WO2023245986A1 - Matériau composite à base de silicium micronique-carbone à structure noyau-enveloppe et son procédé de préparation, électrode et batterie - Google Patents

Matériau composite à base de silicium micronique-carbone à structure noyau-enveloppe et son procédé de préparation, électrode et batterie Download PDF

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WO2023245986A1
WO2023245986A1 PCT/CN2022/135031 CN2022135031W WO2023245986A1 WO 2023245986 A1 WO2023245986 A1 WO 2023245986A1 CN 2022135031 W CN2022135031 W CN 2022135031W WO 2023245986 A1 WO2023245986 A1 WO 2023245986A1
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micron silicon
carbon
core
silicon
shell structure
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PCT/CN2022/135031
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Chinese (zh)
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王胜彬
王世贤
杨琪
俞会根
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北京卫蓝新能源科技有限公司
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 relates to the technical field of lithium batteries, and specifically relates to a core-shell structure micron silicon-carbon composite material and a preparation method thereof, electrodes and batteries including the core-shell structure micron silicon-carbon composite material.
  • Nanostructured silicon can alleviate the breakage of silicon particles to a certain extent and has become an important direction of current research.
  • the disadvantages of nano-silicon are high cost, poor batch stability, high activity, easy to oxidize, easy to agglomerate, and difficult to disperse, which makes its preparation difficult and poor consistency.
  • Micron silicon can solve the above problems, and it has gradually attracted attention due to its low cost, simple preparation process and high first efficiency.
  • micron silicon compared with nano-silicon, micron silicon has a more severe volume expansion effect and poorer electronic conductivity, resulting in a rapid decline in its cycle performance.
  • General core-shell structures are also difficult to withstand the volume expansion of silicon.
  • this application aims to provide a core-shell structure micron silicon-carbon composite material and a preparation method of a core-shell structure micron silicon-carbon composite material, which can effectively improve improve the cycle performance and Coulombic efficiency of the battery.
  • a core-shell structure micron silicon carbon composite material characterized in that it includes:
  • a carbon shell layer covering the core wherein the carbon shell layer includes a dense carbon layer one, a porous carbon layer and a dense carbon layer two from the inside to the outside.
  • the core-shell structure micron silicon-carbon composite material according to item 1 characterized in that the average particle size D50 of the micron silicon is 1 to 8 ⁇ m, and the sphericity is 0.3 to 0.95.
  • the porosity of the dense carbon layer 1 is 10% to 50%, preferably 10% to 30%.
  • the core-shell structure micron silicon carbon composite material according to any one of items 1 to 3, characterized in that the thickness of the porous carbon layer is 5% to 25% of the average particle diameter D50 of the micron silicon, Preferably, it is 10% to 20%;
  • the pores of the porous carbon layer are formed by a pore-forming agent and an etchant, and the pore-forming agent is selected from the group consisting of nano zinc oxide, nano magnesium oxide, nano aluminum oxide, nano silicon oxide, nano copper oxide, and nano iron oxide. and one or more types of nanomanganese oxide;
  • the average particle size D50 of the pore-forming agent is 50 to 500 nm, preferably 50 to 200 nm;
  • the average pore diameter of the pores is not less than the average particle diameter D50 of the pore-forming agent
  • the etchant is selected from one, two or three types of hydrochloric acid, nitric acid and hydrofluoric acid.
  • the core-shell structure micron silicon-carbon composite material according to any one of items 1 to 4, characterized in that the thickness of the second dense carbon layer is 0.05% to 1% of the average particle diameter D50 of the micron silicon. , preferably 0.1% to 0.2%;
  • the porosity of the second dense carbon layer is 5% to 30%, preferably 5% to 25%.
  • the core-shell structure micron silicon-carbon composite material according to any one of items 1 to 5, characterized in that the Shore hardness of the carbon shell layer is 10-50HSD, preferably 25-40HSD.
  • the core-shell structure micron silicon carbon composite material according to any one of items 1 to 6, characterized in that the carbon source of the dense carbon layer one is selected from the group consisting of asphalt, phenolic resin, humic acid, and tannic acid. , one or more of polymerized dopamine, polypyrrole, methane and ethane; or,
  • the carbon source of the porous carbon layer is selected from one or more of asphalt, phenolic resin, humic acid, tannic acid, polymerized dopamine, polypyrrole, methane and ethane; or,
  • the carbon source of the dense carbon layer 2 is selected from one or more of asphalt, phenolic resin, humic acid, tannic acid, polymerized dopamine, polypyrrole, methane and ethane.
  • the core-shell structure micron silicon carbon composite material according to any one of items 1 to 7, characterized in that the core-shell structure micron silicon carbon composite material has a true density of 1.2 to 2.1 g/cc, preferably 1.4 ⁇ 1.8g/cc.
  • a method for preparing core-shell structure micron silicon-carbon composite material characterized in that it includes the following steps:
  • the composite particle two is sintered in an inert atmosphere and dispersed in an etchant to obtain a composite particle three including micron silicon, a dense carbon layer one and a porous carbon layer;
  • the composite particle three is coated with carbon source three and sintered to obtain a core-shell structure micron silicon-carbon composite material including micron silicon, dense carbon layer one, porous carbon layer and dense carbon layer two.
