WO2023229200A1 - 실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지 - Google Patents

실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지 Download PDF

Info

Publication number
WO2023229200A1
WO2023229200A1 PCT/KR2023/004326 KR2023004326W WO2023229200A1 WO 2023229200 A1 WO2023229200 A1 WO 2023229200A1 KR 2023004326 W KR2023004326 W KR 2023004326W WO 2023229200 A1 WO2023229200 A1 WO 2023229200A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfur
carbon composite
silica
coated
carbon
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/KR2023/004326
Other languages
English (en)
French (fr)
Korean (ko)
Inventor
이미진
김민수
손권남
한동협
홍경식
신동석
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.)
LG Energy Solution Ltd
Original Assignee
LG Energy Solution 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
Priority claimed from KR1020220135073A external-priority patent/KR20230165673A/ko
Application filed by LG Energy Solution Ltd filed Critical LG Energy Solution Ltd
Priority to CN202380012754.6A priority Critical patent/CN117616596A/zh
Priority to CA3234875A priority patent/CA3234875A1/en
Priority to JP2024513248A priority patent/JP7823176B2/ja
Priority claimed from KR1020230042280A external-priority patent/KR102654898B1/ko
Publication of WO2023229200A1 publication Critical patent/WO2023229200A1/ko
Anticipated expiration legal-status Critical
Priority to JP2025195494A priority patent/JP2026031573A/ja
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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a sulfur-carbon composite and a lithium sulfur battery containing the same.
  • Secondary batteries are used as high-capacity power storage batteries and high-performance energy sources for portable electronic devices such as mobile phones, camcorders, and laptops.
  • lithium ion secondary batteries have the advantage of higher energy density and larger capacity per area than nickel-manganese batteries or nickel-cadmium batteries, but have disadvantages such as reduced stability due to overheating and low output characteristics.
  • a lithium-sulfur battery refers to a battery system that uses a sulfur-containing material with an S-S bond (sulfur-sulfur bond) as a positive electrode active material and lithium metal as a negative electrode active material.
  • Sulfur the main material of the positive electrode active material, has the advantage of being abundant in resources worldwide, non-toxic, and having a low weight per atom.
  • the sulfur used in lithium- sulfur batteries has an electrical conductivity of 5 Accordingly, sulfur-containing materials are complexed into a sulfur-carbon complex along with a conductive material such as carbon, which can provide electrochemical reaction sites, and are used as a positive electrode active material.
  • This problem can be caused by various causes, such as the presence of sulfur-agglomerates due to non-uniform injection of sulfur into the sulfur-carbon composite, or the sulfur-carbon composite itself is aggregated during electrode manufacturing and is not fed uniformly. It may be due to etc.
  • the problem to be solved by the present invention is to solve the above-mentioned problems
  • the goal is to provide lithium-sulfur batteries with improved performance and uniform quality, and electrodes for use therein that can increase production yield with improved performance, uniform quality, and fewer defects.
  • the present invention seeks to provide a silica-coated sulfur-carbon composite with improved cohesiveness of the sulfur-carbon composite, and a method for manufacturing the same.
  • the present invention seeks to provide a method of improving the flowability of a silica-coated sulfur-carbon composite by improving the surface roughness of the sulfur-carbon composite.
  • silica coated sulfur-carbon composites of the following embodiments are provided.
  • the silica coated sulfur-carbon composite according to the first embodiment includes a sulfur-carbon composite; and silica particles coated on at least a portion of the surface of the sulfur-carbon composite.
  • the angle of repose of the silica-coated sulfur-carbon composite may be 32° or less.
  • the average particle size (D 50 ) of the silica particles may be 10 to 50 nm.
  • the silica particles may be nanoparticles represented by the following formula (1).
  • Equation 1 p is a number where 0 ⁇ p ⁇ 1
  • the thickness of the silica particles coated on at least a portion of the surface of the silica-coated sulfur-carbon composite may be 20 nm to 5 ⁇ m.
  • the silica-coated sulfur-carbon composite may have the characteristics of Formula 2 below.
  • Mp is the mass of the silica particle
  • Mc is the mass of the sulfur-carbon complex
  • St is the surface area of the silica-coated sulfur-carbon composite.
  • the silica-coated sulfur-carbon composite may include the sulfur-carbon composite and the silica particles in a weight ratio of 99.9:0.1 to 80:20.
  • the average particle size (D 50 ) of the sulfur-carbon composite may be 20 ⁇ m to 50 ⁇ m.
  • the sulfur-carbon composite is a porous carbon material; and a sulfur-containing compound supported on at least a portion of the inner and outer surfaces of the pores of the porous carbon material.
  • the average diameter of pores present in the porous carbon material may be 1 to 200 nm.
  • the sulfur-containing compound is inorganic sulfur (S 8 ), lithium polysulfide (Li 2 Sn, 1 ⁇ n ⁇ 8), carbon sulfur polymer (C2Sx)m, 2.5 ⁇ x ⁇ 50, 2 ⁇ m) or mixtures thereof. It may include.
  • the sulfur-carbon composite may include the porous carbon material and the sulfur-containing compound at a weight ratio of 1:9 to 5:5.
  • the ratio of the maximum average particle diameter (D 50 ) of the sulfur-carbon composite to the maximum thickness of the coating layer formed by the silica particles may be 100:1 to 1000:1.
  • It may include 0.01 to 20 wt% of the silica particles and 80 wt% to 99.99 wt% of the sulfur-carbon composite.
  • 60% to 100% of the surface area of the sulfur-carbon composite may be coated with the silica particles.
  • the method for producing a silica-coated sulfur-carbon composite according to the sixteenth embodiment includes coating silica particles on at least a portion of the surface of the sulfur-carbon composite.
  • the step of preparing the sulfur-carbon composite may include mixing a sulfur-containing compound and a porous carbon material.
  • a step of separating the sulfur-carbon complex coated with the silica particles may be further included.
  • the coating step may include mixing the sulfur-carbon composite and the silica particles in a solid state.
  • the weight ratio of the sulfur-carbon composite and the silica particles may be 99.9:0.1 to 80:20.
  • positive electrode active materials, electrodes, and lithium sulfur batteries of the following embodiments are provided.
  • a positive electrode active material including the silica-coated sulfur-carbon composite according to any one of the first to fifteenth embodiments is provided.
  • an electrode comprising a silica-coated sulfur-carbon composite according to any one of the first to fifteenth embodiments is provided.
