WO2024091023A1 - Anode pour batterie secondaire et procédé de fabrication associé - Google Patents

Anode pour batterie secondaire et procédé de fabrication associé Download PDF

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Publication number
WO2024091023A1
WO2024091023A1 PCT/KR2023/016751 KR2023016751W WO2024091023A1 WO 2024091023 A1 WO2024091023 A1 WO 2024091023A1 KR 2023016751 W KR2023016751 W KR 2023016751W WO 2024091023 A1 WO2024091023 A1 WO 2024091023A1
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negative electrode
particles
shell
secondary battery
cathode
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PCT/KR2023/016751
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English (en)
Korean (ko)
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이현정
함미림
박예원
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국민대학교산학협력단
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Publication of WO2024091023A1 publication Critical patent/WO2024091023A1/fr

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    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M2004/027—Negative electrodes

Definitions

  • the present invention relates to a negative electrode, and more specifically, to a negative electrode for secondary batteries and a method of manufacturing the same.
  • lithium secondary batteries with high energy density and voltage, long cycle life, and low self-discharge rate have been commercialized and are widely used, and much research is still ongoing to improve their performance.
  • Lithium-containing cobalt oxide (LiCoO 2 ) is mainly used as the positive electrode active material for these lithium secondary batteries.
  • lithium-containing manganese oxide such as LiMn 2 O 4 with a spinel crystal structure
  • lithium-containing nickel oxide (LiNiO 2 ) are also used. there is.
  • carbon-based active materials are mainly used as negative electrode active materials.
  • Carbon-based active materials include crystalline carbon such as natural graphite and artificial graphite, and amorphous carbon such as soft carbon and hard carbon. There is carbon.
  • the carbon-based active material used as the negative electrode active material has a very low discharge potential of about -3V relative to the standard hydrogen electrode potential, and shows highly reversible charge/discharge behavior due to the uniaxial orientation of the graphene layer, resulting in excellent discharge potential. Electrode life characteristics (cycle life) are shown. In addition, when charging Li ions, the electrode potential is 0V Li/Li + , which is almost similar to that of pure lithium metal, so it has the advantage of being able to obtain higher energy when forming a battery with an oxide-based anode.
  • Si, Sn, and Si x O y are increasing as an anode material that can replace carbon-based anode active materials such as graphite.
  • Silicon-based anode materials have the advantage of achieving high storage capacity compared to graphite, but they have the disadvantage of having a low lifespan due to repeated charging and discharging due to the large volume change that occurs during alloying reactions.
  • various binder materials, conductive materials, and other additives are essentially used to bind them together and manufacture them into a predetermined layer shape, and provide electrons to the negative electrode active material layer realized through these or provide negative electrode active material to the negative electrode active material.
  • a metal current collector was essentially employed to function as a support that physically supports the.
  • binders, conductive materials, additives, or metal current collectors provided in addition to the negative electrode active material do not affect battery capacity, but are inevitably provided, so there is a limit to securing high energy density due to these materials.
  • anode material for secondary batteries that has a high storage capacity, extends battery life according to charging and discharging, and can secure high energy density by omitting materials that are conventionally essential but do not affect battery capacity is being developed. The situation is urgent.
  • the present invention was designed to solve the above-mentioned problems, and has a high storage capacity compared to carbon-based negative active materials such as graphite, but prevents or minimizes shortening of battery life due to volume changes due to charging and discharging, and realizes high energy density.
  • the purpose is to provide a cathode for secondary batteries.
  • the present invention solves the problems of complex processes required to manufacture existing negative electrodes for secondary batteries and the resulting high manufacturing costs and long manufacturing times, thereby simplifying the manufacturing process, thereby lowering the manufacturing cost and shortening the manufacturing time.
  • Another purpose is to provide a method for manufacturing an anode for a secondary battery that is advantageous for large-area use and a composition for forming an anode for a secondary battery required therefor.
  • the present invention can be printed on any substrate without material limitations, can implement a stand-alone negative electrode material that can be driven without a metal current collector, and can also be used to implement an integrated negative electrode material equipped with a metal current collector for secondary batteries.
  • a cathode forming composition There is another object in providing a cathode forming composition.
  • the present invention is (1) a negative electrode active material containing hollow particles containing carbon dispersed in a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) shell and a MXene component containing
  • a method for manufacturing a negative electrode for a secondary battery including the steps of preparing a negative electrode forming composition containing a matrix forming material, and (2) processing the negative electrode forming composition on a substrate to produce a negative electrode having a predetermined thickness.