  • the preparation method according to item 9 or 10 characterized in that the sintering temperature for coating the composite particles three with carbon source three and then sintering is 600 to 1100°C, preferably 700 to 1000°C, preferably The sintering time for coating the composite particles three using carbon source three and then sintering is 2 to 6 hours.
  • the preparation method according to item 10 characterized in that the sintering temperature after coating the composite particles one with a carbon source two and a pore-forming agent is 700 to 1000°C, preferably 800 to 900°C. , it is preferable that the sintering time for coating the composite particles one with the carbon source two and the pore-forming agent and then sintering is 1 to 3 hours.
  • a core-shell structure micron silicon-carbon composite material prepared by the preparation method described in any one of items 9 to 13.
  • micron silicon has an average particle size D50 of 1 to 8 ⁇ m and a sphericity of 0.3 to 0.8.
  • micron silicon is spherical micron Silicon, the interior of which is crystalline silicon and the surface is amorphous silicon.
  • the average particle size D50 of the spherical micron silicon is 1 to 8 ⁇ m, and the sphericity is 0.7 to 0.95;
  • the average particle size D50 of the spherical micron silicon is 2 to 5 ⁇ m;
  • the sphericity of the spherical micron silicon is 0.8 to 0.95;
  • the specific surface area of the spherical micron silicon is 0.5 to 5 m 2 /g, preferably 1 to 4 m 2 /g;
  • the thickness of the amorphous silicon is 1 to 20 nm, preferably 2 to 10 nm.
  • An electrode characterized in that it includes an electrode current collector and an electrode active material layer coated on the surface of the electrode current collector, and the electrode active material layer includes any one of items 1 to 8 and 14.
  • the electrode is a negative electrode.
  • a battery characterized in that it includes a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode is the negative electrode described in item 17.
  • micron silicon-dense carbon layer one-porous carbon layer-dense carbon layer two.
  • Each carbon layer is organically connected and does not exist as a separate component.
  • the dense carbon layer tightly covers the micron silicon, providing inward pressure during circulation, maintaining physical contact between the small particles produced after the micron silicon particles are broken, and at the same time serving as an expansion force transmission medium to transfer stress to the porous carbon layer for absorption ; And avoid direct contact between silicon and the cavities in the porous carbon layer to prevent the fine particles after broken silicon from falling into the cavities and losing electrochemical activity.
  • the porous carbon layer has numerous cavities, which provide reversible compression space and space for the expansion of silicon.
  • the reverse effect of stress is used to compress the dense carbon layer during the delithiation state, so that the dense carbon layer will be released after the electrochemical process.
  • the broken micron silicon particles are tightly packed to maintain ion/electron channels.
  • the dense carbon layer 2 serves as a strong coating layer to maintain the structural integrity and mechanical stability of the porous carbon layer when it is subjected to micron silicon expansion stress.
  • the dense carbon layer 2 is combined with the porous carbon layer to effectively absorb and release the expansion stress.
  • the dense carbon layer isolates the infiltration of electrolyte and avoids side reactions between the many active sites of the porous carbon layer and the electrolyte, thereby improving cycle performance and Coulombic efficiency.
  • the porous carbon layer of the core-shell structure micron silicon-carbon composite material of this application has carbon pillars connecting the dense carbon layer one and the dense carbon layer two.
  • the carbon pillars play the role of conducting ions and electrons during the electrochemical process. Avoid the existence of cavity layers in the core-shell structure from blocking the conduction of isolators and electrons.
  • the core-shell structure micron silicon-carbon composite material of this application can not only alleviate the volume expansion of micron silicon and maintain particle stability; it can also provide an inward pressure for the broken particles after circulation, maintaining the physical properties of the primary particles after being broken. Contact to maintain electron and ion diffusion paths and improve cycle performance.
  • Figure 1 is a schematic structural diagram of a micron silicon-carbon composite material with a core-shell structure according to a specific embodiment of the present application.
  • Figure 2 is a TEM image of spherical micron silicon according to a specific embodiment of the present application.
  • this application provides a core-shell structure micron silicon carbon composite material, which includes:
  • a carbon shell layer covering the core wherein the carbon shell layer includes a dense carbon layer one, a porous carbon layer and a dense carbon layer two from the inside to the outside.
  • the core-shell structure micron silicon-carbon composite material of the present application constructs the cavity in the carbon coating layer, which avoids the obstacles in ion and electron conduction caused by the direct contact between the cavity and silicon.
  • the internal dense carbon layer wraps the micron silicon, and the coating forms inward pressure during circulation, ensuring that the particles after the micron silicon is broken still maintain physical contact and maintain electronic and ion conductivity.
  • the dense carbon layer 2 on the surface is combined with the porous carbon layer inside to jointly absorb and release expansion stress. At the same time, the dense carbon layer isolates the infiltration of electrolyte and avoids side reactions between the many active sites of the porous carbon layer and the electrolyte, thereby improving cycle performance and Coulombic efficiency.
  • Inside-out in this application refers to the direction from the core to the carbon shell.
