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WO2018159938A1 - Structure composite de poche de carbone flexible, procédé permettant de fabriquer cette dernière, électrode comprenant cette dernière et dispositif de stockage d'énergie comprenant ladite électrode - Google Patents

Structure composite de poche de carbone flexible, procédé permettant de fabriquer cette dernière, électrode comprenant cette dernière et dispositif de stockage d'énergie comprenant ladite électrode Download PDF

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Publication number
WO2018159938A1
WO2018159938A1 PCT/KR2018/000605 KR2018000605W WO2018159938A1 WO 2018159938 A1 WO2018159938 A1 WO 2018159938A1 KR 2018000605 W KR2018000605 W KR 2018000605W WO 2018159938 A1 WO2018159938 A1 WO 2018159938A1
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WIPO (PCT)
Prior art keywords
carbonaceous
composite structure
sheet
pocket
flexible carbon
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Ceased
Application number
PCT/KR2018/000605
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English (en)
Korean (ko)
Inventor
강정구
원종호
정형모
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Korea Advanced Institute of Science and Technology KAIST
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Korea Advanced Institute of Science and Technology KAIST
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Priority claimed from KR1020170111350A external-priority patent/KR102062550B1/ko
Application filed by Korea Advanced Institute of Science and Technology KAIST filed Critical Korea Advanced Institute of Science and Technology KAIST
Priority to EP18760706.4A priority Critical patent/EP3550645A4/fr
Priority to CN201880005706.3A priority patent/CN110168786B/zh
Priority to JP2018516477A priority patent/JP6641466B2/ja
Priority to US15/937,914 priority patent/US10985364B2/en
Publication of WO2018159938A1 publication Critical patent/WO2018159938A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • 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 application provides a flexible carbon pocket composite structure including various particles enclosed in a flexible carbon pocket formed by carbonaceous sheets, a method of manufacturing the flexible carbon pocket composite structure, an electrode including the flexible carbon pocket composite structure, and An energy storage device and the like including the electrode.
  • LIBs lithium ion batteries
  • anode material must be scalable and precisely controlled for further processing for commercialization, as well as be able to be used with representative cathode materials for practical full-cell devices.
  • the newly proposed material design methodology should be able to be applied directly to current industrial structures and be realized in the near future.
  • silicon (Si) with a high theoretical capacity of more than 3,500 mAh / g is considered the most promising candidate to replace graphite (372 mah / g).
  • the specific capacitance of the silicon anode which is almost ten times higher than the specific capacitance of graphite, can reduce the weight of the anode side, allowing extraction of the maximum energy density from the full-cell arrangement of LIB.
  • the problems resulting from volume changes during operation are the biggest problem for silicon-based materials.
  • the present application provides a flexible carbon pocket composite structure including various particles enclosed in a flexible carbon pocket formed by carbonaceous sheets, a method of manufacturing the flexible carbon pocket composite structure, an electrode including the flexible carbon pocket composite structure, and the An energy storage device or the like including an electrode is provided.
  • a first aspect of the present disclosure is a flexible carbon pocket, comprising a composite comprising particles enclosed by each of the at least one carbonaceous first pocket formed by a carbonaceous first sheet and a carbonaceous second sheet facing each other. Provide a complex structure.
  • a second aspect of the present disclosure provides an electrode comprising the flexible carbon pocket composite structure of the first aspect of the present disclosure.
  • a third aspect of the present disclosure provides an energy storage device comprising the electrode of the second aspect of the present disclosure.
  • a fourth aspect of the present application provides a method of making the flexible carbon pocket composite structure of the first aspect of the present application, comprising:
  • a layered composite containing particles, polymers and carbonaceous sheets, said layered composite being one or more between two opposing carbonaceous sheets represented by a carbonaceous first sheet and a carbonaceous second sheet.
  • the particles are disposed and the particles are connected by the polymer;
  • the flexible carbon pocket composite structure according to the embodiments herein may be one having good dispersibility in a solvent.
  • the flexible carbon pocket composite structure may have excellent dispersibility in various organic solvents such as water, alcohols, organic solvents, and the like.
  • the flexible carbon pocket composite structure is remarkably compared to the dispersibility of carbon-based materials such as graphene. By having excellent dispersibility, it can be easily applied to the production of electrodes and various devices.
  • Embodiments herein may provide a flexible carbon pocket composite structure comprising silicon and / or other various particle or electrode materials, and applying the flexible carbon pocket composite structure as an anode or cathode of various energy storage devices. This can significantly improve the performance of the energy storage device. Specifically, compared with the case of using only activated carbon in the conventional lithium anode, when manufacturing the electrode using the flexible carbon pocket composite structure, the electrode has a high electrochemical reduction potential, high energy density, non-capacitance specific capacity and weight efficiency (Wh / kg) can be achieved.
  • the flexible carbon pocket composite structure herein is applied as a lithium anode when it contains Si particles to improve electrical conductivity while providing voids provided by the pupils in the flexible carbon pocket composite structure.
  • the void space can accommodate the volume expansion of silicon that occurs during repeated charge / discharge cycles, thereby preventing expansion and pulverization of many active materials for energy storage, and providing excellent charge and discharge rates. rate characteristic) can be achieved.
  • the method for producing the flexible carbon pocket composite structure allows a variety of particles such as silicon particles and carbonaceous sheets such as graphene to be laminated by a polymer and also in a grinding process such as the ball-milling process. Since the layered composite structure of the silicon particles and the graphene sheet can be safely maintained, the flexible carbon pocket composite structure can be mass-produced at high speed without damaging the silicon and graphene active material for lithium anode.
  • 1A is a cross-sectional view of a flexible carbon pocket composite structure in one embodiment of the present disclosure.
  • FIG. 1B is a perspective view of a flexible carbon pocket composite structure in one embodiment of the present disclosure.
  • FIG. 1C is a schematic diagram of a manufacturing process of a graphene flexible carbon pocket composite structure containing silicon nanoparticles according to one embodiment of the present disclosure, and manufactured for a flexible carbon pocket composite structure containing silicon nanoparticles using ECA. Schematic diagram of the process.
  • 1D is a 50 mL scale batch for Si_GPP preparation, in one embodiment of the present disclosure.
  • FIG. 1E is a 500 mL scale batch for preparing Si_GPP using 3.5 g of silicon nanoparticles, 1.5 g of graphene, and 150 g of ECA, in one embodiment of the present disclosure.
  • 1F is a TEM image of a flexible carbon pocket composite structure in one embodiment of the present disclosure.
  • 1G is a TEM image of a flexible carbon pocket composite structure in one embodiment of the present disclosure.
  • FIG. 2a in one embodiment of the present application, a schematic diagram of the anion polymerization process of ECA in the presence of graphene and Si nanoparticles.
  • FIG. 2B is an MALDI-TOF spectrum of poly ECA according to graphene + Si nanoparticles: ECA content ratio and Si_ECA_G sample conditions in a polymerization process.
  • FIG. 2C is a schematic diagram of a manufacturing process of a graphene flexible pocket composite structure containing silicon nanoparticles in an embodiment of the present disclosure.
  • Figure 3 in one embodiment of the present application, as a result of the structural analysis of the Si nanoparticles and graphene composite, a) and b) SEM image of Si_GPP, c) cross section of Si_GPP, d) using the BSE mode
  • the cross section of Si_GPP, e) is a TEM image of Si_GPP, f) is a STEM image of Si_GPP, g) is an element mapping image of Si_GPP, and h) is a high resolution STEM image of Si nanoparticles of Si_GPP.
  • FIG. 4A is an initial charge-discharge profile of a Si_GPP electrode with varying proportions of silicon content and pre-lithiation conditions, as a result of electrochemical performance analysis of Si_GPP half-cells in one embodiment of the present disclosure.
  • FIG. 4B is an electrochemical performance analysis result of Si_GPP half-cell in one embodiment of the present application, and is a result of comparing specific capacitance and initial coulombic efficiency of Si_GPP electrodes using various manufacturing conditions.
  • FIG. 4C is a voltage profile for 7: 3 Si_GPP as a function of various current densities of 200 mA / g to 20 A / g, as a result of electrochemical performance analysis of Si_GPP half-cells, in one embodiment of the present disclosure.
  • FIG. 4D is an electrochemical performance analysis of Si_GPP half-cell, in one embodiment of the present application, at capacity retention at various current densities of 0.1 A / g to 20 A / g and 5 A / g after capacity retention. Cycle performance analysis results.