  • the hollow particles are prepared by: 1-1) manufacturing core-shell particles by coating a silica precursor containing organosilane on a mold particle; and 1-2) preparing the core-shell particles. It can be manufactured including the step of removing the template particles and forming a silica shell.
  • the template particle is a polymer particle
  • the step of forming a polymer layer on the surface of the core-shell particle is further included between steps 1-1) and 1-2), wherein 1-2) )
  • the polymer particles are removed by the heat applied in the step, and the polymer layer can be carbonized into a carbon coating layer.
  • the matrix forming material may be included in an amount of 10 to 90% by weight based on the dry weight of the negative electrode forming composition.
  • the matrix forming material may not include an organic binder.
  • the cathode forming composition may have a viscosity of 1 to 30,000 cps.
  • the substrate may be a non-conductive substrate.
  • step (3) may further include separating the cathode formed to a predetermined thickness from the substrate.
  • the present invention includes a matrix containing MXene particles and a negative electrode active material containing hollow particles containing carbon dispersed in a shell of silicon oxide (SiO x , 0 ⁇ x ⁇ 2) dispersed in the matrix.
  • a negative electrode for secondary batteries Provides a negative electrode for secondary batteries.
  • the hollow particle may have a diameter of 0.01 to 100 ⁇ m and a shell thickness of 0.001 to 10 ⁇ m, and the MXene component may have a size of 10 nm to 50 ⁇ m.
  • the hollow particle may further include a carbon coating layer covering the outer surface of the shell.
  • it may be a stand-alone negative electrode that does not include a current collector.
  • the matrix thickness may be 5 to 500 ⁇ m.
  • the hollow particle may contain more than 15% by weight of carbon in the shell.
  • the present invention is a secondary battery comprising a negative electrode active material containing hollow particles containing carbon dispersed in a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) shell and a matrix forming material containing MXene particles.
  • a cathode forming composition is provided.
  • it may be a stand-alone negative electrode forming composition that can form a negative electrode without a current collector.
  • the present invention provides an electrolyte; Cathode according to the present invention; anode; and a separator disposed between the cathode and the anode.
  • the cathode for secondary batteries according to the present invention has a high storage capacity, but shortening of battery life due to volume changes due to charging and discharging is prevented or minimized, and materials that do not affect battery capacity, which are essential for conventional cathodes, can be omitted. Therefore, it is advantageous to realize high energy density.
  • the manufacturing process is simplified compared to the existing manufacturing process of negative electrodes for secondary batteries, and this allows for reduced manufacturing costs, shortened manufacturing time, and mass production of negative electrodes for secondary batteries, which can be widely applied in the secondary battery field.
  • the negative electrode for secondary batteries according to the present invention can be used as a stand-alone negative electrode material that can be driven without a metal current collector.
  • the negative electrode forming composition for secondary batteries according to an embodiment of the present invention can be printed on any substrate without material limitations, can implement a stand-alone negative electrode material that can be driven without a metal current collector, and can be an integrated negative electrode material equipped with a metal current collector. Since it can also be implemented as an anode material, it can be widely applied in the secondary battery field.
  • Figure 1 is a manufacturing schematic diagram of hollow particles provided in a negative electrode for a secondary battery according to an embodiment of the present invention.
  • Figure 2 is a cross-sectional view of hollow particles provided in a negative electrode for a secondary battery according to an embodiment of the present invention.
  • Figure 3 is a cross-sectional view and a partially enlarged view of a negative electrode for a secondary battery according to an embodiment of the present invention.
  • 4A and 4B are SEM photographs and EDS analysis results of hollow particles used in anodes for secondary batteries according to various embodiments of the present invention.
  • Figures 5a and 5b are graphs showing charge/discharge characteristics of negative electrodes for secondary batteries according to various embodiments of the present invention.
  • Figure 6 shows electrochemical impedance spectroscopy (EIS) measurement results for negative electrodes for secondary batteries according to various embodiments of the present invention.
  • FIG. 7A and 7B are photographs taken after the negative electrode for a secondary battery according to various examples and comparative examples of the present invention was separated from the substrate.
  • the negative electrode for a secondary battery includes (1) a negative electrode active material containing hollow particles containing carbon dispersed in a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) shell and MXene particles; It may be prepared by preparing a cathode forming composition containing a matrix forming material, and (2) processing the cathode forming composition on a substrate to manufacture a cathode having a predetermined thickness.