  • the core-shell structure micron silicon-carbon composite material is composed of: a core formed of micron silicon 1 and a carbon shell layer covering the core, wherein the carbon
  • the shell layer includes a dense carbon layer 2, a porous carbon layer 3 and a dense carbon layer 2 4 from the inside to the outside.
  • the average particle size D50 of the micron silicon of the present application is 1 to 8 ⁇ m, for example, it can be 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.5 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, etc.
  • the sphericity is 0.3 ⁇ 0.95, for example, it can be 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43 ⁇ 0.44 ⁇ 0.45 ⁇ 0.45 ⁇ 0.46 ⁇ 0.47 ⁇ 0.48 ⁇ 0.49 ⁇ 0.5 ⁇ 0.51 ⁇ 0.52 ⁇ 0.53 ⁇ 0.54 ⁇ 0.55 ⁇ 0.56 ⁇ 0.57 ⁇ 0.58 ⁇ 0.59 ⁇ 0.6 ⁇ 0.61 ⁇ 0.62 ⁇ 0.63 ⁇ 0.64 ⁇ 0.65 ⁇ 0.66 ⁇ 0.67 , 0.68, 0.69,
  • the “average particle size D50” in this application refers to the particle size corresponding to when the cumulative particle size distribution number of a sample reaches 50%. Its physical meaning is that particles with a particle size smaller than it account for 50% of the total. Particle size distribution can be detected using conventional instruments used by those skilled in the art, such as using a laser particle size analyzer.
  • the “sphericity” used in this application is a parameter that characterizes the morphology of particles. The closer a particle is to a sphere in shape, the closer its sphericity is to 1.
  • the ratio of the surface area of a sphere with the same volume as the object to the surface area of the object is sphericity.
  • the sphericity of the ball is equal to 1, and the sphericity of other objects is less than 1.
  • the sphericity formula of any particle is: Among them, ⁇ is the particle sphericity, Vp is the particle volume, and Sp is the particle surface area.
  • the sphericity of the present application can be detected, for example, by the specific methods given in the examples, and measured using a dynamic image particle analyzer.
  • the thickness of the dense carbon layer I is 0.05% to 1% of the average particle size D50 of micron silicon, for example, it can be 0.05%, 0.07%, 0.09%, 0.1%, 0.1%, 0.15 %, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%, etc., preferably 0.1% to 0.4%.
  • the dense carbon layer wraps the micron silicon. During circulation, the coating layer forms inward pressure to ensure that the particles after the micron silicon is broken still maintain physical contact and maintain electronic and ion conductivity.
  • the thickness of the dense carbon layer is too small, it will not be able to withstand it. Micron silicon expands and transfers its expansion stress to the porous carbon layer, resulting in the failure of the cladding layer structure and a decrease in the electrochemical performance of the material; if the thickness of the dense carbon layer is too large, the electronic conductive channels are affected, and at the same time the material's electrochemical properties are affected. Specific capacity and first effect.
  • the thickness of the dense carbon layer 1 of the present application can be obtained by measuring multiple points through a transmission electron microscope and taking the average value.
  • it can be 2 points, 3 points, 4 points, 5 points, 6 points, 7 points, 8 points. points, 9 points, 10 points, etc.
  • the porosity of the dense carbon layer one is 10% to 50%, for example, it can be 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, etc., preferably 10% to 30%.
  • the dense carbon layer needs to transfer the expansion force of micron silicon to the porous carbon layer, and it bears a very huge force in this process.
  • the smaller porosity in this application can reduce defects in the carbon layer structure and improve the yield of the material. strength.
  • the porosity of the dense carbon layer 1 of the present application can be measured, for example, by a true density tester.
  • the thickness of the porous carbon layer is 5% to 25% of the average particle diameter D50 of micron silicon, for example, it can be 5%, 6%, 7%, 8%, 9%, 10% , 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., preferably 10 % ⁇ 20%.
  • the thickness of the porous carbon layer of the present application can be obtained by measuring multiple points through a transmission electron microscope and taking the average, for example, it can be 2 points, 3 points, 4 points, 5 points, 6 points, 7 points, or 8 points. points, 9 points, 10 points, etc.
  • the pores of the porous carbon layer are formed by a pore-forming agent and an etchant.
  • the pore-forming agent is added and mixed with the carbon source, and then an etchant that can react with the pore-forming agent is added to form the said pore-forming agent.
  • Porous, reaction products of pore formers and etchants as well as excess etchant can be removed by cleaning and subsequent sintering steps.
  • the pore-forming agent can be selected from one or more of nano zinc oxide, nano magnesium oxide, nano aluminum oxide, nano silicon oxide, nano copper oxide, nano iron oxide and nano manganese oxide; the etchant can be Select one, two or three types from hydrochloric acid, nitric acid and hydrofluoric acid.
  • the average particle size D50 of the pore-forming agent is 50 to 500nm, for example, it can be 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, etc., preferably 50 to 500nm. 200nm.
  • the average pore size of the porous carbon layer is not less than the average particle size D50 of the pore-forming agent.
  • the average pore size of the present application can be measured by gas permeation method.
  • the thickness of the second dense carbon layer is 0.05% to 1% of the average particle diameter D50 of micron silicon, for example, it can be 0.05%, 0.07%, 0.09%, 0.1%, 0.1%, 0.15 %, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%, etc., preferably 0.1% to 0.2%.