  • FIG. 5 is an electrochemical performance analysis of a full-cell using Si_GPP and a representative commercial anode in one embodiment of the present application, where FIG. 5A is a schematic diagram of a full-cell arrangement, and FIG. 5B is half- The voltage profile of the cathode and anode in the cell arrangement.
  • 5 c is a voltage profile of a full-cell array using Si_GPP anodes and various cathodes, and d in FIG. 5 shows the cycle performance of full-cell using LCO, LMO, and LFP and Si_GPP.
  • 5E is a graph comparing the function of the cathode material and the energy density of full-cell using Si_GPP and graphite.
  • FIG. 6 is a schematic diagram of before and after base etching of Si_ECA_G and a Back Scattered Electron (BSE) SEM image according to one embodiment of the present application, a) schematic diagram of Si_ECA_G before base etching, b) BSE image of Si_ECA_G before base etching, ) Schematic of Si_ECA_G after base etching, and d) BSE image of Si_ECA_G after base etching.
  • BSE Back Scattered Electron
  • FIG. 7 is a thermogravimetric analysis (TGA) result of Si_ECA_G obtained at 10 ° C./min rise rate under an argon atmosphere in one embodiment of the present disclosure.
  • FIG. 8 relates to a mass-produced Si_GPP in one embodiment of the present application, wherein FIGS. 8A and 8B are SEM images, FIG. 8C is a STEM image, and FIG. d) and (e) are STEM element mapping images.
  • FIG. 9 is an XRD (X-ray diffraction analysis) pattern of Si_GPP, silicon nanoparticles, and graphene in one embodiment of the present application.
  • Si_GPP and Si_ECA_G are Raman spectrum of Si_GPP and Si_ECA_G in one embodiment of the present application.
  • FIG. 11 is an X-ray photoelectron spectroscopy (XPS) of Si_GPP and Si_ECA_G, and N1s spectra from Cyanogen of ECA (inset) in one embodiment of the present application.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 12 is a TGA (Thermogravimetric Analysis) measurement result of silicon nanoparticles in Si_GPP according to silicon dosage according to an embodiment of the present disclosure.
  • FIG. 14 is a schematic and photograph of an electrical circuit for a pre-lithiation process, in one embodiment of the present disclosure.
  • 15 is a charge-discharge profile of a silicon nanoparticle and silicon + graphene mixture (7: 3 ratio, no GPP structure) in one embodiment of the present application.
  • 16 is a charge-discharge operating profile of a graphite based full-cell, in one embodiment of the present disclosure.
  • 17 is a result of analyzing the cycle performance of the graphite-based full-cell in one embodiment of the present application.
  • step to or “step of” does not mean “step for.”
  • the term "combination (s) thereof" included in the representation of a makushi form refers to one or more mixtures or combinations selected from the group consisting of the components described in the representation of makushi form, It means to include one or more selected from the group consisting of the above components.
  • a first aspect of the present disclosure is a flexible carbon pocket composite, comprising a composite comprising particles enclosed by each of the at least one carbonaceous first pocket formed by a carbonaceous first sheet and a carbonaceous second sheet facing each other. Provide a structure.
  • the mutually opposed carbonaceous first sheet and the carbonaceous second sheet are in contact with each other in at least one region, the carbonaceous first sheet and the carbonaceous second sheet is in contact with each other
  • One or more regions that are not provided may each form the carbonaceous first pocket, but are not limited thereto (see FIG. 1A).
  • the one or more carbonaceous first pockets may be formed spaced apart from each other, but is not limited thereto.
  • the carbonaceous first pocket may be a closed type or partially closed type, but is not limited thereto.
  • the carbonaceous first pocket may, but is not limited to, lapping or partially wrapping the surface of the particles enclosed by it.
  • the carbonaceous first sheet and the carbonaceous second sheet are each independently graphene, graphite, carbon nanotubes, carbon fiber, carbon black, activated carbon, graphene oxide (GO), or It may include, but is not limited to, a sheet containing reduced graphene oxide (rGO).
  • each of the carbonaceous first sheet and the carbonaceous second sheet may have a wrinkle (wrinkle), but is not limited thereto.
  • the carbonaceous first sheet and the carbonaceous second sheet may be flexible in itself, such as a graphene sheet, and the carbonaceous first sheet and the carbonaceous second sheet may have wrinkles.
  • the flexibility may further increase and have elasticity, such that the carbonaceous first pocket may have excellent flexibility, elasticity, and the like, and the flexible carbon pocket composite structure may have excellent flexibility, elasticity, and the like.
  • the corrugated (s) are formed in at least one region in which the mutually opposing carbonaceous first sheet and the carbonaceous second sheet are in contact with each other to form the carbonaceous agent.
  • One pocket may have excellent flexibility, elasticity, and the like, and the flexible carbon pocket composite structure may have excellent flexibility, elasticity, and the like.
  • the mutually opposed carbonaceous first sheet and the carbonaceous second sheet are in contact with each other in at least one region, the carbonaceous first sheet and the carbonaceous second sheet is in contact with each other
  • One or more regions which are not provided may be each forming the carbonaceous first pocket, but are not limited thereto.
  • two or more of the composites included in the flexible carbon pocket composite structure when two or more of the composites included in the flexible carbon pocket composite structure, two or more of the composites contact each other by mutual contact of the carbonaceous first pockets included in each of the composites It may be, but is not limited thereto.
  • the flexible carbon pocket composite structure may include, but is not limited to, a carbonaceous second pocket that encloses one or more of the composites (see FIG. 1B).
  • the carbonaceous second pocket includes a carbonaceous sheet containing graphene, graphite, carbon nanotubes, carbon fibers, carbon black, activated carbon, graphene oxide (GO), or reduced graphene oxide (rGO). May be, but is not limited thereto.
  • the flexible carbon pocket composite structure may have a porosity, but is not limited thereto.
  • the carbonaceous second pocket may include a plurality of carbonaceous sheets, but is not limited thereto.
  • the particles may be semiconductor, conductive or insulating, but is not limited thereto.
  • the particles may include an electrode material material, but are not limited thereto.
  • the particles or the electrode material material can be used without particular limitation materials known in the art, for example, Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn , Al, Co, Ni, Ti, Te, Mn, Fe, W, Ag, Au, Pt, V, Cu, Ga, P, and S may include one or more elements selected from the group consisting of, but It is not limited.
  • the electrode material material may include, but is not limited to, the one or more elements or compounds thereof, or an alloy of the two or more elements.
  • the weight ratio of the carbonaceous sheets and the particles is not particularly limited, for example, may be about 1: 0.001 or more, but is not limited thereto.
  • the weight ratio of the carbonaceous sheets and the particles is about 1: 0.001 or more, about 1: 0.001 to 1,000, about 1: 0.001 to 500, about 1: 0.001 to 100, about 1: 0.001 to 10, about 1: 0.01 to 1,000, about 1: 0.01 to 500, about 1: 0.01 to 100, about 1: 0.01 to 10, about 1: 0.1 to 1,000, about 1: 0.1 to 500, about 1: 0.1 to 10, or about 1: 0.1 to 10, but is not limited thereto.
  • the particles may be nanoparticles or have a size of about 1 ⁇ m or less, but may not be limited thereto.
  • the particle size may be about 1,000 nm or less, about 100 nm or less, about 10 nm or less, or about 1 nm or less, but may not be limited thereto.
  • the particle size may be about 1,000 nm or less, about 500 nm or less, about 100 nm or less, about 10 nm or less, about 5 nm or less, about 1 nm or less, about 1 nm to about 1,000 nm, about 1 nm.
  • the size of the flexible carbon pocket composite structure may be determined by the size of the particles surrounded by the structure or the size of the carbonaceous sheet forming the carbonaceous first pocket, but is not limited thereto. It is not that.
  • the size of the flexible carbon pocket composite structure may be greater than or equal to the size of the particles encapsulated by the structure, or may be equal to or larger than the size of the carbonaceous sheet forming the carbonaceous first pocket, but is not limited thereto. no.
  • the size of the flexible carbon pocket composite is equal to or equal to the sum of the particle size and the thickness of the carbonaceous second pocket. It may be more than, but is not limited thereto.
  • the height of the flexible carbon pocket composite structure may be determined in consideration of the particle size and / or the thickness of the carbonaceous second pocket, and the width of the flexible carbon pocket composite structure is the carbonaceous first pocket. It may be determined in consideration of the width of the carbonaceous sheet and / or the thickness of the carbonaceous second pocket to form a, but is not limited thereto.