  • a lithium sulfur battery including a positive electrode including a silica-coated sulfur-carbon composite according to any one of the first to fifteenth embodiments, a negative electrode including a negative electrode active material, and an electrolyte solution. provided.
  • the silica-coated sulfur-carbon composite according to one embodiment of the present invention has the effect of improving surface fluidity. Due to the increased fluidity of the sulfur-carbon composite, the agglomeration of the silica-coated sulfur-carbon composite may be reduced. As a result, the silica-coated sulfur-carbon composite is uniformly applied on the electrode support, which has the effect of improving battery performance.
  • the silica-coated sulfur-carbon composite according to one embodiment of the present invention has silica particles coated on at least a portion of the surface of the sulfur-carbon composite.
  • silica particles are inserted into the surface of the sulfur-carbon composite with high surface roughness, thereby reducing the roughness of the surface of the sulfur-carbon composite, thereby providing excellent particle fluidity to the sulfur-carbon composite.
  • the silica-coated sulfur-carbon composite according to one embodiment of the present invention reduces the formation of aggregates and can be uniformly applied on the electrode support to manufacture an electrode with uniform loading.
  • electrodes manufactured using this can be manufactured more effectively due to the improved fluidity of the silica-coated sulfur-carbon composite, resulting in improved productivity of lithium-sulfur batteries.
  • Figure 1 shows SEM images of the sulfur-carbon composite according to Comparative Example 1 and the silica-coated sulfur-carbon composite according to Example 1 and Example 2 in the present specification.
  • the SEM image shown at the top is an image with a magnification of 15000
  • the SEM image shown at the bottom is an image with a magnification of 2000.
  • Figure 2 shows the results of measuring the angle of repose of the sulfur-carbon composite according to Comparative Example 1 and the silica-coated sulfur-carbon composite according to Examples 1 and 2 in the present specification.
  • Figure 3 shows a photograph confirming the flowability of the sulfur-carbon composite according to Comparative Example 1 and the silica-coated sulfur-carbon composite according to Example 1 and Example 2 in the present specification.
  • Figure 4 shows SEM images of the sulfur-carbon composite according to Comparative Example 2, and the zinc oxide (ZnO) coated sulfur-carbon composite according to Comparative Example 3 and Comparative Example 4 in the present specification.
  • the SEM image shown at the top is an image with a magnification of 10000
  • the SEM image shown at the bottom is an image with a magnification of 2000.
  • Figure 5 shows the results of measuring the angle of repose of the sulfur-carbon composite according to Comparative Example 2, and the zinc oxide (ZnO) coated sulfur-carbon composite according to Comparative Example 3 and Comparative Example 4 in the present specification.
  • composite refers to a material that combines two or more materials to form physically and chemically different phases while exhibiting more effective functions.
  • One aspect of the present invention seeks to provide a silica-coated sulfur-carbon composite that can be used as a carrier for supporting a positive electrode active material, the positive electrode active material itself, or a conductive material in the positive electrode of a lithium-sulfur battery.
  • the use of the silica-coated sulfur-carbon composite according to one aspect of the present invention is not limited thereto.
  • It includes a sulfur-carbon composite and silica particles coated on at least a portion of the surface of the sulfur-carbon composite.
  • the sulfur-carbon composite may include a sulfur-carbon composite having an outer surface at least partially coated with the silica particles.
  • the entire outer surface of the sulfur-carbon composite may be coated with the silica particles.
  • the silica particles when the sulfur-carbon composite is coated with silica particles, the silica particles may no longer be distinguishable as particles themselves, but appear on the surface of the sulfur-carbon composite.
  • a coating layer can be formed on.
  • the particle size of the sulfur-carbon composite is preferably larger than the particle size of a single silica particle.
  • the particle size may refer to the average particle size (D 50 ) according to ISO 13320:2020 known in the art, but the method of measuring the particle size is not limited thereto.
  • the silica particles may be nanoparticles having a chemical formula according to Formula 1 below.
  • Equation 1 p is a number where 0 ⁇ p ⁇ 1.
  • p may be 0.3 ⁇ p ⁇ 1.
  • p may be 0.5 ⁇ p ⁇ 1.
  • p may be 0.6 ⁇ p ⁇ 1.
  • p may be 0.7 ⁇ p ⁇ 1.
  • p may be 0.8 ⁇ p ⁇ 1.
  • p may be 0.9 ⁇ p ⁇ 1.
  • p may be 1.
  • the silica-coated sulfur-carbon composite according to one embodiment of the present invention includes a sulfur-carbon composite and silica particles coated on at least a portion of the surface of the sulfur-carbon composite.
  • the silica particles coated on at least a portion of the surface of the sulfur-carbon composite react with surrounding moisture (H 2 O) to form a hydroxyl group (-OH) on the surface of the sulfur-carbon composite. It can be granted.
  • Equation 1 may vary depending on the amount of surrounding moisture. Accordingly, the sulfur-carbon composite having at least a portion of the surface coated with silica particles as described above may exhibit reduced roughness and improved fluidity due to the insertion of silica particles, but the mechanism of the present invention It is not limited to this.
  • the fluidity can be measured by the angle of repose, as described later.
  • the roughness of the silica-coated sulfur-carbon composite can be measured according to ISO-25718:2016, which is known in the art, but the roughness measurement method is not limited thereto.
  • the silica-coated sulfur-carbon composite may have the characteristic of reducing the angle of repose by improving fluidity compared to the sulfur-carbon composite not coated with silica particles.
  • the angle of repose of the silica-coated sulfur-carbon composite may have the characteristic of lowering the angle of repose by more than 5% compared to the sulfur-carbon composite before the silica particles are coated. More specifically, the angle of repose of the silica-coated sulfur-carbon composite is 6% or more, 6.5% or more, 7% or more, 8% or more, 9% or more, and 10% or more compared to the sulfur-carbon composite before the silica particles are coated. , it may have the characteristic of being smaller by 15% or more, 20% or more, 25% or more, or 30% or more.
  • the phenomenon that the angle of repose of the silica-coated sulfur-carbon composite is lower than the angle of repose of the sulfur-carbon composite before coating may reflect the improvement in fluidity of the sulfur-carbon composite.
  • the angle of repose may vary depending on the specific sulfur-carbon complex used.