  • the second dense carbon layer is coated on the porous carbon layer, which plays the role of closing the porous carbon layer and isolating the electrolyte.
  • the thickness of the dense carbon layer 2 of the present application can be obtained by measuring multiple points through a transmission electron microscope and taking the average value. For example, it can be 2 points, 3 points, 4 points, 5 points, 6 points, 7 points, 8 points. points, 9 points, 10 points, etc.
  • the porosity of the second dense carbon layer is 5% to 30%, for example, it can be 5%, 7%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc., preferably 5% to 25%.
  • the second dense carbon layer cooperates with the two inner coating layers to alleviate the expansion of micron silicon. It will be affected by the expansion of micron silicon during the cycle. If the porosity is too high, the structure will There are many defects, and the yield strength of the structure decreases, which will cause the structure to be destroyed during the cycle; at the same time, the dense carbon layer 2 also plays a role in isolating the electrolyte. Excessive porosity will lead to the penetration of the electrolyte, thereby reducing the electrochemical performance of the material. .
  • the porosity of the dense carbon layer 2 of the present application can be measured, for example, by a true density tester.
  • the Shore hardness of the carbon shell layer is 10-50HSD, for example, it can be 20HSD, 25HSD, 30HSD, 35HSD, 40HSD, 45HSD, etc., preferably 25-40.
  • the Shore hardness of the carbon shell layer in this application refers to the Shore hardness of the carbon shell layer including dense carbon layer one, porous carbon layer and dense carbon layer two.
  • “Shore hardness” in this application refers to a method of testing and expressing the hardness of materials. It is measured using a Shore hardness tester. For example, the material can be mixed with a binder and then pressed into tablets. The pressure is the limit when the particles are not broken.
  • the maximum pressure it can withstand can be observed and adjusted with SEM), and then measured using this piece.
  • the Shore hardness that is too small cannot maintain the structure of the coating layer itself and the stress generated by silicon expansion. Only an appropriate Shore hardness can be maintained. Its own structure is stable and its digestion volume expands.
  • the true density of the core-shell structure micron silicon carbon composite material is 1.2-2.1g/cc, for example, it can be 1.2g/cc, 1.3g/cc, 1.4g/cc, 1.5g/cc , 1.6g/cc, 1.7g/cc, 1.8g/cc, 1.9g/cc, 2.0g/cc, 2.1g/cc, etc., preferably 1.4 to 1.8g/cc.
  • the “true density” in this application refers to the actual mass of solid matter per unit volume of the material in an absolutely dense state, that is, the density after removing internal pores or gaps between particles. The true density of this application is measured using a powder true density tester.
  • the sample can be placed in the true density tester, using helium as the medium, gradually pressurizing the measuring chamber to a specified value, and then the helium expands into the expansion chamber.
  • the equilibrium pressure of the two processes is automatically recorded by the instrument. According to the law of conservation of mass, after calibrating the volumes of the measurement chamber and the expansion chamber through the standard ball, the volume of the sample is determined and the true density is calculated.
  • the mass ratio of the carbon shell to the core is 0.16-0.5:1, preferably 0.22-0.36:1, for example, it can be 0.16:1, 0.18:1, 0.2:1, 0.22:1 , 0.28:1, 0.3:1, 0.32:1, 0.36:1, 0.38:1, 0.4:1, 0.42:1, 0.46:1, 0.48:1, 0.5:1, etc.
  • the carbon sources of the first dense carbon layer, the porous carbon layer and the second dense carbon layer may be exactly the same, may be completely different, or may not be exactly the same.
  • the carbon source in this application is not limited and can be any carbon source.
  • the carbon source of each layer can be selected from one of asphalt, phenolic resin, humic acid, tannic acid, polymerized dopamine, polypyrrole, methane and ethane. Or two or more, preferably one or two or more selected from the group consisting of asphalt, phenolic resin and humic acid.
  • the carbon source of the dense carbon layer I is selected from one or more of asphalt, phenolic resin and humic acid; and/or the carbon source of the porous carbon layer is selected from asphalt. , one or more of phenolic resin and humic acid; and/or the carbon source of the dense carbon layer 2 is selected from one or more of asphalt, phenolic resin and humic acid.
  • this application also provides a method for preparing a core-shell structure micron silicon-carbon composite material, which includes the following steps:
  • the composite particle three is coated with carbon source three and sintered to obtain a core-shell structure micron silicon-carbon composite material including micron silicon, dense carbon layer one, porous carbon layer and dense carbon layer two.
  • the preparation method of the core-shell structure micron silicon carbon composite material of the present application includes the following steps:
  • the composite particle three is coated with carbon source three and sintered to obtain a core-shell structure micron silicon-carbon composite material including micron silicon, dense carbon layer one, porous carbon layer and dense carbon layer two.
  • This application does not specifically limit the etching time of the etchant, as long as the etchant is excessive.