  • a negative electrode active material containing hollow particles containing carbon dispersed in a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) shell and MXene particles
  • step (1) forming a matrix containing a negative electrode active material containing hollow particles containing carbon dispersed in a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) shell and a MXene component. Steps are performed to prepare a cathode forming composition containing the material.
  • the negative electrode active material includes hollow particles made of a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) shell.
  • the hollow particles made of the silicon oxide ( SiO SiO
  • the hollow particles 30 may be prepared by: 1-1) manufacturing core-shell particles by coating a silica precursor (2) containing an organosilane on a mold particle (1); (FIG. 1 (a), (b)), and 1-2) including the step of removing the template particle (1) from the core-shell particle and forming a silica shell (FIG. 1 (c)) can be manufactured.
  • step 1-1) is a step of manufacturing core-shell particles, and can be implemented by coating a silica precursor (2) containing an organosilane on the template particle (1).
  • the template particles 1 can be removed from the core-shell particles by dissipation by heat and/or by dissolving in organic solvents such as acids to form hollow particles. It can be used without restrictions.
  • the template particles 1 1 may be, for example, inorganic particles or polymer particles.
  • the inorganic particle may be a metal salt or metal oxide that can be easily dissolved in a solvent or solution that does not dissolve the silicon oxide constituting the shell, and may be, for example, magnesium hydroxide or zinc oxide.
  • the polymer particles are polyacrylonitrile-based, polyethylene-based, polystyrene-based, polyvinyl chloride-based, poly(meth)acrylic acid-based, polymethyl (meth)acrylate-based, polyethyl (meth)acrylate-based, and polybutyl.
  • (meth)acrylate type polyhexyl (meth)acrylate type, poly dodecyl (meth)acrylate type, poly stearyl (meth)acrylate type, polybenzyl (meth)acrylate type, poly cyclohexyl (meth)acrylate type ) It may be any one selected from the group consisting of acrylate-based, polyacrylamide-based, polyvinyl acetate-based, and polymers polymerized with vinyl-based monomers, or a mixture of two or more of these.
  • the polymer particles can be manufactured by, for example, emulsifier-free polymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, etc., and from the viewpoint of particle uniformity, it is preferable to use emulsifier-free polymerization or dispersion polymerization. It can be manufactured.
  • emulsifier-free polymerization can be performed using monomers, cross-linking agents, and initiators, and in this case, polymerization can be performed by further including molecular weight regulators, electrolytes, ionic monomers, etc.
  • the polymer particles may be polystyrene particles.
  • the polystyrene particles are produced by adding distilled water, styrene monomer, sodium dodecyl sulfate (SDS) as a surfactant, and potassium persulfate as a polymerization initiator to the reactor, followed by emulsion polymerization under a nitrogen atmosphere. It may be polymerized through, and through this, polystyrene particles with a negative charge on the surface can be obtained.
  • SDS sodium dodecyl sulfate
  • the diameter of the mold particle 1 corresponds to the hollow diameter of the hollow particle to be implemented, and may be appropriately selected in consideration of the hollow diameter of the desired hollow particle.
  • the diameter of the template particle may be 0.01 to 100 ⁇ m.
  • the silica precursor (2) containing the organosilane may be a known silica precursor that forms silica through heat treatment, and non-limiting examples thereof include dimethyldimethoxysilane (DMDMS), diethyldiethoxysilane ( DEDEOS), diisobutyldimethoxysilane (DIBDMS), diphenyldimethoxysilane (DPDMS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), vinyl trimethoxysilane (VTMS), tetra Ethoxysilane (TEOS), tetramethoxysilane (TEMS), phenyltrimethoxysilane, phenyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyl It is one type or a mixture of two or more types selected from the group
  • the silica precursor (2) containing the organosilane is mixed with the solution containing the template particles (1) and then stirred at a temperature of 20 to 25 ° C. for 2 to 10 hours to form the silica precursor (2) on the template particles (1). 2) can be prepared as formed core-shell particles.
  • step 1-2 the template particle 1 is removed from the core-shell particle to form the hollow part 10 and the silica shell 20 is formed from the silica precursor 2. .
  • Steps 1-2) may be performed in one or two steps depending on the material of the mold particle (1) provided in the core-shell particle.