  • the size of the flexible carbon pocket composite structure may be one having a size of nanometer to micrometer or more, but is not limited thereto.
  • the size of the flexible carbon pocket composite structure is not particularly limited and may be adjusted according to the size of the carbonaceous natto sheet forming the flexible carbon pocket composite structure and the stacking of the composites.
  • the size of the flexible carbon pocket composite structure may be about 100 ⁇ m or less, about 10 ⁇ m or less, about 1 ⁇ m or less, about 800 nm or less, about 600 nm or less, about 500 nm or less, about 400 nm or less, about 300 nm or less, about 200 nm or less, about 100 nm or less, about 50 nm or less, about 10 nm or less, about 10 nm to about 100 ⁇ m, about 10 nm to about 50 ⁇ m, about 10 nm to about 10 ⁇ m, about 10 nm To about 1 ⁇ m, about 10 nm to 500 nm, about 10 nm to about 100 nm, about 100 nm to about 100 ⁇ m, about 100 nm to about 50 ⁇ m, about 100 nm to about 10 ⁇ m, or about 100 nm to about 1 ⁇ m, but may not be limited thereto.
  • the flexible carbon pocket composite structure may be one having excellent dispersibility in a solvent.
  • the flexible carbon pocket composite structure may have excellent dispersibility in various organic solvents such as water, alcohols, organic solvents, and the like.
  • the flexible carbon pocket composite structure is remarkably compared to the dispersibility of carbon-based materials such as graphene. By having excellent dispersibility, it can be easily applied to the production of electrodes and various devices.
  • the zeta potential of the flexible carbon pocket composite structure can be measured by a method known in the art, it is easy for those skilled in the art that the value may vary depending on the type of solvent. I can understand it.
  • the zeta potential of the flexible carbon pocket composite structure can be about +10 mV or more or about -10 mV or less so that the flexible carbon pocket composite structure has good dispersibility in a solvent.
  • the zeta potential of the flexible carbon pocket composite structure may be about +10 mV or more or about -10 mV or less, about +20 mV or more or about -20 mV or less, about +30 mV or more, or about -30 mV or less, About +50 mV or more or about -50 mV or less, about +60 mV or more or about -60 mV or less, about +80 mV or more or about -80 mV or less, about +100 mV or more or about -100 mV or less, about ⁇ 10 mV to about ⁇ 100 mV, about ⁇ 10 mV to about ⁇ 80 mV, about ⁇ 10 mV to about ⁇ 60 mV, or about ⁇ 10 mV to about ⁇ 40 mV, but may not be limited thereto.
  • a second aspect of the present disclosure provides an electrode comprising the flexible carbon pocket composite structure according to the first aspect of the present disclosure.
  • the electrode may be used as an anode or a cathode, but is not limited thereto.
  • a third aspect of the present application provides an energy storage device comprising an electrode according to the second aspect of the present application comprising the flexible carbon pocket composite structure.
  • the electrode may be used as an anode or a cathode of the energy storage device, but is not limited thereto.
  • the energy storage device may be a battery or a capacitor, or a battery-capacitor hybrid, but is not limited thereto.
  • the energy storage device may be a lithium ion battery, sodium ion battery, lithium air battery, sodium air battery, lithium metal battery, sodium metal battery, lithium ion hybrid capacitor, or sodium ion hybrid capacitor. However, it is not limited thereto.
  • the particles as Si, Fe, Ni, Co, Al, Ge, Sn, Mn, Ti, V, Cu, Zn, W, Ag, Pt, Ga, P, Au, Sb, Te
  • the electrode material including at least one element selected from the group consisting of Pb, Bi, and Cd may be used as an anode, but may not be limited thereto.
  • the particles may include, but may not be limited to, the elements, compounds or alloys containing the elements.
  • the electrode material including S as the particles may be used as a cathode, but may not be limited thereto.
  • the particles may be alloyed with other metal components that may be used as the electrode material, but may not be limited thereto.
  • the electrode of the second aspect of the present application and the energy storage device of the third aspect of the present application will be described, and the contents described for the first aspect of the present disclosure will be described for the first aspect of the present disclosure, even if the description is omitted below. Both can be applied to the second aspect of the present application and the third aspect of the present application.
  • the flexible carbon pocket composite structure includes a composite comprising particles enclosed by each of at least one carbonaceous first pocket formed by a carbonaceous first sheet and a carbonaceous second sheet facing each other. It may include.
  • the mutually opposed carbonaceous first sheet and the carbonaceous second sheet are in contact with each other in at least one region, the carbonaceous first sheet and the carbonaceous second sheet is in contact with each other
  • One or more regions which are not provided may be each forming the carbonaceous first pocket, but are not limited thereto.
  • the one or more carbonaceous first pockets may be formed spaced apart from each other, but is not limited thereto.
  • the carbonaceous first pocket may be a closed type or partially closed type, but is not limited thereto.
  • the carbonaceous first pocket may, but is not limited to, lapping or partially wrapping the surface of the particles enclosed by it.
  • the carbonaceous first sheet and the carbonaceous second sheet are each independently graphene, graphite, carbon nanotubes, carbon fiber, carbon black, activated carbon, graphene oxide (GO), or It may include, but is not limited to, a sheet containing reduced graphene oxide (rGO).
  • each of the carbonaceous first sheet and the carbonaceous second sheet may have a wrinkle (wrinkle), but is not limited thereto.
  • the carbonaceous first sheet and the carbonaceous second sheet may be flexible in itself, such as a graphene sheet, and the carbonaceous first sheet and the carbonaceous second sheet may have wrinkles.
  • the flexibility may further increase and have elasticity, such that the carbonaceous first pocket may have excellent flexibility, elasticity, and the like, and the flexible carbon pocket composite structure may have excellent flexibility, elasticity, and the like.
  • the corrugated (s) are formed in at least one region in which the mutually opposing carbonaceous first sheet and the carbonaceous second sheet are in contact with each other to form the carbonaceous agent.
  • One pocket may have excellent flexibility, elasticity, and the like, and the flexible carbon pocket composite structure may have excellent flexibility, elasticity, and the like.
  • the mutually opposed carbonaceous first sheet and the carbonaceous second sheet are in contact with each other in at least one region, the carbonaceous first sheet and the carbonaceous second sheet is in contact with each other
  • One or more regions which are not provided may be each forming the carbonaceous first pocket, but are not limited thereto.
  • two or more of the composites included in the flexible carbon pocket composite structure when two or more of the composites included in the flexible carbon pocket composite structure, two or more of the composites contact each other by mutual contact of the carbonaceous first pockets included in each of the composites It may be, but is not limited thereto.
  • the flexible carbon pocket composite structure may include, but is not limited to, a carbonaceous second pocket that encloses one or more of the composite.
  • the carbonaceous second pocket includes a carbonaceous sheet containing graphene, graphite, carbon nanotubes, carbon fibers, carbon black, activated carbon, graphene oxide (GO), or reduced graphene oxide (rGO). May be, but is not limited thereto.
  • the flexible carbon pocket composite structure may have a porosity, but is not limited thereto.
  • the carbonaceous second pocket may include a plurality of carbonaceous sheets, but is not limited thereto.
  • the particles may be semiconductor, conductive or insulating, but is not limited thereto.
  • the particles may include an electrode material material, but are not limited thereto.
  • the particles or the electrode material material can be used without particular limitation materials known in the art, for example, Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn , Al, Co, Ni, Ti, Te, Mn, Fe, W, Ag, Au, Pt, V, Cu, Ga, P, and S may include one or more elements selected from the group consisting of, but It is not limited.
  • the electrode material material may include, but is not limited to, the one or more elements or compounds thereof, or an alloy of the two or more elements.
  • the weight ratio of the carbonaceous sheets and the particles is not particularly limited, for example, may be about 1: 0.001 or more, but is not limited thereto.
  • the weight ratio of the carbonaceous sheets and the particles is about 1: 0.001 or more, about 1: 0.001 to 1,000, about 1: 0.001 to 500, about 1: 0.001 to 100, about 1: 0.001 to 10, about 1: 0.01 to 1,000, about 1: 0.01 to 500, about 1: 0.01 to 100, about 1: 0.01 to 10, about 1: 0.1 to 1,000, about 1: 0.1 to 500, about 1: 0.1 to 10, or about 1: 0.1 to 10, but is not limited thereto.
  • the particles may be nanoparticles or have a size of about 1 ⁇ m or less, but may not be limited thereto.
  • the particle size may be about 1,000 nm or less, about 100 nm or less, about 10 nm or less, or about 1 nm or less, but may not be limited thereto.