  • the sintering temperature for coating micron silicon with the second carbon source and then sintering is 700 to 1000°C, for example, it can be 700°C, 720°C, 740°C, 760°C, 780°C, 800°C, 820°C, 840°C, 860°C, 880°C, 900°C, 920°C, 940°C, 960°C, 980°C, 1000°C, etc., preferably 800 ⁇ 900°C, preferably using carbon Source 2 coats the micron silicon and then sinters the sintering time for 1 to 3 hours.
  • the sintering temperature for coating the composite particles three with carbon source three and then sintering is 600 to 1100°C, for example, it can be 600°C, 620°C, 640°C, 660°C, 680°C, 700°C, 720°C, 740°C, 760°C, 780°C, 800°C, 820°C, 840°C, 860°C, 880°C, 900°C, 920°C, 940°C, 960°C, 980°C, 1000°C, 1020°C , 1040°C, 1060°C, 1080°C, 1100°C, etc., preferably 700 to 1000°C, and the sintering time for coating the composite particles three with carbon source three and then sintering is preferably 2 to 6 hours.
  • the sintering device in this application. Any device that can pass into the atmosphere and heat up the sintering can be used.
  • it can be a dry rotary kiln, an electric furnace, a tube furnace, a box furnace, a roller kiln, etc.
  • it can be used Oxygen-acetylene flame, oxygen-hydrogen flame, etc. sintering.
  • the sintering of the present application is performed under an inert gas.
  • the inert atmosphere of the present application is not limited and can be any inert atmosphere, such as nitrogen or argon.
  • the coating is solid phase coating.
  • a mechanical fusion machine can be used for solid phase coating.
  • both the porous carbon layer and the dense carbon layer are solid phase coatings, and the dense carbon layer one can be solid phase coating, gas phase coating, or liquid phase coating.
  • the dense carbon layer The first carbon layer is solid phase coating.
  • the sintering includes cooling.
  • the composite particles are dispersed in an etchant, stirred, filtered, washed, and dried to obtain micron silicon, Composite particles of dense carbon layer one and porous carbon layer three.
  • the present application also provides a core-shell structure micron silicon-carbon composite material prepared by any of the aforementioned preparation methods.
  • the micron silicon can be crystalline silicon or amorphous silicon-coated crystal. Spherical micron silicon in the state of silicon.
  • the average particle diameter D50 of the crystalline micron silicon of the present application is 1 to 8 ⁇ m, for example, it can be 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.5 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, etc.
  • the sphericity is 0.3 ⁇ 0.8, for example, it can be 0.3, 0.31, 0.32, 0.33, 034, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.45, 0.46, 0.48, 0.48, 0.5, 0.51, 0.52, 0.54, 0.55, 0.57, 0.58, 0.59, 0.62, 0.64, 0.66, 0.67, 0.68, 0.69, 0.68, 0.69, 0.68, 0.69, 0.69, 0.69, 0.69, 0.
  • the interior of the spherical micron silicon in this application is crystalline silicon and the surface is amorphous silicon.
  • the average particle size D50 of the spherical micron silicon is 1 to 8 ⁇ m, for example, it can be 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.5 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, etc.
  • the sphericity is 0.7 ⁇ 0.95, for example, it can be 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, etc.
  • Micron silicon in the existing technology is irregularly shaped crystalline silicon with many edges and corners on the surface. Crystalline silicon has anisotropy and anisotropic expansion. During the silicon lithium insertion process, anisotropic volume expansion easily causes failure at the edges and corners. or destroy particle integrity.
  • the spherical micron silicon in this application has a certain thickness of amorphous silicon on the surface. The amorphous silicon is isotropic and expands in the same direction, so that the spherical micron silicon exerts uniform force on its outer coating layer in all directions, which is beneficial to maintaining the Particle structural stability during electrochemical processes.
  • the average particle size D50 of the spherical micron silicon of the present application is 2 to 5 ⁇ m; the sphericity of the spherical micron silicon is 0.8 to 0.95.
  • the specific surface area of the spherical micron silicon of the present application is 0.5-5m 2 /g, for example, it can be 0.5m 2 /g, 1m 2 /g, 1.5m 2 /g, 2m 2 / g, 2.5 m 2 /g, 3m 2 /g, 3.5m 2 /g, 4m 2 /g, 4.5m 2 /g, 5m 2 /g, etc., preferably 1 to 4m 2 /g.
  • the specific surface area of the spherical micron silicon of the present application can be detected by the specific method given in the embodiment, and measured using the BET specific surface tester.
  • the spherical micron silicon particle size distribution of the present application is moderate and the sphericity is high.
  • Such structural advantages enable it to have a lower specific surface area, higher particle fluidity and higher tap density, thereby reducing the difficulty of subsequent processes and having It is beneficial to maintain the stability of the particle structure during the electrochemical process.
  • the thickness of the amorphous silicon in the spherical micron silicon of the present application is 1 to 20nm, for example, it can be 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm , 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, etc., preferably 2 to 10nm.
  • the thickness of amorphous silicon can be obtained by averaging multiple measurements through a transmission electron microscope, for example, it can be 2 points, 3 points, 4 points, 5 points, 6 points, 7 points, 8 points, 9 points, 10 points, etc.
  • the structure of the spherical micron silicon of the present application is shown in the TEM picture of Figure 2.