  • the silica precursor 2 can be formed into a silica shell 20 through heat treatment. If the mold particles 1 are removed through heat treatment, the mold particles 1 are removed through step 1, which is the heat treatment step. All formation of the silica shell 20 can be performed. On the other hand, if the template particles 1 are removed by a solvent or solution, the removal of the template particles 1 and the formation of the silica shell 20 are each performed in separate steps, so it takes 1-2 steps over two steps. ) steps can be performed.
  • the removal of the mold particles 1 may be performed using a known method suitable for removing the mold particles 1 considering the material of the mold particles 1 provided.
  • the mold particles 1 are inorganic particles, an acidic solution, etc. may be used.
  • Inorganic particles can be removed by dissolving them, and in the case of polymer particles, they can be removed by dissipating them by applying heat.
  • the specific method and conditions for this can follow known methods, so the present invention is not particularly limited thereto.
  • the heat treatment for forming the silica shell 20 can be performed under known conditions considering the material of the silica precursor to form the silica shell 20, for example, at a rate of 1 to 20°C/min in an inert atmosphere. It can be formed by raising the temperature and then heat treating it at a temperature of 300 to 1000°C for 1 to 5 hours.
  • the core-shell particles may be made by using vinyltrimethoxysilane or a mixture of vinyltrimethoxysilane and tetraethoxysilane as a silicon precursor, and using template particles that are polymer particles. , through this, it can be more advantageous to remove the template particles through a single heat treatment and at the same time implement hollow particles 30 in which the carbonized carbon is dispersed and distributed in the silica shell.
  • the mold particle 1 is a polymer particle, and a polymer layer is formed on the surface of the core-shell particle between steps 1-1) and 1-2). It further includes the step of forming, wherein the polymer particles are removed by the heat applied in step 1-2), and the polymer layer is carbonized into a carbon coating layer, thereby surrounding the hollow portion 10 as shown in FIG.
  • the hollow particle 30 implemented through the above-described method may have a diameter of 0.01 to 100 ⁇ m and a shell thickness of 0.001 to 10 ⁇ m, which may be more advantageous in achieving the purpose of the present invention. .
  • the hollow particles 30 prepared through the above-described method are included as a negative electrode active material, and may further include known negative electrode active materials in addition to the above-described hollow particles 30.
  • the negative electrode active material may be a crystalline graphite such as natural graphite or artificial graphite, a carbon-based material such as non-graphitizable carbon or easily graphitizable carbon, or a silicon-based material similar to the hollow particles 30.
  • the further included negative electrode active material may be hollow or non-hollow in shape.
  • other than the hollow particles 30, which are silicon oxide shells 20 in which carbon 22 is dispersed in the silicon oxide matrix 21 other types of negative electrode active materials, especially non-hollow particles, are used at an excessively high rate.
  • the matrix forming material is a shape-retaining material capable of forming a sheet shape with a predetermined thickness and is also a binding material that combines with the negative electrode active material dispersed in the implemented matrix.
  • Known matrix forming materials used in electrode production can be used.
  • the MXene component is included in order to develop mechanical strength and electrode formability sufficient to realize an independent negative electrode by mixing with the negative electrode active material including the hollow particles 30 described above without a current collector. If the MXene component is included, a negative electrode matrix can be created by combining it with the negative electrode active material without including a separate organic binder.
  • the MXene component since the MXene component has electrical conductivity, it can be used in the conventional natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, carbon nanotube, and fullerene provided in the cathode.
  • the MXene component may include at least one layer in which crystal cells with an empirical formula of M n+ 1 Here, each N or a combination thereof, and n may be 1, 2, 3, or 4.
  • M may be Sc, Y, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, or a combination thereof.
  • the MXene component may be free standing two-dimensional assemblies with continuous independent crystal structures, or may be stacked assemblies in which the crystal structures are stacked.
  • atoms, ions, or molecules may be intercalated between at least some of the layers, where the intercalated atoms or ions may be lithium.
  • the MXene component can be manufactured through known methods, and the present invention is not particularly limited thereto.
  • a crystalline compound represented by MAX (where A is a group 13 or 14 element) can be obtained by acid etching with HF, LiF, NH 4 HF 2 , or HCl-LiF mixed solution.
  • the size of the MXene component may be 10 nm to 50 ⁇ m, and through this, it can be mixed with hollow particles within the above-described preferred size range to create a stand-alone negative electrode with excellent strength without a current collector. Purpose of the present invention. It may be more advantageous to achieve.