  • the decrease in the angle of repose can be calculated according to Equation 3 below.
  • Rb is the angle of repose of the sulfur-carbon complex before coating
  • Ra is the angle of repose of the silica-coated sulfur-carbon composite.
  • the silica-coated sulfur-carbon composite has improved fluidity as described above, so that the angle of repose may be 32° or less.
  • the “angle of repose” may represent a value measured according to a method commonly used in the art to measure the angle of repose of a sample, and methods for measuring the angle of repose include, for example, US Pharmacopoeia 1174 and EP An example is the Angle of Repose Method described in Pharmacopoeia 2.9.76.
  • the angle of repose can be measured, for example, according to the following method. First, place the funnel at a height of 7.5 cm above the ground, center it and fix it using a level, and then block the bottom of the funnel to prevent the inserted sample from being discharged downward.
  • the bottom of the funnel was opened and the sample was allowed to freely fall and pile up on the disk (diameter 13 cm) located at the bottom. Next, the angle of repose ( ⁇ ) of the stacked sample pile was measured.
  • the angle of repose is, for example, 5° to 32°, 5° to 31.5°, 5° to 31°, 10° to 31°, 5° to 30.5°, 5° to 30° , 10° to 30°, 15° to 28°, 15.5° to 27°, 20° to 26.5° or 23° to 26°, or 5° to 30.3°, or 5° to 25.5°, or 5° to 23°. °, or 23° to 30.3°, or 23° to 25.5°, or 25.5° to 30.3°.
  • the silica-coated sulfur-carbon composite may satisfy Equation 4 below.
  • Mc mass of sulfur-carbon complex
  • the angle of repose can be determined depending on the content of the silica particles used for the specific content of the sulfur-carbon composite to obtain the silica-coated sulfur-carbon composite.
  • a silica-coated sulfur-carbon composite that satisfies Equation 4 can ideally exhibit excellent fluidity and low density.
  • the silica-coated sulfur-carbon composite that satisfies Equation 4 may have a beneficial effect in improving the high capacity and/or performance of an electrode using the same, such as a positive electrode, and the performance of a lithium-sulfur battery using the same.
  • the silica-coated sulfur-carbon composite may satisfy the following formula 5A.
  • Mc mass of sulfur-carbon complex
  • the weight of the silica particles based on the weight of the silica-coated sulfur-carbon composite can be determined according to the specific surface area of the porous carbon material.
  • the large specific surface area of the porous carbon material may mean that the external surface area of the porous carbon material is large, and therefore the external surface of the sulfur-carbon composite may also be large.
  • Coating the large outer surface of the sulfur-carbon composite may mean that silica particles can be used in large quantities. Therefore, as the specific surface area of the porous carbon material increases, the amount of silica particles used may increase.
  • the silica-coated sulfur-carbon composite when the silica-coated sulfur-carbon composite satisfies Equation 5A, it can exhibit advantageous effects in terms of fluidity and low density of the silica-coated sulfur-carbon composite.
  • the specific surface area of the porous carbon material can be measured by the BET measurement method according to ISO 9277:2010, known in the art, and when measured by this method, most of the sulfur-containing compounds in the silica-coated sulfur-carbon composite, preferably There is nothing left at all. Therefore, most preferably, the specific surface area of the porous carbon material in the silica-coated sulfur-carbon composite is approximately similar to that of the sulfur-carbon composite and/or the porous carbon material that may not have been used in the formation of the silica-coated sulfur-carbon composite. In other words, it may be the same.
  • the silica-coated sulfur-carbon composite may satisfy the following formula 5B.
  • Mc mass of sulfur-carbon complex
  • the weight of the silica particles based on the weight of the silica-coated sulfur-carbon composite can be determined according to the specific surface area of the porous carbon material. Accordingly, the amount of silica particles may have a lower limit for silica coated sulfur-carbon composites comprising porous carbon materials with higher specific surface areas to provide silica coated sulfur-carbon composites with improved flow properties.
  • the specific surface area can be measured by BET according to ISO 9277:2010, as known to those skilled in the art.
  • a silica-coated sulfur-carbon composite satisfying Equation 5B can exhibit advantageous effects in terms of excellent fluidity and low density.
  • the average particle size (D 50 ) of the silica particles coated on at least a portion of the surface of the sulfur-carbon composite is, for example, 10 to 50 nm, or 10 to 40 nm, or 15 to 50 nm. It may be 40 nm, or 10 to 15 nm.
  • the average particle size (D 50 ) of the silica particles satisfies this range, it can be advantageous in terms of improving the uniformity of the silica particle coating and the cohesion of the sulfur-carbon composite.
  • the average particle size (D 50 ) means the particle size at 50% of the cumulative distribution of particle numbers according to particle size.
  • the particle size may be a value measured using a particle size analyzer (PSA) of a silica-coated sulfur-carbon composite coated with silica particles, but the method of measuring the particle size is not limited thereto.
  • PSDA particle size analyzer
  • a particle size analyzer for measuring the average particle diameter D50 can be used according to ISO13320:2020, known in the art, but the measurement method is not limited thereto.
  • the thickness of the silica particles coated on at least a portion of the surface of the silica-coated sulfur-carbon composite is, for example, 20 nm to 5 ⁇ m, 40 nm to 5 ⁇ m, or 40 nm to 1 ⁇ m. It can be.
  • the silica-coated sulfur-carbon composite can achieve low density and improve fluidity, but the present invention is not limited thereto.
  • the silica-coated sulfur-carbon composite may have an optimal balance between excellent fluidity and low density when the coating thickness is within the above-mentioned range.
  • the thickness of the silica particle coating can be confirmed through a differential scanning electron microscope (SEM), but the measurement method is not limited thereto.
  • the ratio of the maximum average particle diameter (D 50 ) of the sulfur-carbon composite to the maximum thickness of the coating layer formed by the silica particles may be, for example, 100:1 to 1000:1.
  • a silica-coated sulfur-carbon composite that satisfies the above ratio may exhibit advantageous effects in terms of excellent fluidity and low density, but the present invention is not limited thereto.
  • the average particle diameter of the silica-coated sulfur-carbon composite can be measured according to the method described above, the thickness of the coating layer can also be measured according to the method described above, and the ratio may be a value without a unit.