  • the part with visible lattice stripes on the left side of the figure is the crystalline silicon 5 inside the spherical micron silicon; the part without the lattice stripes on the right side is the spherical micron silicon.
  • the thickness of the amorphous silicon in the outer layer is 10 nm.
  • This application can simply prepare the spherical micron silicon of this application through the following method, which method includes the following steps:
  • the crystalline micron silicon is sintered, kept warm, cooled and crushed under an inert atmosphere to obtain spherical micron silicon.
  • the crystalline micron silicon is crystalline micron silicon of the related art.
  • the average particle size D50 of the crystalline micron silicon is 1 to 8 ⁇ m, for example, it can be 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, or 5.5 ⁇ m.
  • the sphericity of the crystalline micron silicon is 0.3 to 0.7, for example, it can be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, etc.
  • the average particle size D50 of the spherical micron silicon of the present application is less than or equal to the average particle size D50 of the crystalline micron silicon.
  • the sphericity of the spherical micron silicon of the present application is greater than the sphericity of the crystalline micron silicon.
  • the inert atmosphere is not limited and can be any inert atmosphere, such as nitrogen or argon.
  • the sintering temperature is 1300-1600°C, for example, it can be 1300°C, 1310°C, 1320°C, 1330°C, 1340°C, 1350°C, 1360°C, 1370°C, 1380°C, 1390°C, 1400°C, 1410°C, 1420°C, 1430°C, 144°C, 1450°C, 1460°C, 1470°C, 1480°C, 1490°C, 1500°C, 1510°C, 1520°C, 1530°C, 1540°C, 1550°C, 1560°C , 1570°C, 1580°C, 1590°C, 1600°C, etc., preferably 1400 to 1500°C.
  • the sintering device in this application. Any device capable of heating up sintering can be used.
  • it can be a dry rotary kiln, an electric furnace, a tube furnace, a box furnace, a roller kiln, etc., and for example, an oxygen-acetylene flame can be used. , oxygen-hydrogen flame and other sintering.
  • the temperature is raised to the sintering temperature at a heating rate of 1 to 10°C/min, preferably 3 to 6°C/min.
  • the heating rate can be, for example, 1°C/min, 1.5°C/min, 2°C/min, 2.5°C/min, 3°C/min, 3.5°C/min, 4°C/min, 4.5°C/min, 5°C/min, 5.5°C/min, 6°C/min, 6.5°C/min, 7°C/min, 7.5°C/min, 8°C/min, 8.5°C/min, 9°C/min, 9.5°C/min, 10°C/min, etc.
  • the sintering temperature is higher than 1300°C.
  • the temperature starts to rise to the sintering temperature at a heating rate of 3 to 6°C/min.
  • the heating rate needs to be adjusted so that it is not too fast to avoid the rapid melting of the silicon edges and the adhesion of the particles.
  • the adhesion can be opened by crushing, the crushing process may create edges and corners.
  • the holding time is 0.5-10h, for example, it can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5 h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, etc., preferably 0.5 to 4h. If the heat preservation time is too short, the edges and corners are not fully melted, and the sphericity is not high; if the heat preservation time is too long, the edges and corners are fully melted and may cause contact transfer between the particles, resulting in adhesion.
  • the cooling rate is 10-100°C/min, for example, it can be 10°C/min, 15°C/min, 20°C/min, 25°C/min, 30°C/min, 35°C/min. min, 40°C/min, 45°C/min, 50°C/min, 55°C/min, 60°C/min, 65°C/min, 70°C/min, 75°C/min, 80°C/min, 85°C/ min, 90°C/min, 95°C/min, 100°C/min, etc., preferably 50 to 80°C/min. Controlling the cooling rate, crystal dislocations form a layer of amorphous silicon.
  • Controlling the cooling rate at 10-100°C/min can make the thickness of amorphous silicon reach 1-20nm.
  • the cooling device in this application, and any device capable of cooling can be used, for example, it can be a method of purging a low-temperature inert atmosphere.
  • the core-shell structure composite material including spherical micron silicon of the present application When used in a lithium-ion battery, the spherical micron silicon expands isotropically, and its spherical structure improves the continuity of the surface coating, and the coating layer is evenly stressed during expansion. , the composite material overcomes the huge expansion effect of micron silicon, thereby reducing the deformation of the battery during cycling and improving the safety performance of the battery. At the same time, the composite material maintains structural stability during the cycle, avoiding the growth of the irreversible SEI film at the interface and the infiltration of electrolyte, thus improving the cycle performance of the battery.
  • the present application also provides an electrode.
  • the electrode of the present application includes an electrode current collector and an electrode active material layer coated on the electrode current collector.
  • the electrode active material layer at least contains spherical micron silicon as the electrode active material.
  • the spherical micron silicon is any of the aforementioned spherical micron silicon or spherical micron silicon prepared by any of the foregoing preparation methods of the present application.
  • the electrode active material layer may also include any of the core-shell structure composite materials mentioned above in this application.
  • the electrode of the present application is preferably a negative electrode.
  • the electrode active material of the present application can be a negative electrode active material, which is not particularly limited, and negative electrode active materials commonly used in this technical field can be used.
  • the electrode active material uses the spherical micron silicon of the present application as the main component.