  • the size of the MXene component refers to the line segment with the largest length among the line segments connecting two different points on the surface of the component.
  • the content of the matrix forming material containing the MXene component can be determined considering the size and shape of the hollow particles provided as the negative electrode active material. For example, if the hollow particle size is large and the porosity is high, the content of the MXene component may be determined. Even if this content is small, it may be possible to implement a stand-alone electrode. If the size of the hollow particles is small and the porosity is small, and conversely, if the content of the MXene component is small, it may not be easy to implement a stand-alone electrode. Accordingly, the content of the matrix forming material containing the MXene component may be 10 to 90% by weight based on the dry weight of the negative electrode forming composition.
  • the matrix forming material containing the MXene component is provided in an amount of less than 10% by weight, it may be difficult for the realized negative electrode to be a stand-alone negative electrode without a current collector, or even if it is implemented, it may be difficult to develop sufficient mechanical strength.
  • the matrix forming material containing the MXene component is included in an amount exceeding 90% by weight, there may be a problem of capacity reduction.
  • the above-mentioned negative electrode forming composition may further include a dispersion medium in addition to the hollow particles and matrix forming material.
  • the dispersion medium may be a known dispersion medium suitable for dispersing silicon oxide hollow particles and MXene components, and the present invention is not particularly limited thereto.
  • the dispersion medium may be distilled water.
  • the negative electrode forming composition may further be provided with additives provided in the electrode forming composition, such as a thickener, but preferably may not be provided with these additives, and through this, a negative electrode capable of realizing increased battery energy density and capacity. It can be advantageous to manufacture. Accordingly, the negative electrode forming composition according to an embodiment of the present invention does not contain any components other than a dispersion solvent that is removed after drying, and as a negative electrode active material, hollow particles and matrix forming materials consisting of a silicon oxide shell with carbon dispersed in a silicon oxide matrix are used. It can be made of only the romaxine component, which is advantageous for manufacturing a cathode that can realize further increased battery energy density and capacity, and is advantageous for demonstrating a synergistic effect on the mechanical strength of the realized cathode.
  • the negative electrode forming composition may have a viscosity of 1 to 30,000 cps, which may be more advantageous in achieving the purpose of the present invention.
  • step (2) a cathode having a predetermined thickness is manufactured by treating the above-described cathode forming composition on a substrate.
  • the substrate is a known substrate used to form a cathode, it can be used without limitation.
  • the substrate may be a current collector used to form a cathode.
  • the substrate may be a non-conductive substrate that cannot be used as a current collector.
  • a hydrophilic substrate can be used to easily separate from the substrate to implement an independent electrode.
  • the contact angle is 90° or less, more preferably A substrate of 70° or less can be used, which allows for easier separation without cracks or other damage to the cathode formed during the separation process on the substrate.
  • the cathode forming composition according to an embodiment of the present invention may not be suitable for forming a cathode having a predetermined thickness, or separation of the formed cathode may not be easy and may be difficult during the separation process. There is a risk that cracks or cuts in the cathode may occur.
  • an example of a substrate having a contact angle of 90° or less may be a PTFE substrate modified to be hydrophilic, but is not limited thereto.
  • the method of treating the cathode forming composition on the substrate may be a known method of treating the electrode forming material on the substrate, and may be, for example, coating.
  • the coating comma It may be coated by a coater, spin coating, doctor blade, impregnation, etc., and preferably coated by a doctor blade.
  • the specific conditions of these coating methods can be changed by appropriately adopting the known conditions according to each coating method, so the present invention is not particularly limited thereto.
  • the amount of the cathode forming composition treated on the substrate can be appropriately changed considering the thickness of the cathode to be implemented, the viscosity of the cathode forming composition, etc.
  • the cathode forming composition before drying may be treated to a thickness of 50 ⁇ m or more, Through this, it can be easy to implement a cathode with a thickness of 5 ⁇ m or more after drying.
  • a drying process may be performed, and the drying may be natural drying at room temperature or drying using heat such as hot air.
  • step (3) may further include the step of separating the cathode formed to a predetermined thickness from the substrate, and through this, an independent cathode can be implemented.
  • the anode 100 for a secondary battery according to an embodiment of the present invention implemented through the above-described method includes a matrix containing an MXene component 40 and silicon oxide dispersed in the matrix.
  • the hollow particle 30 improves the non-covalent bond between the dispersed carbon 22 and the silicon oxide matrix 21 and the MXene component 40, so that it can be formed without the need for components such as organic binders. It is advantageous to be implemented as a stand-alone cathode that exhibits sufficient mechanical strength.