  • the particle size may be about 1,000 nm or less, about 500 nm or less, about 100 nm or less, about 10 nm or less, about 5 nm or less, about 1 nm or less, about 1 nm to about 1,000 nm, about 1 nm.
  • the size of the flexible carbon pocket composite structure may be determined by the size of the particles surrounded by the structure or the size of the carbonaceous sheet forming the carbonaceous first pocket, but is not limited thereto. It is not that.
  • the size of the flexible carbon pocket composite structure may be greater than or equal to the size of the particles encapsulated by the structure, or may be equal to or larger than the size of the carbonaceous sheet forming the carbonaceous first pocket, but is not limited thereto. no.
  • the size of the flexible carbon pocket composite is equal to or equal to the sum of the particle size and the thickness of the carbonaceous second pocket. It may be more than, but is not limited thereto.
  • the height of the flexible carbon pocket composite structure may be determined in consideration of the particle size and / or the thickness of the carbonaceous second pocket, and the width of the flexible carbon pocket composite structure is the carbonaceous first pocket. It may be determined in consideration of the width of the carbonaceous sheet and / or the thickness of the carbonaceous second pocket to form a, but is not limited thereto.
  • the size of the flexible carbon pocket composite structure may be one having a size of nanometer to micrometer or more, but is not limited thereto.
  • the size of the flexible carbon pocket composite structure is not particularly limited and may be adjusted according to the size of the carbonaceous natto sheet forming the flexible carbon pocket composite structure and the stacking of the composites.
  • the size of the flexible carbon pocket composite structure may be about 100 ⁇ m or less, about 10 ⁇ m or less, about 1 ⁇ m or less, about 800 nm or less, about 600 nm or less, about 500 nm or less, about 400 nm or less, about 300 nm or less, about 200 nm or less, about 100 nm or less, about 50 nm or less, about 10 nm or less, about 10 nm to about 100 ⁇ m, about 10 nm to about 50 ⁇ m, about 10 nm to about 10 ⁇ m, about 10 nm To about 1 ⁇ m, about 10 nm to 500 nm, about 10 nm to about 100 nm, about 100 nm to about 100 ⁇ m, about 100 nm to about 50 ⁇ m, about 100 nm to about 10 ⁇ m, or about 100 nm to about 1 ⁇ m, but may not be limited thereto.
  • the flexible carbon pocket composite structure may be one having excellent dispersibility in a solvent.
  • the flexible carbon pocket composite structure may have excellent dispersibility in various organic solvents such as water, alcohols, organic solvents, and the like.
  • the flexible carbon pocket composite structure is remarkably compared to the dispersibility of carbon-based materials such as graphene. By having excellent dispersibility, it can be easily applied to the production of electrodes and various devices.
  • the zeta potential of the flexible carbon pocket composite structure can be measured by a method known in the art, it is easy for those skilled in the art that the value may vary depending on the type of solvent. I can understand it.
  • the zeta potential of the flexible carbon pocket composite structure can be about +10 mV or more or about -10 mV or less so that the flexible carbon pocket composite structure has good dispersibility in a solvent.
  • the zeta potential of the flexible carbon pocket composite structure may be about +10 mV or more or about -10 mV or less, about +20 mV or more or about -20 mV or less, about +30 mV or more or about -30 mV, About +50 mV or more or about -50 mV or less, about +60 mV or more or about -60 mV or less, about +80 mV or more or about -80 mV or less, about +100 mV or more or about -100 mV or less, about ⁇ 10 mV to about ⁇ 100 mV, about ⁇ 10 mV to about ⁇ 80 mV, about ⁇ 10 mV to about ⁇ 60 mV, or about ⁇ 10 mV to about ⁇ 40 mV, but may not be limited thereto.
  • the energy storage device may be a battery or a capacitor, or a battery-capacitor hybrid, but may not be limited thereto.
  • the energy storage device may be a lithium ion battery, sodium ion battery, lithium air battery, sodium air battery, lithium metal battery, sodium metal battery, lithium ion hybrid capacitor, or sodium ion hybrid capacitor. However, this may not be limited.
  • An energy storage device may include the electrode material as an anode and / or a cathode, and may include an electrolyte, but may not be limited thereto.
  • the anode and / or cathode apply or paste the carbonaceous structure onto a foil of gold, such as a Cu foil. It may be formed by a method known in the art, such as, but may not be limited thereto.
  • An energy storage device may include the electrode as an anode and / or a cathode and include an electrolyte and a separator, but may not be limited thereto.
  • the electrolyte and the separator can be used without particular limitation those appropriately selected by those skilled in the art.
  • the separator is commonly used in lithium ion batteries, lithium ion hybrid capacitors, and the like, and is a component that separates the cathode and the anode to prevent electrical contact between electrodes. Permeability and current blocking characteristics are required.
  • the separator is positioned between the anode and the cathode to prevent a short circuit, and may be used without particular limitation that is commonly used in the art.
  • the main material of the separator for example, PE, PP, PE / PP laminated structure or PE / PP phase separation structure, but is not limited thereto.
  • the separator may be a porous polymer membrane, which serves as a conduit for lithium ions reciprocating between the electrodes.
  • the cathode, anode, and separator may together form a “battery stack”.
  • the battery stack and electrolyte are hermetically sealed in a metallic cell casing, which also provides contact with external circuitry.
  • the electrode material may be selected based on combinations known in the art as cathode active materials and anode active materials and their miscibility with selected electrolytes.
  • the active material may be applied in the form of a suspension of nanoparticles having an average particle size (eg, diameter) in the range of about 10 nm to about 1000 nm, but is not limited thereto, and some materials may be in an appropriate size range. Commercially available.
  • the electrolyte is a component that facilitates ion exchange between the anode and the cathode.
  • the ionic liquid electrolyte or the gel polymer electrolyte having low volatility and flammability is mainly used, but is not limited thereto.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • organic solvent examples include ester solvents such as methyl acetate, ethyl acetate, butyrolactone, and caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a C 2 to C 20 linear, branched or cyclic hydrocarbon group, which may include a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • LiPF 6 -EC / DEC as the liquid electrolyte
  • LiBF 4 + PEO as the solid polymer electrolyte
  • LiPF 6 -EC / DMC + PVdF-HFP as the gel polymer electrolyte
  • LiTFSI-EMITFSI as the ionic liquid electrolyte
  • the carbonaceous structure according to an embodiment of the present application has a high specific surface area and high porosity, and thus, when used as an electrode material of the energy storage device, the carbonaceous structure is easy to move and store ions and has many active sites. It has the effect of realizing power density and excellent charge / discharge capacity ratio.
  • the particles included in the flexible carbon pocket composite structure is Sb, Pb, Bi, Zn, Al
  • the conventional lithium anode contains only active carbon Since it has a high electrochemical reduction potential in comparison with the case, it can have a high energy density, specific capacity and weight efficiency (Wh / kg), and in terms of stability, it is included in the flexible carbon pocket composite structure Due to the flexibility, elasticity, etc.
  • the electrolyte is a component that facilitates ion exchange between the anode and the cathode.
  • the ionic liquid electrolyte or the gel polymer electrolyte having low volatility and flammability is mainly used, but is not limited thereto.
  • LiPF 6 -EC / DEC as the liquid electrolyte
  • LiBF 4 + PEO as the solid polymer electrolyte
  • LiPF 6 -EC / DMC + PVdF-HFP as the gel polymer electrolyte
  • LiTFSI-EMITFSI LiTFSI-EMITFSI
  • a fourth aspect of the present application provides a method of making the flexible carbon pocket composite structure of the first aspect of the present application, comprising:
  • the method for producing the flexible carbon pocket composite structure in (b), before the heat treatment of the layered composite, after pulverizing the layered composite to form a particle body of the layered composite
  • it may further include forming a carbonaceous second pocket that encloses one or more of the composite, but is not limited thereto.
  • the polymer may be removed by heat treatment including heating at a temperature capable of decomposing or evaporating the polymer, or may be removed using a suitable solvent capable of dissolving the polymer.
  • the present invention is not limited thereto.
  • the heating temperature and the solvent for the removal of the polymer may be appropriately selected and used by those skilled in the art according to the specific kind of the polymer used.
  • the pulverization of the layered composite is used to mass-produce the flexible carbon pocket composite structure, but may be performed using a ball-milling, grinding, blender or sieve, It is not limited to this.