  • 60% to 100% of the surface area of the sulfur-carbon composite may be coated with the silica particles.
  • the surface area of the sulfur-carbon composite coated with the silica particles is 65% to 100%, 70& to 100%, 75% to 100%, 80% to 100%, 85% to 100%, and 90% to 90%. It may be 100%, 95% to 100%, or 95% to 99%, but the present invention is not limited thereto.
  • the sulfur-carbon composite may have an external surface and a specific surface area, and the surface area of the sulfur-carbon composite coated with the silica particles is measured based on 100% of the entire outer surface of the sulfur-carbon composite. It can be a value.
  • the area of the outer surface of the silica particle-coated sulfur-carbon composite can be measured, for example, through SEM image analysis of the surface of the silica-coated sulfur-carbon composite. Specifically, it can be measured at 15,000 times magnification for an area of 10 ⁇ m
  • the specific surface area may have a value similar to the internal area, and the specific surface area may be measured by the BET method according to ISO 9277:2010, known in the art, but is not limited thereto.
  • the thickness of the silica particles coated on the silica-coated sulfur-carbon composite is determined by the weight ratio of the silica particles and the total weight of the silica-coated sulfur-carbon composite based on the total weight of the silica-coated sulfur-carbon composite. It can be estimated from the correlation of the area ratio coated with the silica particles among the surface area.
  • the silica-coated sulfur-carbon composite may have the characteristics of Formula 2 below.
  • Mp is the mass of the silica particle
  • Mc is the mass of the sulfur-carbon complex
  • St is the surface area of the silica-coated sulfur-carbon composite.
  • the “area of the area coated with silica particles” may be measured according to a method for measuring the area coated with silica particles on the surface of a sulfur-carbon composite, for example, using a scanning electron microscope (SEM). It can be measured using .
  • SEM scanning electron microscope
  • the “surface area of the silica-coated sulfur-carbon composite” may be a specific surface area value measured by, for example, the BET method.
  • it may be a value calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77K) using BELSORP-mini II from BEL Japan.
  • the method of measuring the specific surface area may be performed according to ISO 9277:2010, which is known in the art, but the measurement method is not limited thereto.
  • the silica-coated sulfur-carbon composite is 0.01 to 20% by weight of the silica particles, specifically 0.01 to 10% by weight, more specifically 1 to 10% by weight, 1 based on the total weight. It may contain from 5% by weight or from 1 to 3% by weight.
  • the silica-coated sulfur-carbon composite is 80% by weight to 99.99% by weight, specifically 90% by weight to 99.99% by weight, more specifically 90% by weight to 99% by weight, based on the total weight, It may contain 95% to 99% by weight or 97% to 99% by weight.
  • the content of the silica particles and the sulfur-carbon complex is in the above-mentioned range, it can have the advantageous effect of exhibiting excellent fluidity and improved density, and electrodes and lithium-sulfur batteries using the same have improved performance, especially capacity and/or It can be advantageous in indicating lifespan.
  • the silica-coated sulfur-carbon composite may include the sulfur-carbon composite and the silica particles in a weight ratio of 99.9:0.1 to 80:20. That is, the weight ratio of the sulfur-carbon composite to the silica particles may range from 99.9:0.1 to 80:20, for example.
  • the weight ratio of the sulfur-carbon composite and the silica particles is 99.9:0.1 to 90:10, or 99:1 to 90:10, or 99:1 to 95:5, or 97:3 to 90:10. , or 99:1 to 97:3.
  • the silica-coated sulfur-carbon composite can achieve low density and improve fluidity, but the present invention is not limited thereto.
  • the silica-coated sulfur-carbon composite has technical significance in that silica particles are inserted into the surface of the sulfur-carbon composite commonly used in the anode of a lithium-sulfur battery, thereby reducing the roughness. Accordingly, the specific type, shape, etc. of the sulfur-carbon composite is not particularly limited. The roughness can be measured according to the method described above.
  • the average particle size (D 50 ) of the sulfur-carbon composite may be 20 ⁇ m to 50 ⁇ m, but the present invention is not limited thereto.
  • the method for measuring the average particle size (D 50 ) is the same as described in the average particle size of silica particles.
  • the sulfur-carbon composite may refer to a composite including a sulfur-containing compound supported on at least a portion of the inner and outer surfaces of the pores of a porous carbon material.
  • the sulfur-containing compound may be located on at least a portion of the inner surface of the pores of the porous carbon material.
  • the inner surface of the pores of the porous carbon material may be the specific surface of the porous carbon material.
  • the sulfur-containing compound may be located on at least a portion of the outer surface of the porous carbon material.
  • the porous carbon material provides a framework on which a sulfur-containing compound, which is a positive electrode active material, can be fixed uniformly and stably, and complements the electrical conductivity of the sulfur-containing compound to enable an electrochemical reaction to proceed smoothly.
  • the sulfur-containing compound may directly contact the surface of the porous carbon material, such as the inner surface of the pores of the porous carbon material, that is, the outer surface of the pores of the porous carbon material and/or the specific surface of the porous carbon material.
  • a sulfur-containing compound in direct contact with the porous carbon material can have a technical effect in which an electrochemical reaction can occur, which makes the silica-coated sulfur-carbon composite suitable for use in electrodes, such as an anode. and can be used in lithium-sulfur batteries.
  • the porous carbon material may be generally manufactured by carbonizing precursors of various carbon materials.
  • the porous carbon material includes irregular pores inside, and the average diameter of the pores may be in the range of 1 to 200 nm, for example, 1 to 100 nm, 10 to 80 nm, or 20 to 50 nm.
  • the average diameter of the pores may be measured according to ISO 15901:2019, known in the art, but is not limited thereto.
  • the porosity (or porosity) of the porous carbon material may be in the range of 10 to 90% of the total volume of the porous carbon material.
  • the porosity of the porous carbon material can be measured according to a method known in the art according to ISO 15901:2019, but the measurement method is not limited thereto.
  • the average diameter and porosity of the pores of the porous carbon material are within the above-mentioned range, not only is impregnation with a sulfur-containing compound possible, but there is also the advantage of securing the mechanical strength of the sulfur-carbon composite and applying it to the manufacturing process of electrodes.