  • the MXene component forms a matrix
  • the non-hollow silicon oxide particles are used alone or in a higher content than the hollow particles 30 relative to the total weight of the negative electrode active material, or in more than 10% by weight of the negative electrode active material, an independent negative electrode can be formed. It can be difficult. Additionally, even in the case of hollow silicon oxide particles, if they do not contain carbon, it may be difficult to implement a stand-alone cathode with sufficient strength.
  • the hollow particles 30 may contain 15% by weight or more of carbon in the particles, for example, 20% by weight or more, and through this, can be used as an independent cathode. It can have improved mechanical strength and is effective in suppressing the expansion of hollow particles due to charging and discharging during use, which can be advantageous for exhibiting increased durability. If the dispersed carbon content is less than 15% by weight, it may be difficult to achieve the above synergistic effect. However, the carbon may be included in the hollow particles in an amount of 75% by weight or less, and if it exceeds 75% by weight, it may be difficult to implement a battery with high energy density and capacity.
  • the negative electrode for the secondary battery may be made of a negative electrode active material including the hollow particles 30 in a matrix composed only of the MXene component 40 without an organic binder, as described above, and even more preferably
  • the negative electrode active material may also be made of the hollow particles 30, and through this, a negative electrode capable of realizing further increased battery energy density and capacity can be realized, and it can be advantageous because a synergistic effect is expressed in the mechanical strength of the implemented negative electrode. there is.
  • the matrix thickness may be adjusted differently depending on the purpose and the presence or absence of a current collector, and may be 1 to 1000 ⁇ m for one example and 5 to 500 ⁇ m for another example.
  • the negative electrode 100 can be used as an independent electrode, but is not limited thereto, and may further include a current collector on one side of the matrix where the negative electrode active material is dispersed.
  • the current collector can be used without limitation in the case of a current collector used in a negative electrode for a secondary battery, and as a non-limiting example, it may be implemented with copper, gold, nickel, an alloy thereof, or a combination thereof.
  • the present invention includes a secondary battery employing the above-described negative electrode, and the secondary battery includes an electrolyte, a positive electrode, a negative electrode according to an embodiment of the present invention, and a separator disposed between the positive electrode and the negative electrode.
  • the secondary battery may include all common secondary batteries including lithium secondary batteries, such as lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries.
  • lithium secondary batteries such as lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries.
  • the secondary battery may have a known shape such as a cylindrical shape using a can, a square shape, a pouch shape, or a coin shape.
  • the positive electrode may be a known positive electrode employed in a typical lithium secondary battery.
  • the positive electrode may be a positive electrode active material layer coated on a current collector.
  • the current collector may be employed without limitation as long as it is a conductive metal and is not reactive in the voltage range of the secondary battery.
  • it may be made of aluminum, nickel, or a combination thereof.
  • the cathode active material layer can be used without limitation if it is a known cathode active material layer employed in a typical lithium secondary battery.
  • the positive electrode active material layer may include a binder component forming a matrix and a positive electrode active material, and may further include a conductive agent, a dispersant, etc. as other additives.
  • the separator may be used without limitation in the case of a known separator used in a typical lithium secondary battery.
  • it may be a porous polymer film, a porous fiber web, or a laminate of these alone or in combination.
  • the porous polymer film may be made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer.
  • the porous fibrous web may be formed of, for example, high melting point glass fiber, polyethylene terephthalate fiber, etc., but is not limited thereto.
  • the electrolyte can be used without limitation in the case of lithium salt, which is known as an electrolyte for lithium secondary batteries.
  • anions of lithium salt include F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 )
  • the electrolyte may be an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, etc., but is not limited thereto.
  • a lithium secondary battery can be used as a power source for various electronic devices.
  • the above electronic devices can be used in mobile devices such as portable phones, smartphones, game consoles, portable televisions, laptops, and calculators, as well as wireless home appliances such as vacuum cleaners, razors, toothbrushes, fans, hair dryers, and blenders, but are limited to these. no.
  • the hollow particles containing carbon dispersed in the silica shell prepared through Preparation Example 1 below and the MXene particles were mixed at a weight ratio of 3:7, and the viscosity was adjusted by adding 1 ml distilled water to prepare a composition for manufacturing a secondary battery negative electrode in the form of a slurry. did.