  • the grinding may be performed in a short time within about 1 hour to pulverize the layered composite and to granulate to form a particle body of the layered composite in which a plurality of the particles are aggregated, and thus, the flexible carbon pocket in a short time.
  • Complex structures can be mass produced.
  • the method of manufacturing the flexible carbon pocket composite structure allows various particles such as silicon particles and the like and carbonaceous sheets such as graphene to be laminated by a polymer and also pulverization such as the ball-milling process. Since the layered composite structure of the silicon particles and the graphene sheet can be safely maintained in the process, the flexible carbon pocket composite structure can be mass-produced at high speed without damage to the silicon and graphene active material for lithium anode.
  • the carbonaceous first sheet and the carbonaceous second sheet may be formed by a process including connecting the carbonaceous first sheet by the polymer, but is not limited thereto.
  • the method for producing the flexible carbon pocket composite structure in the (a), the polymer forming monomer is polymerized on the surface of each of the carbonaceous sheets and the surface of each of the particle (s)
  • the carbonaceous first sheet and the carbonaceous second sheet and the at least one particle may be connected by the polymer, but is not limited thereto.
  • the monomer for forming the polymer in the (a) may be to include an anionic polymerizable monomer, but is not limited thereto.
  • the polymer in (a) may be formed by polymerizing the anionic polymerizable monomer, if necessary may further use a polymerization initiator, but is not limited thereto.
  • the polymerization initiator may be used without particular limitation those known in the art.
  • the anionic polymerizable monomer for polymer formation may be used without particular limitation those known in the art, for example, C 1-10 alkyl cyanoacrylate; Acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, sulfopropyl acrylate or methacrylate or other water soluble forms or other polymerizable carboxylic or sulfonic acids, sulfomethylated It may include, but is not limited to, base addition salts such as acrylamide, allyl sulfonate, styrene sulfonic acid, sodium vinyl sulfonate.
  • base addition salts such as acrylamide, allyl sulfonate, styrene sulfonic acid, sodium vinyl sulfonate.
  • the C 1-10 alkyl included in the C 1-10 alkyl cyanoacrylate is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or these It may include all possible isomers of linear or branched.
  • the method for producing the flexible carbon pocket composite structure in the (a), the polymer monomer by the moisture present on the surface of each of the carbonaceous sheets and the surface of each of the particles It may be polymerized, but is not limited thereto.
  • the solvent in (a), is removed by evaporation by the heat of reaction generated during the polymerization of the polymer monomer, or removed after the polymerization to remove the pores (pore) in the flexible carbon pocket composite structure It may be formed, but is not limited thereto.
  • the solvent in (a), may be one having a boiling point of 100 °C or less as it can dissolve the polymer, but is not limited thereto.
  • the solvent may be, for example, methanol, isopropyl alcohol, or other alcohols or organic solvents having a boiling point of 100 ° C. or lower.
  • the particle body of the layered composite obtained by the grinding may be one having a size of micrometer or more, but is not limited thereto.
  • the method for producing the flexible carbon pocket composite structure is not included in the external surface of the particle body before removing the polymer from the particle body obtained by the grinding of the layered composite. It may further include removing the particles that are not, but is not limited thereto. Removing the non-inclusion particles present on the outer surface of the particle body may be performed by dissolving and removing the particles using a solvent capable of dissolving the particles. For example, when the particles include Si, the removal of the non-inclusion particles may be performed using a basic solution, but is not limited thereto.
  • the basic solution may include a strong basic aqueous solution containing potassium hydroxide, calcium hydroxide, and the like, but is not limited thereto.
  • the embodiments of the present disclosure it is possible to provide a manufacturing method capable of ultra-fast mass production of the flexible carbon pocket composite structure.
  • carbonaceous materials such as graphene are easily damaged and silicon is exposed to LIBs such as volume expansion, SEI layer growth and destruction. May cause problems.
  • the method for producing the flexible carbon pocket composite structure various particles such as silicon particles and carbonaceous sheets such as graphene and the like are laminated by a polymer and also such as the ball-milling process Since the layered composite structure of the silicon particles and the graphene sheet can be safely maintained in the grinding process, the flexible carbon pocket composite structure can be mass-produced at high speed without damage to the silicon and graphene active material for lithium anode.
  • the flexible carbon pocket composite structure includes a composite comprising particles enclosed by each of at least one carbonaceous first pocket formed by a carbonaceous first sheet and a carbonaceous second sheet facing each other. It may include.
  • the mutually opposed carbonaceous first sheet and the carbonaceous second sheet are in contact with each other in at least one region, the carbonaceous first sheet and the carbonaceous second sheet is in contact with each other
  • One or more regions which are not provided may be each forming the carbonaceous first pocket, but are not limited thereto.
  • the one or more carbonaceous first pockets may be formed spaced apart from each other, but is not limited thereto.
  • the carbonaceous first pocket may be a closed type or partially closed type, but is not limited thereto.
  • the carbonaceous first pocket may, but is not limited to, lapping or partially wrapping the surface of the particles enclosed by it.
  • the carbonaceous first sheet and the carbonaceous second sheet are each independently graphene, graphite, carbon nanotubes, carbon fiber, carbon black, activated carbon, graphene oxide (GO), or It may include, but is not limited to, a sheet containing reduced graphene oxide (rGO).
  • each of the carbonaceous first sheet and the carbonaceous second sheet may have a wrinkle (wrinkle), but is not limited thereto.
  • the carbonaceous first sheet and the carbonaceous second sheet may be flexible in itself, such as a graphene sheet, and the carbonaceous first sheet and the carbonaceous second sheet may have wrinkles.
  • the flexibility may further increase and have elasticity, such that the carbonaceous first pocket may have excellent flexibility, elasticity, and the like, and the flexible carbon pocket composite structure may have excellent flexibility, elasticity, and the like.
  • the corrugated (s) are formed in at least one region in which the mutually opposing carbonaceous first sheet and the carbonaceous second sheet are in contact with each other to form the carbonaceous agent.
  • One pocket may have excellent flexibility, elasticity, and the like, and the flexible carbon pocket composite structure may have excellent flexibility, elasticity, and the like.
  • the mutually opposed carbonaceous first sheet and the carbonaceous second sheet are in contact with each other in at least one region, the carbonaceous first sheet and the carbonaceous second sheet is in contact with each other
  • One or more regions which are not provided may be each forming the carbonaceous first pocket, but are not limited thereto.
  • two or more of the composites included in the flexible carbon pocket composite structure when two or more of the composites included in the flexible carbon pocket composite structure, two or more of the composites contact each other by mutual contact of the carbonaceous first pockets included in each of the composites It may be, but is not limited thereto.
  • the flexible carbon pocket composite structure may include, but is not limited to, a carbonaceous second pocket that encloses one or more of the composite.
  • the carbonaceous second pocket includes a carbonaceous sheet containing graphene, graphite, carbon nanotubes, carbon fibers, carbon black, activated carbon, graphene oxide (GO), or reduced graphene oxide (rGO). May be, but is not limited thereto.
  • the flexible carbon pocket composite structure may have a porosity, but is not limited thereto.
  • the carbonaceous second pocket may include a plurality of carbonaceous sheets, but is not limited thereto.
  • the particles may be semiconductor, conductive or insulating, but is not limited thereto.
  • the particles may include an electrode material material, but are not limited thereto.
  • the particles or the electrode material material can be used without particular limitation materials known in the art, for example, Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn , Al, Co, Ni, Ti, Te, Mn, Fe, W, Ag, Au, Pt, V, Cu, Ga, P, and S may include one or more elements selected from the group consisting of, but It is not limited.
  • the electrode material material may include, but is not limited to, the one or more elements or compounds thereof, or an alloy of the two or more elements.
  • the weight ratio of the carbonaceous sheets and the particles is not particularly limited, for example, may be about 1: 0.001 or more, but is not limited thereto.
  • the weight ratio of the carbonaceous sheets and the particles is about 1: 0.001 or more, about 1: 0.001 to 1,000, about 1: 0.001 to 500, about 1: 0.001 to 100, about 1: 0.001 to 10, about 1: 0.01 to 1,000, about 1: 0.01 to 500, about 1: 0.01 to 100, about 1: 0.01 to 10, about 1: 0.1 to 1,000, about 1: 0.1 to 500, about 1: 0.1 to 10, or about 1: 0.1 to 10, but is not limited thereto.
  • the particles may be nanoparticles or have a size of about 1 ⁇ m or less, but may not be limited thereto.
  • the particle size may be about 1,000 nm or less, about 100 nm or less, about 10 nm or less, or about 1 nm or less, but may not be limited thereto.