  • the present invention is not limited thereto.
  • the shape of the porous carbon material may be used without limitation as long as it is commonly used in the positive electrode of a lithium sulfur battery, such as spherical, rod, needle, plate, tube, or bulk shape.
  • the porous carbon material may be used without limitation as long as it has a porous structure and is commonly used in the industry.
  • the porous carbon material includes graphene; Carbon black such as Denka black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Carbon nanotubes (CNTs) such as single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs); Carbon fibers such as graphite nanofibers (GNF), carbon nanofibers (CNF), and activated carbon fibers (ACF); Graphite such as natural graphite, artificial graphite, and expanded graphite; It may be activated carbon or two or more of these, but is not limited thereto.
  • Carbon black such as Denka black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black
  • Carbon nanotubes such as single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotube
  • the porous carbon material has a specific surface area of, for example, 300 to 2000 m 2 /g, 400 to 1800 m 2 /g, 450 to 1500 m 2 /g, or 500 to 1200 m 2 /g. It could be.
  • the non-target may be measured according to the BET method according to ISO 15901:2019, known in the art, but is not limited thereto.
  • Porous carbon materials that can have a higher specific surface area can have the effect of reducing the density of the silica-coated sulfur-carbon composite and improving the electrochemical reaction of sulfur-containing compounds.
  • porous carbon materials that may have a specific surface area exceeding the above range may have poor mechanical properties and may no longer be suitable for use in electrodes or lithium-sulfur batteries, but the present invention is not limited thereto. .
  • the type of the sulfur-containing compound supported on the porous carbon material is not particularly limited as long as it can be used as a positive electrode active material for a lithium-sulfur battery.
  • the sulfur-containing compounds include inorganic sulfur (S 8 ), lithium polysulfide (Li 2 S n , 1 ⁇ n ⁇ 8), carbon sulfur polymer (C 2 S x ) m (2.5 ⁇ x ⁇ 50, 2 ⁇ m) or a mixture of two or more of them, but is not limited thereto.
  • the sulfur-containing compound may be inorganic sulfur (S 8 ).
  • the sulfur-carbon composite may include the porous carbon material and the sulfur-containing compound in a weight ratio of 1:9 to 1:1.
  • the weight ratio of the porous carbon material and the sulfur-containing compound in the sulfur-carbon composite is 1:1.5 to 1:7, 1:2 to 1:5, 1:2.5 to 1:4, and 1:2.7 to 1. :3.5, 1:2.8 to 1:3.5 or 1:3.
  • the weight ratio of the porous carbon material and the sulfur-containing compound is within the above-described range, advantageous effects may be shown in terms of reducing resistance of the positive electrode active material layer and improving battery performance, but the present invention is not limited thereto.
  • the concentration of silica may be higher on the external surface compared to the specific surface of the porous carbon material.
  • the inner surface of the pores of the porous carbon material is mostly supported by a sulfur-containing compound.
  • the concentration of silica that can enter the surface (specific surface) inside the pores of the porous carbon material may be lower than the concentration of silica present on the outer surface of the silica-coated sulfur-carbon composite.
  • the silica-coated sulfur-carbon composite can exhibit advantageous effects in terms of excellent fluidity and density.
  • the concentration of silica can be determined by the weight of silica particles divided by each surface. Therefore, the concentration of silica particles on the inner surface of the pores of the porous carbon material can be determined by dividing the weight of the silica particles by the specific surface area of the porous carbon material. The concentration of silica particles on the outer surface of the porous carbon material may be determined by the weight of the silica particles divided by the outer surface of the porous carbon material.
  • the surface of the porous carbon material of the silica-coated sulfur-carbon composite can be estimated by subtracting the amount of the sulfur-containing compound from the silica-coated sulfur-carbon composite.
  • Specific surface area can be determined by BET according to ISO 9277:2010, as known to those skilled in the art. However, the specific surface area measurement method is not limited to this.
  • a method for producing the above-described silica-coated sulfur-carbon composite is provided.
  • the method for producing the silica-coated sulfur-carbon composite includes coating silica particles on at least a portion of the surface of the sulfur-carbon composite.
  • the coating step can be performed by uniformly mixing the sulfur-carbon composite and silica particles.
  • mixing for the coating may be mixing the sulfur-carbon composite and the silica particles at a weight ratio of 99.9:0.1 to 80:20.
  • the sulfur-carbon composite and the silica particles have a range of 99.9:0.1 to 90:10, or 99:1 to 90:10, or 99:1 to 95:5, or 97:3 to 90:10, or It may be mixed at a weight ratio of 99:1 to 97:3.
  • the silica-coated sulfur-carbon composite can achieve low density and improve fluidity, but the present invention is not limited thereto.
  • mixing for the coating may be performed so that the sulfur-carbon composite and silica particles are uniformly distributed.
  • the coating step may include mixing the sulfur-carbon composite and the silica particles in a solid state.
  • the sulfur-carbon composite and the silica particles may be in a powder form, and may be mixed in a solid state by adding the sulfur-carbon composite and the silica particles into a powder mixer.
  • the sulfur-carbon composite and the silica particles are mixed in solid form, the mixing is not limited and can be done by various methods as long as simple mixing of them is possible.
  • mixing for the coating can be performed by adding the materials to a mixer such as a bead mill or acoustic mixer.
  • the mixing for the coating is performed for 60 seconds to 60 minutes, specifically at 1,300 rpm, while stirring in the mixer at 1,000 rpm to 2,000 rpm to ensure uniformity of the silica coating. to 2,000 rpm, or 1,400 rpm to 2,000 rpm, or 1,500 rpm to 2,000 rpm, or 1,000 rpm to 1,500 rpm for 15 minutes to 60 minutes, or 15 minutes to 30 minutes, or 60 seconds to 30 minutes, or 30 minutes to 30 minutes. It may be carried out for 60 minutes, but the mixing time may vary depending on the content of the substances, and the present invention is not limited thereto.
  • mixing for the coating may be performed for, for example, 60 seconds to 60 minutes, specifically 15 minutes to 60 minutes, and more specifically 15 minutes to 30 minutes. In another embodiment of the present invention, mixing for the coating may be performed for, for example, 60 seconds to 30 minutes, or 30 minutes to 60 minutes, but is not limited thereto.