  • the electrode active material layer may also contain other electrode active materials. Next, other electrode active materials will be described.
  • Examples of the negative electrode active material include highly crystalline carbon graphite (natural graphite, artificial graphite, etc.), low crystalline carbon (soft carbon), hard carbon, carbon black (Ketjen Black (registered trademark), acetylene black , channel carbon black, lamp black, oil furnace carbon black, thermal carbon black, etc.), fullerene, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon filaments and other carbon materials.
  • examples of negative electrode active materials include Si, Ge, Sn, Pb, Al, In, Zn, H, Ca, Sr, Ba, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, and Hg.
  • the negative electrode active material include metal materials such as lithium metal and lithium-transition metal composite oxides such as lithium-titanium composite oxides (for example, lithium titanate Li 4 Ti 5 O 12 ).
  • the material is not limited to these materials, and conventionally known materials that can be used as negative electrode active materials for lithium ion batteries can be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the electrode current collector of the present application may be a negative electrode current collector, which is made of conductive material.
  • the thickness of the electrode current collector is usually about 0.1 to 1000 ⁇ m, preferably about 1 to 100 ⁇ m.
  • the shape of the electrode current collector is not particularly limited.
  • the material constituting the electrode current collector is not particularly limited. For example, it can be copper.
  • the electrode may be prepared by forming the active material layer on the electrode current collector using conventionally known methods, but is not limited thereto. Those skilled in the art can select a suitable method to manufacture electrodes according to the type of battery to be manufactured.
  • the electrode using the electrode active material can be produced by a conventional method. That is, the electrode active material and the conductive agent, as well as the binder and thickener used as needed, can be dry-mixed into a sheet, and the sheet-shaped material can be pressed onto the electrode current collector, or These materials are dissolved or dispersed in a liquid medium to form a slurry, and the slurry is applied to an electrode current collector and dried to form an electrode active material layer on the electrode current collector, thereby obtaining an electrode.
  • the conductive agent may contain any other component that can be used as a conductive agent.
  • it may also include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite; carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke.
  • metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite; carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke.
  • These conductive agents may be used alone or in combination of two or more in any combination and ratio.
  • the electrode active material layer may further contain a binder.
  • a binder used to produce the electrode active material layer.
  • it may be a material that can be dissolved or dispersed in the liquid medium used in producing the electrode.
  • the solvent used to form the slurry is not particularly limited as long as it can dissolve or disperse the electrode active material, the conductive agent, the binder and, if necessary, the thickener.
  • Water-based solvents can be used. Solvents and any solvent in organic solvents.
  • the electrode active material layer may also contain a thickener.
  • a thickening agent there are no particular restrictions.
  • the present application also provides a battery, which includes a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode is the aforementioned negative electrode of the present application.
  • a battery in this application refers to a single physical module that includes one or more battery cells to provide higher voltage and capacity.
  • the battery mentioned in this application may include a battery module or a battery pack.
  • the battery cells of this application may include one or more of lithium ion secondary batteries, lithium ion primary batteries, lithium sulfur batteries, sodium lithium ion batteries, sodium ion batteries and magnesium ion batteries. This application does not limited.
  • the battery cell of the present application may be in the shape of a cylinder, a flat body, a rectangular parallelepiped or other shapes, and the embodiments of the present application are not limited to this. Battery cells are generally divided into three types according to packaging methods: cylindrical battery cells, prismatic battery cells and soft-pack battery cells. This application is not limited thereto.
  • the separator is usually disposed between the positive electrode and the negative electrode.
  • any known separator can be used.
  • resins, glass fibers, inorganic substances, etc. can be used, and materials in the form of porous sheets or nonwoven fabrics that are excellent in liquid retention are preferably used.
  • Electrolyte is filled between the positive and negative electrodes.
  • the electrolyte may be an aqueous electrolyte or a non-aqueous electrolyte.
  • the electrolyte may be an electrolyte, a polymer gel electrolyte, or a solid polymer electrolyte.
  • reagents or instruments used are conventional reagents that can be purchased commercially if the manufacturer is not indicated. or instrument.
  • 1kg of crystalline micron silicon with a D50 of 5 ⁇ m and a sphericity of 0.3 is heated to 1400°C at a rate of 5°C/min in a nitrogen atmosphere. After being kept for 5 hours, it is cooled to room temperature at a rate of 50°C/min. Take it out and crush it to obtain a D50 of 4 ⁇ m, spherical micron silicon with a sphericity of 0.8.
  • 1kg of crystalline micron silicon with a D50 of 6 ⁇ m and a sphericity of 0.5 is heated to 1500°C at 10°C/min in a nitrogen atmosphere. After being kept for 2 hours, it is cooled to room temperature at a rate of 100°C/min. Take it out and crush it to obtain a D50 of 6 ⁇ m. , spherical micron silicon with a sphericity of 0.9.
  • 1kg of crystalline micron silicon with a D50 of 2 ⁇ m and a sphericity of 0.6 is heated to 1400°C at 3°C/min in a nitrogen atmosphere. After being kept for 4 hours, it is cooled to room temperature at a rate of 60°C/min, taken out, and crushed to obtain a D50 of 2 ⁇ m spherical micron silicon with a sphericity of 0.95.