  • the particle size may be about 1,000 nm or less, about 500 nm or less, about 100 nm or less, about 10 nm or less, about 5 nm or less, about 1 nm or less, about 1 nm to about 1,000 nm, about 1 nm.
  • the size of the flexible carbon pocket composite structure may be determined by the size of the particles surrounded by the structure or the size of the carbonaceous sheet forming the carbonaceous first pocket, but is not limited thereto. It is not that.
  • the size of the flexible carbon pocket composite structure may be greater than or equal to the size of the particles encapsulated by the structure, or may be equal to or larger than the size of the carbonaceous sheet forming the carbonaceous first pocket, but is not limited thereto. no.
  • the size of the flexible carbon pocket composite is equal to or equal to the sum of the particle size and the thickness of the carbonaceous second pocket. It may be more than, but is not limited thereto.
  • the height of the flexible carbon pocket composite structure may be determined in consideration of the particle size and / or the thickness of the carbonaceous second pocket, and the width of the flexible carbon pocket composite structure is the carbonaceous first pocket. It may be determined in consideration of the width of the carbonaceous sheet and / or the thickness of the carbonaceous second pocket to form a, but is not limited thereto.
  • the size of the flexible carbon pocket composite structure may be one having a size of nanometer to micrometer or more, but is not limited thereto.
  • the size of the flexible carbon pocket composite structure is not particularly limited and may be adjusted according to the size of the carbonaceous natto sheet forming the flexible carbon pocket composite structure and the stacking of the composites.
  • the size of the flexible carbon pocket composite structure may be about 100 ⁇ m or less, about 10 ⁇ m or less, about 1 ⁇ m or less, about 800 nm or less, about 600 nm or less, about 500 nm or less, about 400 nm or less, about 300 nm or less, about 200 nm or less, about 100 nm or less, about 50 nm or less, about 10 nm or less, about 10 nm to about 100 ⁇ m, about 10 nm to about 50 ⁇ m, about 10 nm to about 10 ⁇ m, about 10 nm To about 1 ⁇ m, about 10 nm to 500 nm, about 10 nm to about 100 nm, about 100 nm to about 100 ⁇ m, about 100 nm to about 50 ⁇ m, about 100 nm to about 10 ⁇ m, or about 100 nm to about 1 ⁇ m, but may not be limited thereto.
  • the flexible carbon pocket composite structure may be one having excellent dispersibility in a solvent.
  • the flexible carbon pocket composite structure may have excellent dispersibility in various organic solvents such as water, alcohols, organic solvents, and the like.
  • the flexible carbon pocket composite structure is remarkably compared to the dispersibility of carbon-based materials such as graphene. By having excellent dispersibility, it can be easily applied to the production of electrodes and various devices.
  • Graphene powder and silicon nanoparticles were mixed in acetone by weight ratio (1: 9, 2: 8, 3: 7 and 4: 6) using sonication. Then cyanoacrylate glue monomer was added to the mixed solution and shaken by hand immediately for several hours. At this time, the amount of cyanoacrylate glue monomer was adjusted according to the amount of graphene and acetone used. The glue monomer used the same weight as the acetone and it was equivalent to tens of times the graphene weight. The cyanoacrylate glue monomer started the polymerization reaction in a few seconds, and the reaction was completed within 1 minute.
  • the mixture of polymerized cyanoacrylate, graphene and silicone was dried in a 60 ° C. vacuum oven for less than 30 minutes.
  • the fully cured mixture was ground to a suitable size for milling using a hammer and transferred into a vial of a ball milling machine (8000M Mixer / Mill, SPEX SamplePrep).
  • a ball mill was run for 10 minutes and a powder of the mixture was obtained.
  • the powder obtained was etched in 1 M potassium hydroxide (KOH) solution for less than 1 minute.
  • the etched powder is named Si_ECA_G.
  • the etched powder was heat treated in H 2 and Ar atmosphere for 30 minutes at 673K using a well-sealed tube-furnace. According to the above procedure, Si_GPP, a flexible carbon pocket composite structure, was obtained.
  • Si_GPP was dispersed using acetone solvent and placed on a Cu mesh grid. Local element information and element mapping were obtained using an Energy Dispersive Spectrometry (EDS) attached to the TEM.
  • EDS Energy Dispersive Spectrometry
  • Si_GPP and Si_ECA_G were dispersed in acetone solvent and added dropwise onto a small piece of silicon wafer.
  • a backscattered electron (BSE) detector attached to the SEM was used to obtain an image of the distinguished silicon particles.
  • BSE backscattered electron
  • 5 mg of Si_GPP was dispersed in Nafion 117 solution and then also added dropwise onto the silicon wafer.
  • An ion beam cross section polisher IB09010CP, JEOL was used to make cross section samples using ion beams.
  • XPS spectra of Si_GPP and Si_ECA_G were obtained using Thermo VG Scientific's Sigma Probe equipped with a 350W Al anode X-ray light source with multi-anode, pulse coefficient and hemispherical analyzer. The spectrum was collected using an incident photon energy of 1486.6 eV and corrected for the work function of the detector.
  • Powder X-ray data was obtained by a fast 1D detector (D / teX Ultra) in reflective Bragg-Brentano geometry using Johansson type Ge (111) monochromatic filter Cu K ⁇ 1 radiation at 1200 W (40 KV, 30 mA) power. Collected using a equipped SmartLab ⁇ -2 ⁇ diffractometer. The powder of Si_GPP, silicon nanoparticles and pure graphene was mounted on a holder stage and scanned at a scan rate of 2 ° / min in continuous mode.
  • the weight ratio of pure silicon in Si_GPP samples was determined using TGA (TG209 F1 Libra, NETZSCH). Pyrolysis was measured when Si_GPP was produced as Si_ECA_G by heat treatment.
  • MALDI-TOF data was collected using Bruker autoflex III (Bruker Daltonics).
  • the molecular weight of polymerized ECA was determined by the above analysis.
  • Si_GPP was dissolved in CHCl 3 and HCCA ( ⁇ -Cyano-4-hydroxycinnamic acid) matrix was used.
  • the working electrode for the anode is Si-GPP (80% by weight), carbon black (Super-P, 10% by weight) and poly (vinylidene fluoride) binder (PAA, 10% by weight in N-methyl-2-pyrrolidone (NMP) %) was mixed to form a slurry.
  • the slurry was pasted into pure copper foil using a doctor blade and dried overnight at 70 ° C. in a vacuum oven.
  • the electrochemical performance of the prepared samples was investigated using a CR2032 type battery assembled in an argon-filled glove box using pure lithium metal (Honjo Chemical Co.) as the counter / reference electrode.
  • the electrodes were cycled in a potential range of 0.01 V to 1.5 V (vs. Li / Li + ) for silicon nanoparticles or Si_GPP electrodes at room temperature using a battery cycler (Wonatech, WBCS-3000).
  • the electrodes for representative cathodes are cathode materials such as lithium cobalt oxide (LiCoO 2 , LCO), lithium manganese oxide (LiMnO 2 , LMO), lithium iron phosphate (LiFePO 4 , LFP), Super in NMP, Super -P (3 wt%) and binder (PVDF, 3 wt%) were prepared by mixing to form a slurry. The slurry was pasted into pure Al foil using a doctor blade and dried overnight at 70 ° C. in a vacuum oven.
  • the electrochemical performance of these representative cathode materials was investigated using a CR2032 type cell assembled in an argon-filled glove box using lithium metal as the counter / reference electrode.
  • the electrolyte used was 1: 1 (v / v) ethylene carbonate / diethyl carbonate (EC / DEC) layer 1 M LiPF 6 It was an electrolyte.
  • Celgard 2400 polypropylene was used as separator. Charge-discharge measurements were performed at different current densities in the potential range of 3 V to 4.5 V (vs. Li / Li + ).
  • Si_GPP electrodes were assembled into half-cells using Li metal and separators as counter metal / reference electrodes.
  • the cell was lithiated for 30 minutes after being installed in a lithiation circuit with a variable resistor.
  • the cells were disassembled and prepared in half-cell and full-cell arrangements.
  • Graphite based full-cell using the representative cathode material as the cathode was prepared using a coin-type cell.
  • the Si_GPP electrode was pre-lithiated to obtain maximum initial coulombic efficiency to prevent Li ion loss during operation.
  • the anode and cathode were arranged in full-cell.