  • the mixing for the coating is performed in a mixer at 1,000 rpm to 2,000 rpm, specifically 1,400 rpm to 2,000 rpm, 1,500 rpm to 2,000 rpm, or 1,000 rpm to ensure uniform mixing. It may be performed at 1,500 rpm, but is not limited thereto.
  • the mixing for the coating is performed, for example, at room temperature (25 ⁇ 1°C) to minimize shape deformation of the sulfur-carbon composite and to uniformly coat the silica particles.
  • room temperature 25 ⁇ 1°C
  • the present invention is not limited thereto.
  • the sulfur-carbon composite and the silica particles are referred to as described above regarding the silica-coated sulfur-carbon composite.
  • the method for producing the silica-coated sulfur-carbon composite may further include preparing the sulfur-carbon composite before coating the silica particles.
  • preparing the sulfur-carbon composite may include mixing the porous carbon material and the sulfur-containing compound.
  • manufacturing the sulfur-carbon composite may include mixing and molding the porous carbon material and the sulfur-containing compound.
  • mixing of the porous carbon material and the sulfur-containing compound can be performed using a commonly used mixer, where the mixing time, temperature, and speed are also optional depending on the content and conditions of the raw materials. It can be performed by adjusting .
  • the step of molding the mixed porous carbon material and the sulfur-containing compound as described above may include heating their mixture.
  • the heating is not particularly limited as long as it is the temperature at which the sulfur-containing compound melts, and may be, for example, heating to a temperature of 110°C to 180°C, specifically 115°C to 180°C.
  • a step of separating the sulfur-carbon complex coated with the silica particles may be further included.
  • the silica-coated sulfur-carbon composite prepared in this way includes a sulfur-carbon composite with improved cohesiveness because at least a portion of the surface is coated with silica, and thus may exhibit improved fluidity.
  • a method for improving the flowability of the above-described silica-coated sulfur-carbon composite is provided.
  • the method of improving the flowability of the silica-coated sulfur-carbon composite includes coating silica particles on at least a portion of the surface of the sulfur-carbon composite.
  • the above-described method for producing the silica-coated sulfur-carbon composite is used.
  • a positive electrode active material including the silica-coated sulfur-carbon composite is provided.
  • the silica coating-sulfur carbon composite itself can be used as a positive electrode active material.
  • the silica coating-sulfur carbon composite may be used as a positive electrode active material along with a sulfur-containing compound, if necessary.
  • an electrode comprising the silica-coated sulfur-carbon composite is provided.
  • the electrode may include a porous carbon material, and each porous carbon material may be coated with silica particles. Additionally, the porous carbon material may be derived from the silica-coated sulfur-carbon composite.
  • the electrode may include a silica-coated sulfur-carbon composite, and in this case, the silica-coated sulfur-carbon composite may include a porous carbon material coated with silica particles. At this time, the silica particles may form a silica coating layer between the porous carbon material and/or the sulfur-carbon composite.
  • the presence of the sulfur-carbon composite or porous carbon material of the silica-coated sulfur-carbon composite may vary depending on whether the electrode is in a charged or discharged state when used in a lithium-sulfur battery.
  • the electrode is a current collector; and an electrode active material layer including a plurality of silica coating-sulfur carbon composites on at least one surface of the current collector.
  • the electrode may be used as at least one of a cathode and an anode for use in a lithium secondary battery.
  • the electrode may be used as a positive electrode for use in a lithium-sulfur battery, but the use of the present invention is not limited thereto.
  • a lithium sulfur battery including the silica coated sulfur-carbon composite is provided.
  • the lithium-sulfur battery includes a positive electrode containing the above-described silica-coated sulfur-carbon composite, a negative electrode containing a negative electrode active material, and an electrolyte solution.
  • the above-described silica-coated sulfur-carbon composite may be included as a carrier for supporting the positive electrode active material on the positive electrode, the positive electrode active material itself, or a conductive material.
  • a lithium-sulfur battery including the above-described silica-coated sulfur-carbon composite can have improved performance.
  • a lithium-sulfur battery containing the silica-coated sulfur composite according to the present invention can have improved capacity. Therefore, the lithium-sulfur battery according to the present invention can have improved performance and capacity.
  • the silica-coated sulfur-carbon composite can improve the dispersibility of the silica-coated sulfur-carbon composite in an electrode, such as a positive electrode, and accordingly, a lithium-sulfur battery using the same can be advantageous in terms of performance and capacity. This may indicate an effect.
  • the above-described effect may be achieved because the formation of aggregates of the silica-coated sulfur-carbon composite on the electrode, such as the anode, is minimized.
  • Performance improvements can be measured by comparing a lithium-sulfur battery comprising a silica coated sulfur-carbon composite as described above to a lithium-sulfur battery comprising a sulfur-carbon composite that is not coated with silica particles.
  • the positive electrode, negative electrode, positive electrode active material, negative electrode active material, and electrolyte may be used without particular limitation as long as they can be used in a lithium sulfur battery within a range that does not impair the purpose of the present invention.
  • the positive electrode may include a positive electrode current collector and a positive electrode active material layer applied to one or both sides of the positive electrode current collector
  • the negative electrode may include a negative electrode current collector and a negative electrode active material layer applied to one or both sides of the negative electrode current collector. may include.
  • the positive electrode current collector supports the positive electrode active material and is not particularly limited as long as it has high conductivity without causing chemical changes in the battery, and the negative electrode current collector supports the negative electrode active material and does not cause chemical changes in the battery. There is no particular limitation as long as it has high conductivity without causing .