  • the prepared composition for producing an anode was bladed at 3.8 cm/s and 70 ⁇ m thick on a hydrophilic surface-modified PTFE substrate with a contact angle of 70° and then dried at room temperature to prepare an anode for a secondary battery with a thickness of about 10 ⁇ m.
  • polystyrene template particles To prepare polystyrene template particles, the emulsion was polymerized under a nitrogen atmosphere by adding 36 ml of distilled water, 1M styrene monomer, 2mM SDS (sodium dodecyl sulfate) as a surfactant, and 10 mM PPS (potassium persulfate) as a polymerization initiator, through which a negative charge was added to the surface. Polystyrene template particles with a diameter of about 250 nm were obtained.
  • a mixed solution was prepared by adding 0.88 ml of NH 4 OH to a 5% by weight polystyrene template particle dispersion solution, and then 50mM vinyltrimethoxysilane was added while stirring the mixed solution. was added. Afterwards, the mixture was stirred at room temperature for 5 hours and washed with ethanol to prepare core-shell particles.
  • the prepared core-shell particles were heat-treated at 800°C for 2 hours at a rate of 5°C/min in an argon atmosphere to produce carbon dispersed in a silica shell with a hollow diameter of about 250 nm and a shell thickness of about 20 to 30 nm. Hollow particles were prepared.
  • Example 2 It was manufactured in the same manner as in Example 1, except that the silicon precursor for producing hollow particles in the Preparation Example was changed to tetraethoxysilane (TEOS), and the hollow particles prepared as in Preparation Example 2 below were used for secondary batteries. The cathode was manufactured.
  • TEOS tetraethoxysilane
  • 0.414 g of the same polystyrene template particles prepared in Preparation Example 1 were added to a mixed solution of 30 ml of ethanol, 0.5 ml of DI, and 1 ml of NH4OH as a dispersion medium, and then 5.4 vol% TEOS was added while stirring, followed by stirring at room temperature for 12 hours. .
  • core-shell particles were prepared by washing using ethanol. The prepared core-shell particles were heat-treated at 800°C for 2 hours at a rate of 5°C/min in an argon atmosphere to produce hollow particles containing carbon dispersed in a silica shell with a thickness of approximately 20 to 30 nm.
  • Example 1 Element (% by weight) Example 1
  • Example 2 C 51.00 13.68 O 24.71 43.84 Si 24.29 42.48 total 100.00 100.00
  • EIS was measured using the same coin cell manufacturing as used for the above charge/discharge characteristics.
  • the EIS analysis results evaluated through a frequency of 10 6 -1 Hz and an alternating voltage of 10 mV are shown in Figure 6 below.
  • a negative electrode for a secondary battery was manufactured in the same manner as in Example 1, except that instead of hollow particles, the same content was replaced with non-heavy-sized silica particles with a diameter of 100 nm.
  • Example 1 The matrix in which the negative electrode active material was dispersed in the negative electrode according to Example 1, Example 2, and Comparative Example 1 was separated from the substrate and the separated matrix was observed. In Examples 1 and 2, photographs were taken and the results were reported. It is shown in Figure 7a (Example 1) and Figure 7b (Example 2).
  • Example 1 As can be seen in FIGS. 7A and 7B, the observation results show that the matrix in which the negative electrode active material according to Example 2 and Comparative Example 1 is dispersed is difficult to use as a stand-alone electrode due to tearing occurring in the process of separation from the substrate. In the case of Example 1, it can be seen that it can be used as a stand-alone electrode because it maintains its shape intact after being separated from the substrate.

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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un composite de carbone poreux-catalyseur métallique et, plus précisément, un composite de carbone-catalyseur métallique et un procédé de préparation associé, le composite pouvant être utilisé en tant que catalyseur pour diverses réactions électrochimiques. Par conséquent, des particules de catalyseur métallique disposées en son sein sont uniformément dispersées et réparties sur la surface externe d'une structure de carbone poreux et à l'intérieur de celle-ci et peuvent être formées pour être plus petites et plus uniformes. De plus, le composite de carbone poreux-catalyseur métallique mis en œuvre a une taille de particule régulée pour être petite et uniforme de façon à avoir une dispersibilité accrue dans une solution et peut ainsi être plus facilement appliqué à diverses solutions de revêtement.
PCT/KR2023/016751 2022-10-26 2023-10-26 Anode pour batterie secondaire et procédé de fabrication associé WO2024091023A1 (fr)

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