  • the mass of the two electrodes must equally adjust the overall charge, and in this embodiment also consider the excess 10% mass of the anode material. For example, the mass ratio of LFP to Si_GPP was determined to be 9.72.
  • the total mass of active material of the anode was 1.4 mg cm -2 and LFP was 13 mg cm -2 .
  • CV and gravimetric charge / discharge data at various scan rates were measured using a multichannel potentiometer (Biologic, VSP).
  • C A is the specific capacitance of the anode electrode
  • C C is the specific capacitance of the cathode electrode
  • V n is the nominal potential of the full-cell.
  • the high performance anodes of silicon-embedded GPP are also paired with a representative cathode to create a powerful full-cell.
  • the various advantages of the superglu process of the present application which is dynamic, scalable, easy and cost-effective, can simultaneously realize mass production for precise control and commercialization of materials.
  • FIG. 1C-1G show the design overall process of ultrafast mass production of graphene flexible pockets encapsulating silicon nanoparticles and the effectiveness of such mass production process.
  • FIG. 1C shows a schematic of a manufacturing process for graphene flexible pockets encapsulating silicon nanoparticles using ECA: i) Polymerization of Super Glue (Inset) Using Graphene and Silicon Nanoparticles, ii ) Intermediate product (Si_ECA_G) after polymerization, ball-milling, and etching process (insertion rate: ECA polymer fixes silicon nanoparticles on the surface and layers of graphene to prevent agglomeration of silicon nanoparticles), iii) heat treatment Post Si_GPP structure (insertion: shows internal phase diagram of Si_GPP).
  • FIG. 1D shows a 50 mL scale batch for Si_GPP preparation: i) Polymerization step with 466 mg of silicon nanoparticles, 200 mg of graphene and 20 g of ECA (Inset: Graphene and Silicon Nanoparticles) Cross-sectional view of polymerized ECA containing particles), ii) grinding step using a high energy ball-mill to produce ECA, Si and graphene composites in a few micro-sized (insertion: comparison with US 50 cent coin) Amount of one composite powder), iii) As a final step in the production of Si_GPP, the amount of silicon and graphene contained in the synthesized Si_GPP is exactly the same as the amount of silicon and graphene used in the first step (insertion: 50 The amount of Si_GPP powder compared to cent coins). 1E shows a 500 mL scale batch for preparing Si_GPP using 3.5 g of silicon nanoparticles, 1.5 g of graphene and 150 g of ECA.
  • FIGS. 1F and 1G are TEM photographs of the flexible carbon pocket composite structure in this embodiment.
  • the silicon nanoparticles are each surrounded by a graphene first pocket (inner pocket). It can be confirmed, and also it can be seen that the graphene second pocket is formed outside the first pocket.
  • Figure 2a in this embodiment, is a schematic diagram of the anionic polymerization process of ECA in the presence of graphene and Si nanoparticles
  • Figure 2b is graphene + Si nanoparticles in the polymerization process according to the content ratio of ECA and Si_ECA_G sample conditions MALDI-TOF spectrum of poly ECA.
  • FIG. 3 is, as a result of the structural analysis of the Si and graphene composite in this embodiment, a and b in Fig. 3 is an SEM image of Si_GPP, c) is a cross-section of Si_GPP, d in Fig. 3 is Si_GPP using the BSE mode 3E is a TEM image of Si_GPP, FIG. 3F is a STEM image of Si_GPP, g of FIG. 3 is an element mapping image of Si_GPP, and h of FIG. 3 is a high-resolution STEM image of silicon nanoparticles of Si_GPP.
  • FIG. 4A to 4D show the results of electrochemical performance analysis of Si_GPP half-cells in this embodiment
  • FIG. 4A is the initial charge-discharge profile of Si_GPP electrodes using various ratios of silicon content and pre-lithiation conditions.
  • 4B is a result of comparing specific capacitance and initial coulombic efficiency of Si_GPP electrodes using various manufacturing conditions.
  • 4C is the voltage profile for 7: 3 Si_GPP as a function of various current densities of 200 mA / g to 20 A / g
  • FIG. 4D is at various current densities of 0.1 A / g to 20 A / g after capacity retention. Capacity retention and cycle performance analysis at 5 A / g.
  • FIG. 5 shows the results of electrochemical performance analysis of a full-cell using Si_GPP and a representative commercial anode as a comparative example in this embodiment, in which FIG. 5A is a schematic diagram of a full-cell arrangement, and FIG. 5B is a half.
  • 5c is a voltage profile of a full-cell array using Si_GPP anodes and various cathodes
  • d in FIG. 5 shows the cycle performance of full-cell using LCO, LMO, and LFP and Si_GPP.
  • 5E is a graph comparing the energy density of full-cells with Si_GPP and graphite as a function of cathode material.
  • FIG. 6 is a schematic of before and after base etching of Si_ECA_G and Back Scattered Electron (BSE) SEM images: a) schematic of Si_ECA_G before base etching, b) BSE image of Si_ECA_G before base etching, c) schematic of Si_ECA_G after base etching, d ) BSE image of Si_ECA_G after base etching.
  • BSE Back Scattered Electron
  • 8 (a) and (b) are SEM images of mass-produced Si_GPP; 8 (c) is a STEM image of mass produced Si_GPP; (D) and (e) of FIG. 8 show STEM elemental mapping images (blue: carbon, red: silicon) of Si_GPP mass-produced.
  • the polymerized ECA was capturing the graphene sheet, the silicon nanoparticles were trapped in the matrix of the ECA polymer, and their separated structures could be preserved for later processing. Even after subsequent processes such as a mechanical ball-milling process to obtain the micro-size structure and a washing process to remove the external silicon by the concentrated basic solution, the ECA polymer can preserve the homogeneity of the graphene sheet / silicon nanoparticle mixture. there was.
  • the intermediate product (Si_ECA_G) has a pocket-shaped structure with a mixture of graphene sheets and ECA polymer, as can be seen in the SEM (Scanning Electron Microscopy) image of Si_ECA_Gs of FIG.
  • the ball-milled complex was spherical and had an average size of less than 20 ⁇ m.
  • the silicon nanoparticles in Si_ECA_Gs were uniformly attached in an ECA / graphene matrix such as raisins bread.
  • the brighter portions representing the silicon nanoparticles were evenly distributed in the ECA_G matrix.
  • no silicon nanoparticles were detected on the Si_ECA_G surface, and small holes formed by removing silicon nanoparticles from the surface were detected (FIG. 6D). .
  • Si_GPP After annealing the Si_ECA_G to remove the ECA, the final product of the process, Si_GPP, was obtained.
  • the ECA matrix of Si_ECA_Gs could be easily removed by evaporation under annealing conditions (90% evaporated at 200 ° C., 10% evaporated at 350 ° C. under argon). While the ECA evaporated, the graphene sheet contracted on the silicon nanoparticle clusters (FIG. 1A ii inset), and the remaining graphene sheets contained thick carbon pockets containing the silicon nanoparticle clusters captured by the inner graphene sheet. Formed (FIG. 1A iii). Silicon nanoparticles trapped in graphene flexible pockets with an inner carbon shell (Si_GPP) for the anode material were obtained after the above manufacturing process.
  • Si_GPP production using an instant polymerization reaction to cover silicon nanoparticles using internal and external carbon pockets is a commercially available silicon-based anode for LIB. It is a promising methodology for materials.
  • SEM and transmission electron microscopy (TEM) were measured by SEM and transmission electron microscopy (TEM).
  • Si_GPP As can be seen in the SEM image of a of FIG. 3, spherical Si_GPP of less than 10 ⁇ m was observed with uniform size and shape distribution. Individual Si_GPP exhibited a spherical shape with carbon warping on the surface (FIG. 3 b). Silicon nanoparticles were not detected on the Si_GPP surface. In order to identify the silicon nanoparticles in the carbon pocket, the cross section of Si_GPP was analyzed by SEM to observe the inside of Si_GPP (FIGS. 3c and d). As the cut surface of Si_GPP, a thin layer of graphene sheets was placed in a thick outer pocket shell formed of graphene sheets (FIG. 3C).
  • FIG. 3 d shows a TEM photograph of Si_GPP single particle. Dark areas representing silicon nanoparticles were detected in the outer carbon shell. Because of the micro size of Si_GPP, only subsurface silicon particles were detected by TEM analysis. The distribution of silicon nanoparticles in GPP was distinguished by scanning transmission electron microscopy (STEM) analysis (FIG. 3 f), and the elemental mapping of Si_GPP (G in FIG. 3) showed that the silicon element distribution (red) in the carbon element GPP (blue) ).