  • the negative electrode active material is a material capable of reversibly intercalating or deintercalating lithium (Li + ), or a material capable of reacting with lithium ions to reversibly form a lithium-containing compound. Any material that can be used can be used without particular restrictions.
  • the negative electrode active material may include lithium metal, lithium alloy, or a mixture thereof.
  • the lithium alloy includes, for example, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium ( It may be Ca), strontium (Sr), barium (Ba), radium (Ra), aluminum (Al), tin (Sn), or an alloy of two or more of these metals.
  • the electrolyte solution is not particularly limited as long as it can be used in a lithium-sulfur battery, and may include, for example, a lithium salt and a solvent.
  • the solvent may be, for example, an ether-based compound, a carbonate-based compound, or a mixed solvent thereof, but is not limited thereto.
  • the lithium salt is not limited as long as it can be used in the electrolyte for lithium-sulfur batteries, for example, LiSCN, LiBr, LiI, LiPF 6 , LiBF 4 , LiB 10 Cl 10 , LiSO 3 CF 3 , LiCl, LiClO 4 , LiSO 3 CH 3 , LiB(Ph) 4 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 CF 3 ) 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiFSI, lithium chloroborane, low grade It may include, but is not limited to, lithium aliphatic carboxylic acid or a mixture of two or more thereof.
  • the lithium sulfur battery may further include a separator interposed between the positive electrode and the negative electrode.
  • the separator separates or insulates the anode and the cathode from each other and enables lithium ion transport between the anode and the cathode, and may be made of a porous non-conductive or insulating material.
  • This separator may be an independent member such as a film, or may be a coating layer added to the anode and/or cathode.
  • the material constituting the separator may include, for example, polyolefin such as polyethylene and polypropylene, glass fiber filter paper, silica material, or two or more of these, but is not limited thereto.
  • the shape of the lithium-sulfur battery is not particularly limited, and may be of various shapes such as cylindrical, stacked, or coin-shaped.
  • the method of manufacturing the lithium sulfur battery includes processes such as lamination, stacking, or folding of the separator and electrode in addition to winding, which is a general process for battery manufacturing. may be applied, but is not limited thereto.
  • Sulfur (S 8 )-carbon (CNT) composite (sulfur (S 8 ) raw material: H sulfur corp., carbon (CNT) raw material: Nano C corp, S 8 70 wt%, CNT 30 wt%) 99 parts by weight and silica 1 part by weight of particles ( [ SiO 2 ]
  • silica-coated sulfur-carbon composite was prepared in which silica particles were coated on at least a portion of the surface of the sulfur-carbon composite.
  • the thickness of the silica particle coating was 40 nm to 5 ⁇ m (average 2.5 ⁇ m).
  • Example 1 In addition to mixing 97 parts by weight of the sulfur-carbon composite and 3 parts by weight of silica particles ([SiO 2 ] x [SiO(OH) 2 ] 1-x, 0.5 ⁇ x ⁇ 1 , D 50 15 nm), Example 1 and A silica-coated sulfur-carbon composite was prepared according to the same method.
  • Example 1 In addition to mixing 90 parts by weight of the sulfur-carbon composite and 10 parts by weight of silica particles ([SiO 2 ] x [SiO(OH) 2 ] 1-x, 0.5 ⁇ x ⁇ 1 , D 50 15 nm), Example 1 and A silica-coated sulfur-carbon composite was prepared according to the same method.
  • Example 1 The sulfur-carbon composite itself used in Example 1 was prepared as Comparative Example 1 without mixing silica particles with the sulfur-carbon composite and coating the silica particles on at least a portion of the surface of the sulfur-carbon composite.
  • the average particle size (D 50 ) of the silica particles was measured by the particle size at 50% of the cumulative distribution of particle numbers according to particle size using a particle size analyzer (PSA).
  • PSD 50 particle size analyzer
  • the thickness of the silica particle coating was confirmed through a differential scanning electron microscope (SEM).
  • the sulfur-carbon composite according to Comparative Example 1 which was not coated with silica particles, was confirmed to have a rough surface due to the porosity of the sulfur-carbon composite, whereas Examples 1 and 2 had a rough surface due to the porosity of the sulfur-carbon composite. It was confirmed that silica particles were coated to form a smooth surface.
  • the silica-coated sulfur-carbon composites according to Examples 1 and 2 the surface of Example 2, which had a larger amount of silica particles coated, was confirmed to be smoother.
  • the angle of repose was measured according to the following angle of repose test. The results are shown in Table 1, Figures 2 and 3 below.
  • the funnel was placed at a height of 7.5 cm above the ground, centered and fixed using a level, and then the bottom of the funnel was blocked to prevent the inserted sample from being discharged downward.
  • the bottom of the funnel was opened and the sample was allowed to freely fall and pile up on the disk (diameter 13 cm) located at the bottom.
  • the angle of repose ( ⁇ ) of the stacked sample pile was measured.
  • Rb is the angle of repose of the sulfur-carbon complex before coating
  • Ra is the angle of repose of the silica-coated sulfur-carbon composite.
  • Example 1 Example 2
  • Example 3 Angle of repose (°) 32.6 30.3 25.5
  • zinc oxide (ZnO) was used as follows. An experiment was performed.
  • Sulfur (S 8 )-carbon (CNT) composite for performing Experimental Example 2 (sulfur (S 8 ) raw material: H sulfur corp., carbon (CNT) raw material: Nano C corp, S 8 75 wt%, CNT 25 wt %) was prepared.
  • a zinc oxide-coated sulfur-carbon composite was prepared according to the same method as in Comparative Example 3, except that 95 parts by weight of the sulfur-carbon composite and 5 parts by weight of ZnO were mixed.
  • the sulfur-carbon composite according to Comparative Example 2 without zinc oxide coating was confirmed to have a rough surface due to the porosity of the sulfur-carbon composite.
  • Comparative Example 3 and Comparative Example 4 it was confirmed that some zinc oxide was inserted into the surface of the sulfur-carbon composite due to mixing with zinc oxide, but the zinc oxide was not uniformly coated on the surface, but was agglomerated and attached in many cases. was observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Secondary Cells (AREA)
  • Silicon Compounds (AREA)
PCT/KR2023/004326 2022-05-27 2023-03-30 실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지 Ceased WO2023229200A1 (ko)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202380012754.6A CN117616596A (zh) 2022-05-27 2023-03-30 二氧化硅涂覆的硫碳复合物及包含其的锂硫电池
CA3234875A CA3234875A1 (en) 2022-05-27 2023-03-30 Silica coated sulfur-carbon composite and lithium-sulfur battery comprising the same
JP2024513248A JP7823176B2 (ja) 2022-05-27 2023-03-30 シリカコーティング硫黄－炭素複合体及びこれを含むリチウム硫黄電池
JP2025195494A JP2026031573A (ja) 2022-05-27 2025-11-14 シリカコーティング硫黄－炭素複合体及びこれを含むリチウム硫黄電池

