材料及其制备和在锂离子电池中的应用
KR20250077161A (ko) * 2023-11-23 2025-05-30 주식회사 이큐브머티리얼즈 탄소나노튜브와 카본블랙 복합 네트워크형 리튬이온이차전지용 실리콘 음극재

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150055178A (ko) * 2013-11-11 2015-05-21 재단법인 철원플라즈마 산업기술연구원 리튬 이차전지용 음극 활물질 제조방법 그리고 리튬 이차 전지
KR20150113314A (ko) * 2014-03-27 2015-10-08 전자부품연구원 음극소재, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법
KR20150137946A (ko) * 2014-05-29 2015-12-09 국립대학법인 울산과학기술대학교 산학협력단 음극 활물질, 이의 제조 방법, 이를 포함하는 음극판, 및 리튬 이차전지
KR20160147672A (ko) * 2015-06-15 2016-12-23 울산과학기술원 리튬 이차 전지용 음극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
KR20170086870A (ko) * 2016-01-19 2017-07-27 강원대학교산학협력단 팽창흑연이 포함된 리튬 이차전지용 음극 활물질, 그 제조방법 및 리튬 이차전지용 음극 활물질을 포함하는 리튬 이차전지

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5143437B2 (ja) * 2007-01-30 2013-02-13 日本カーボン株式会社 リチウムイオン二次電池用負極活物質の製造方法、負極活物質及び負極
JP6000017B2 (ja) * 2011-08-31 2016-09-28 株式会社半導体エネルギー研究所 蓄電装置及びその作製方法
JP2015125794A (ja) * 2013-12-25 2015-07-06 古河電気工業株式会社 複合体粒子及びその製造方法並びにそれを用いた負極及び非水電解質二次電池
JP2016051557A (ja) * 2014-08-29 2016-04-11 国立大学法人山形大学 リチウムイオン二次電池用負極材及びその製造方法並びにリチウムイオン二次電池
KR20160049980A (ko) * 2014-10-28 2016-05-10 레르 리키드 쏘시에떼 아노님 뿌르 레뜌드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 규소/탄소 복합재, 규소 합금/탄소 복합재, 및 그의 제조 방법
CN104577084A (zh) * 2015-01-20 2015-04-29 深圳市贝特瑞新能源材料股份有限公司 一种锂离子电池用纳米硅复合负极材料、制备方法及锂离子电池
CN110790263B (zh) * 2015-05-13 2021-12-24 储晞 三维石墨烯生产方法、装置、复合电极材料及制备与应用
KR102063809B1 (ko) * 2016-12-29 2020-01-08 울산과학기술원 리튬 이차 전지용 음극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
JP2018181791A (ja) * 2017-04-21 2018-11-15 尾池工業株式会社 負極活物質、及びリチウム二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150055178A (ko) * 2013-11-11 2015-05-21 재단법인 철원플라즈마 산업기술연구원 리튬 이차전지용 음극 활물질 제조방법 그리고 리튬 이차 전지
KR20150113314A (ko) * 2014-03-27 2015-10-08 전자부품연구원 음극소재, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법
KR20150137946A (ko) * 2014-05-29 2015-12-09 국립대학법인 울산과학기술대학교 산학협력단 음극 활물질, 이의 제조 방법, 이를 포함하는 음극판, 및 리튬 이차전지
KR20160147672A (ko) * 2015-06-15 2016-12-23 울산과학기술원 리튬 이차 전지용 음극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
KR20170086870A (ko) * 2016-01-19 2017-07-27 강원대학교산학협력단 팽창흑연이 포함된 리튬 이차전지용 음극 활물질, 그 제조방법 및 리튬 이차전지용 음극 활물질을 포함하는 리튬 이차전지

Also Published As

Publication number Publication date
CN112243540A (zh) 2021-01-19
US20210013499A1 (en) 2021-01-14
JP7540947B2 (ja) 2024-08-27
JP2022532455A (ja) 2022-07-15

Similar Documents

Publication Publication Date Title
WO2020235748A1 (ko) 리튬 이차전지용 실리콘-흑연 복합 전극 활물질, 이를 포함하는 전극 및 리튬 이차전지, 이러한 실리콘-흑연 복합 전극 활물질의 제조방법
WO2019151774A1 (ko) 음극 활물질, 상기 음극 활물질의 제조 방법, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지
WO2021112300A1 (ko) 이차전지용 전극 활물질, 이를 포함하는 전극 및 이차전지, 이러한 전극 활물질의 제조방법
WO2016108645A1 (ko) 실리콘계 음극 활물질 및 이의 제조 방법
WO2019112390A1 (ko) 리튬 이차전지용 음극 활물질 및 이의 제조방법
WO2016153322A1 (ko) 실리콘계 음극 활물질 및 이의 제조 방법
WO2016137024A1 (ko) 실리콘 음극 활물질 및 이의 제조 방법
WO2014084502A1 (ko) 규소계 복합체 및 이의 제조방법
WO2019093830A1 (ko) 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지
WO2013005887A1 (ko) 실리콘-탄소 코어쉘을 이용한 리튬이차전지용 음극활물질 및 이의 제조방법
WO2019093820A1 (ko) 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지
WO2019066129A2 (ko) 복합음극활물질, 이의 제조 방법 및 이를 포함하는 음극을 구비한 리튬이차전지
WO2019050216A2 (ko) 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지
WO2022055309A1 (ko) 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지
WO2020138629A1 (ko) 복합 음극활물질, 이의 제조 방법, 및 이를 포함한 음극을 구비한 리튬 이차 전지
WO2023106856A1 (ko) 리튬이차전지
WO2022119197A1 (ko) 탄소-실리콘 복합체 및 이의 제조방법
KR102091942B1 (ko) 리튬 이차전지용 실리콘-흑연 복합 전극 활물질의 제조방법
WO2020091148A1 (ko) 리튬 이차전지용 실리콘-흑연 복합 전극 활물질, 이를 포함하는 전극 및 리튬 이차전지, 이러한 실리콘-흑연 복합 전극 활물질의 제조방법
CN114864888A (zh) 一种二氟草酸硼酸锂掺杂包覆SiO/C复合材料及其制备方法和应用
KR102715100B1 (ko) 리튬 이차전지용 전극 활물질의 제조방법
WO2018203731A1 (ko) 음극 활물질, 상기 음극 활물질을 포함하는 음극, 상기 음극을 포함하는 이차 전지 및 상기 음극 활물질의 제조 방법
WO2025033765A1 (ko) 리튬 이차전지의 음극재용 전구체, 이로부터 제조된 음극재 및 그 제조방법
WO2021221276A1 (ko) 리튬 이차전지용 음극재, 이의 제조방법 및 리튬 이차전지
WO2024172408A1 (ko) 이차전지용 음극 및 이를 포함하는 리튬 이차전지

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2020552214

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 19929884

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19929884

Country of ref document: EP

Kind code of ref document: A1