  • Figure 3 h shows a high resolution STEM image of silicon nanoparticles located deep inside of GPP.
  • the Raman spectrum of Si_GPP shows a major peak at about 512 cm ⁇ 1 representing Si crystalline nanoparticles and another two peaks around 1350 cm ⁇ 1 and 1598 cm ⁇ 1, representing the D and G bands of graphene, respectively. (FIG. 10).
  • the Si_GPP some movement of the 2D peak (2700 cm - 1) is a clear graphene shrinkage caused by evaporation of the ECA.
  • ECA evaporation can be confirmed by X-ray photoelectron spectroscopy (XPS), which shows that the N1s spectrum from the cyanogen of ECA disappears after ECA evaporation (FIG. 11).
  • XPS X-ray photoelectron spectroscopy
  • the content of silicon in Si_GPP is confirmed by thermogravimetric analysis (TGA) measurement (FIG. 7), which indicates that the proportion of silicon nanoparticles in Si_GPP varies from 60% to 90% as Si input.
  • the zeta potential of Si_GPP of this example was measured using water as a diluent.
  • the zeta potential of Si_GPP was measured to be -36.36 mV, and as a comparative example, the zeta potential of graphene was measured to be 7.39 mV.
  • Increasing the zeta potential of the Si_GPP indicates that the dispersed partner can be maintained for a long time if the Si_GPP is significantly superior in dispersibility in a solvent such as water as compared to conventional graphene.
  • Si_GPP electrodes were assembled in a half-cell arrangement using Li metal as the counter and reference electrode.
  • various Si_GPPs having different Si contents of 60% to 90% were prepared and these were made under 0.01 to 1.5 V (vs. Li / Li + ) using a current density of 100 mA / g.
  • the initial charge and discharge operation of was tested.
  • 4A shows the initial charge and discharge profiles of Si_GPP with different silicon ratios. All Si_GPP electrodes exhibit a representative silicon alloying plateau under 0.1 V (vs Li / Li + ) and dealloy around 0.4 V.
  • the alloy / dealloy peaks of Si_GPP in cyclic voltammetric measurements represent a representative silicon-based electrode (FIG. 13), which is consistent with the voltage profile of the Si_GPP electrode of FIG. 4A. Because of the irreversible reaction at the first discharge by the formation of the SEI layer, the initial coulombic efficiency (ICE) did not reach 80%, but the irreversible reaction at the first discharge was clearly disappeared after pre-lithiation.
  • ICE initial coulombic efficiency
  • the irreversible charge / discharge capacity was optimized according to the silicon content, and the 7 (Si): 3 (carbon) weight ratio (7: 3) showed the highest ICE of 70% (FIG. 4B). .
  • the 7 (Si): 3 (carbon) weight ratio (7: 3) showed the highest ICE of 70% (FIG. 4B).
  • the 7: 3 sample was chosen as a further study to evaluate electrochemical performance as anode electrode in half-cell and full-cell arrangement.
  • a circuit for achieving pre-lithiation using a 100 ohm resistor was designed to control the lithiation rate (FIG. 14), with a 30-minute pre- The lithiation period was applied.
  • the irreversible reaction by SEI layer formation and SiO x lithiation at the initial discharge was completed after pre-lithiation (FIG. 4A), leading to 99.3% ICE (FIG. 4B).
  • the charge / discharge capacity of the 7: 3 Si_GPP electrode was evaluated under various current densities. 4C shows the voltage profile of the Si_GPP electrode at a current density of 0.2 to 20 A / g.
  • a specific capacitance of 1700 mAh / g at a current density of 0.2 A / g corresponds to a capacity at 0.1 A / g.
  • the voltage profile operates stably and the capacity of the Si_GPP electrode is due to the Si-Li alloy flatness corresponding to the CV of Si_GPP (FIG. 13).
  • FIG. 15 shows the charge-discharge profile of a silicon nanoparticle and a silicon + graphene mixture (7: 3 ratio, no GPP structure), the first cycle being operated at a current density of 100 mA g ⁇ 1 and then 200 mA g A current density of -1 was applied to the electrode.
  • the silicon nanoparticles showed unstable cycle characteristics, but the silicon graphene mixture showed low specific capacitance during repeated charge-discharge.
  • Discharge capacity of 134.0, 100.2 and 162.1 mAh / g cathode in the first cycle is full with commercial graphite-a was comparable to the capacity of the cell (Fig. 16), which is the cathode Li ion is not consumed by the non-reversible reaction during operation Indicated.
  • the initial CE of the full-cell at 0.1 C rate was 86.86% (using LCO), 93.07% (using LMO) and 94.55% (using LFP) and reached 99.75% during this cycle maintenance at 1 C rate (FIG. 5D). .
  • Si_GPP / LFP showed only a 24% capacity drop compared to capacity at 0.1 C rate at 3 C rate. Compared to G / LFP, Si_GPP / LFP showed higher rate performance than G / LFP, indicating that the high performance of Si_GPP at high current density improves the overall characteristics of the full-cell arrangement (FIG. 18).
  • the high performance of the anode material can play an important role in improving the energy density of the full-cell by reducing the weight of the full-cell integration resulting from the significantly increased weight capacity of the anode.
  • the experimental energy densities of conventional graphite / cathode systems were 293.6 (using LCO), 283.2 (using LMO) and 348.8 (using LFP) Wh / kg, respectively, as shown in FIG. 5E. .
  • the energy density of the full-cell using the Si_GPP anode was proved to be 448.1 (using LCO), 351.5 (using LMO) and 489.3 Wh / kg (using LFP) (FIG. 5E).
  • full-cell integration with the Si_GPP anode showed up to 68% higher enhanced energy density than full-cell with commercial graphite.
  • the high performance of the Si_GPP electrode can be a promising candidate to replace current anode electrodes for full-cell devices with high energy density using various cathodes.
  • NMC Li- [Co 1/3 Ni 1/3 Mn 1/3 ] O 2
  • NCA 05 ] O 2
  • Si_GPP can be prepared by mass production process using instant polymerization of commercially available 'super glue' ECA.
  • the dynamic (within seconds) reaction of the ECA provided a new methodology to satisfy mass production as well as well controlled micro-size structures.
  • the inner thin layer graphene and outer thick carbon pockets where silicon nanoparticles provide conductivity are uniformly enclosed in the GPP structure with outer thick carbon pockets that stabilize the SEI layer during operation, resulting in high capacity, charge and discharge rate performance. And good cycle holding power.
  • Strong full-cell performance arranged using representative commercial cathodes has been observed to have up to 68% improved energy density compared to commercial graphite based full-cells.

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Abstract

La présente invention se rapporte : à une structure composite de poche de carbone flexible comprenant des particules fonctionnelles qui sont incluses dans une poche de carbone flexible formée par des feuilles carbonées; à un procédé permettant de fabriquer la structure composite de poche de carbone flexible, au moyen duquel les structures composites de poche de carbone flexibles peuvent être produites en masse à une vitesse très élevée; à une électrode comprenant la structure composite de poche de carbone flexible; et à un dispositif de stockage d'énergie comprenant l'électrode.
PCT/KR2018/000605 2017-02-28 2018-01-12 Structure composite de poche de carbone flexible, procédé permettant de fabriquer cette dernière, électrode comprenant cette dernière et dispositif de stockage d'énergie comprenant ladite électrode Ceased WO2018159938A1 (fr)

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EP18760706.4A EP3550645A4 (fr) 2017-02-28 2018-01-12 Structure composite de poche de carbone flexible, procédé permettant de fabriquer cette dernière, électrode comprenant cette dernière et dispositif de stockage d'énergie comprenant ladite électrode
CN201880005706.3A CN110168786B (zh) 2017-02-28 2018-01-12 柔性碳质袋复合结构，其制造方法，包括其的电极及包括该电极的储能装置
JP2018516477A JP6641466B2 (ja) 2017-02-28 2018-01-12 柔軟性炭素ポケット複合構造体、その製造方法、それを含む電極及び前記電極を含むエネルギー貯蔵デバイス
US15/937,914 US10985364B2 (en) 2017-02-28 2018-03-28 Pliable carbonaceous pocket composite structure, method for preparing the same, electrode, including the same, and energy storage device including the electrode

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KR1020170111350A KR102062550B1 (ko) 2017-02-28 2017-08-31 유연성 탄소 포켓 복합 구조체, 이의 제조방법, 이를 포함하는 전극 및 상기 전극을 포함하는 에너지 저장 디바이스
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