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20220065671 2022-05-27
KR10-2022-0065671 2022-05-27
KR10-2022-0135073 2022-10-19
KR1020220135073A KR20230165673A (ko) 2022-05-27 2022-10-19 실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지
KR10-2023-0042280 2023-03-30
KR1020230042280A KR102654898B1 (ko) 2022-05-27 2023-03-30 실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지

Publications (1)

Publication Number Publication Date
WO2023229200A1 true WO2023229200A1 (ko) 2023-11-30

Family

ID=88919514

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/004326 Ceased WO2023229200A1 (ko) 2022-05-27 2023-03-30 실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지

Country Status (4)

Country Link
JP (2) JP7823176B2 (https=)
KR (1) KR102838227B1 (https=)
CA (1) CA3234875A1 (https=)
WO (1) WO2023229200A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119495704A (zh) * 2025-01-15 2025-02-21 四川大学 一种锂硫电池复合正极及锂硫电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006553A (zh) * 2015-07-11 2015-10-28 中国计量学院 一种硫/碳/氧化物复合电极材料的制备方法
KR20180048309A (ko) * 2016-11-02 2018-05-10 주식회사 엘지화학 황-탄소 복합체 및 이를 포함하는 리튬-황 전지
CN111224076A (zh) * 2018-11-26 2020-06-02 中国科学院大连化学物理研究所 一种抑制锂硫电池中聚硫离子飞梭的电极及制备和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101417347B1 (ko) * 2012-09-24 2014-07-08 현대자동차주식회사 유황 다공성 도전재 나노복합체를 함유한 리튬유황 이차전지용 양극 및 그 제조방법
CN107706360A (zh) 2017-07-25 2018-02-16 深圳市沃特玛电池有限公司 一种锂离子电池复合负极材料的制备方法
CN107768617B (zh) 2017-09-15 2019-04-30 深圳启辰新能源科技有限公司 锂硫电池复合正极材料及其制备方法
EP3869591A1 (en) * 2020-02-19 2021-08-25 Vito NV Method for applying a functional compound on sulphur particles and sulphur particles resulting therefrom

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006553A (zh) * 2015-07-11 2015-10-28 中国计量学院 一种硫/碳/氧化物复合电极材料的制备方法
KR20180048309A (ko) * 2016-11-02 2018-05-10 주식회사 엘지화학 황-탄소 복합체 및 이를 포함하는 리튬-황 전지
CN111224076A (zh) * 2018-11-26 2020-06-02 中国科学院大连化学物理研究所 一种抑制锂硫电池中聚硫离子飞梭的电极及制备和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BRENNAN CAMPBELL, BELL JEFFREY, HOSSEINI BAY HAMED, FAVORS ZACHARY, IONESCU ROBERT, OZKAN CENGIZ S., OZKAN MIHRIMAH: "SiO 2 -coated sulfur particles with mildly reduced graphene oxide as a cathode material for lithium–sulfur batteries", NANOSCALE, ROYAL SOCIETY OF CHEMISTRY, UNITED KINGDOM, vol. 7, no. 16, 18 February 2015 (2015-02-18), United Kingdom , pages 7051 - 7055, XP055275459, ISSN: 2040-3364, DOI: 10.1039/C4NR07663J *
RAJKUMAR P., DIWAKAR K., RADHIKA G., KRISHNAVENI K., SUBADEVI R., SIVAKUMAR M.: "Effect of silicon dioxide in sulfur/carbon black composite as a cathode material for lithium sulfur batteries", VACUUM., PERGAMON PRESS., GB, vol. 161, 1 March 2019 (2019-03-01), GB , pages 37 - 48, XP093112545, ISSN: 0042-207X, DOI: 10.1016/j.vacuum.2018.12.016 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119495704A (zh) * 2025-01-15 2025-02-21 四川大学 一种锂硫电池复合正极及锂硫电池

Also Published As

Publication number Publication date
KR102838227B1 (ko) 2025-07-24
CA3234875A1 (en) 2023-11-30
JP2026031573A (ja) 2026-02-24
JP7823176B2 (ja) 2026-03-03
KR20240050311A (ko) 2024-04-18
JP2024532392A (ja) 2024-09-05

Similar Documents

Publication Publication Date Title
WO2021034109A1 (ko) 규소·산화규소-탄소 복합체, 이의 제조방법 및 이를 포함하는 리튬 이차전지용 음극 활물질
WO2021066458A1 (ko) 복합 음극 활물질, 이의 제조방법, 및 이를 포함하는 음극
WO2017111542A1 (ko) 리튬 이차전지용 음극활물질 및 이를 포함하는 리튬 이차전지용 음극
WO2022139516A1 (ko) 양극 활물질, 그 제조 방법, 이를 포함하는 양극재, 양극 및 리튬 이차 전지
WO2023018187A1 (en) Negative electrode active material, negative electrode including same, secondary battery including same and method for preparing negative electrode active material
WO2021118144A1 (ko) 음극 활물질, 이의 제조방법, 이를 포함하는 음극 및 이차전지
WO2020067793A1 (ko) 황-탄소 복합체 및 그 제조방법
WO2024029802A1 (ko) 리튬이차전지, 전지 모듈 및 전지 팩
WO2021029534A1 (ko) 표면에 인산 음이온이 흡착된 옥시수산화질산철, 이의 제조방법, 상기 표면에 인산 음이온이 흡착된 옥시수산화질산철을 포함하는 리튬 이차전지용 양극 및 이를 포함하는 리튬 이차전지
WO2021034097A1 (ko) 이차전지 및 이의 제조방법
WO2023229200A1 (ko) 실리카 코팅 황-탄소 복합체 및 이를 포함하는 리튬황 전지
WO2023282683A1 (ko) 리튬 이차 전지용 음극, 리튬 이차 전지용 음극의 제조 방법 및 음극을 포함하는 리튬 이차 전지
WO2024123064A1 (ko) 질소 도핑된 고흑연화 다공성 탄소 구조체, 이를 포함하는 리튬-황 전지 및 이의 제조방법
WO2023059039A1 (ko) 전극, 이를 포함하는 이차전지, 및 이의 제조 방법
WO2021096113A1 (ko) 유기 화합물 기반의 리튬 이차 전지 및 그 제조 방법
WO2026014890A1 (ko) 양극 활물질의 제조방법
WO2025264045A1 (ko) 양극 활물질, 이를 포함하는 양극 및 리튬 이차전지
WO2024225854A1 (ko) 양극 활물질, 양극 및 리튬이차전지
WO2025264061A1 (ko) 양극 활물질, 이를 포함하는 양극 및 리튬 이차전지
WO2024215064A1 (ko) 양극재, 이를 포함하는 양극 및 리튬 이차전지
WO2026089365A1 (ko) 양극 활물질 및 이의 제조방법
WO2025259023A1 (ko) 양극 활물질, 양극 및 리튬 이차전지
WO2024225853A1 (ko) 양극 활물질, 양극 및 리튬이차전지
WO2026095636A1 (ko) 양극 활물질, 양극 및 리튬 이차전지
WO2025150844A1 (ko) 양극재, 이를 포함하는 양극 및 리튬 이차전지

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 202380012754.6

Country of ref document: CN

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

Ref document number: 23811977

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024513248

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 3234875

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 202417029230

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23811977

Country of ref document: EP

Kind code of ref document: A1