  • 1kg of crystalline micron silicon with a D50 of 4 ⁇ m and a sphericity of 0.3 is heated to 1450°C at a rate of 5°C/min in a nitrogen atmosphere. After incubation for 5 hours, it is cooled to room temperature at a rate of 80°C/min. Take it out and crush it to obtain a D50 of 3 ⁇ m. , spherical micron silicon with a sphericity of 0.8.
  • the difference between this embodiment and Embodiment 3 is that the cooling rate is 50°C/min.
  • the thickness of the dense carbon layer one is 20 nm
  • the thickness of the porous carbon layer is 1 ⁇ m
  • the thickness of the second dense carbon layer is 5 nm.
  • Embodiment 2-1 The difference between this embodiment and Embodiment 2-1 is that the sphericity of crystalline micron silicon is 0.3.
  • the thickness of the dense carbon layer one is 14 nm
  • the thickness of the porous carbon layer is 0.8 ⁇ m
  • the thickness of the second dense carbon layer is 4 nm.
  • Embodiment 2-1 The difference between this embodiment and Embodiment 2-1 is that the D50 of crystalline micron silicon is 8 ⁇ m.
  • the thickness of the dense carbon layer one is 12 nm
  • the thickness of the porous carbon layer is 0.64 ⁇ m
  • the thickness of the second dense carbon layer is 3.2 nm.
  • Embodiment 2-1 The difference between this embodiment and Embodiment 2-1 is that the pore-forming agent is nano-alumina.
  • the thickness of the dense carbon layer one is 20 nm
  • the thickness of the porous carbon layer is 0.92 ⁇ m
  • the thickness of the second dense carbon layer is 5 nm.
  • Example 2-1 The difference between this embodiment and Example 2-1 is that the average particle size D50 of the pore-forming agent is 50 nm.
  • the thickness of the dense carbon layer one is 20 nm
  • the thickness of the porous carbon layer is 1.24 ⁇ m
  • the thickness of the second dense carbon layer is 3.6 nm.
  • Example 2-1 The difference between this embodiment and Example 2-1 is that the average particle size D50 of the pore-forming agent is 500 nm.
  • the thickness of the dense carbon layer one is 20 nm
  • the thickness of the porous carbon layer is 0.76 ⁇ m
  • the thickness of the second dense carbon layer is 6 nm.
  • Example 2-1 The difference between this embodiment and Example 2-1 is that the carbon sources in steps (1), (2) and (4) are all phenolic resins.
  • the thickness of the dense carbon layer one is 16 nm
  • the thickness of the porous carbon layer is 0.68 ⁇ m
  • the thickness of the second dense carbon layer is 4 nm.
  • Example 2-1 The difference between this embodiment and Example 2-1 is that the carbon sources in steps (1), (2) and (4) are all humic acid.
  • the thickness of the dense carbon layer one is 16 nm
  • the thickness of the porous carbon layer is 1.12 ⁇ m
  • the thickness of the second dense carbon layer is 6 nm.
  • Embodiment 2-1 The difference between this embodiment and Embodiment 2-1 is that the amount of nano-magnesium oxide is 100g.
  • the thickness of the dense carbon layer one is 20 nm
  • the thickness of the porous carbon layer is 0.2 ⁇ m
  • the thickness of the second dense carbon layer is 5 nm.
  • Embodiment 2-1 The difference between this embodiment and Embodiment 2-1 is that the amount of nano-magnesium oxide is 250g.
  • the thickness of the dense carbon layer one is 20 nm
  • the thickness of the porous carbon layer is 0.6 ⁇ m
  • the thickness of the second dense carbon layer is 5 nm.
  • the thickness of the dense carbon layer one is 18 nm
  • the thickness of the porous carbon layer is 0.88 ⁇ m
  • the thickness of the second dense carbon layer is 4 nm.
  • the thickness of the dense carbon layer one is 24 nm
  • the thickness of the porous carbon layer is 1.24 ⁇ m
  • the thickness of the second dense carbon layer is 7.2 nm.
  • Example 2-11 The difference between this embodiment and Example 2-11 is that the crystalline micron silicon with a D50 of 4 ⁇ m and a sphericity of 0.8 is replaced with the D50 of 4 ⁇ m, a sphericity of 0.8 and a crystalline interior prepared in Example 1-1. Silicon, spherical micron silicon with amorphous silicon surface.
  • the thickness of the carbon layer is 55nm.
  • the core-shell structure composite material (90wt%) obtained in Examples 2-1 to 2-13 was mixed with conductive agent (1wt% CNT and 3wt% SP), binder (4wt% CMC and 2wt% SBR) and deionized Mix water into a slurry, apply it, dry it and cut it to obtain a lithium electrode sheet, where "wt%" represents the percentage of each component in the total weight of the core-shell structure composite material, conductive agent and binder. Assemble the lithium electrode sheet and conventional electrolyte into a button half cell, and perform charge and discharge tests. The test conditions are: in the voltage range of 5mV-0.8V, activate at 0.1C/0.1C for 2 turns, and cycle at 0.3C/0.3C. After testing, the electrochemical performance parameters of the batteries made with the materials of Examples 2-1 to 2-13 are as shown in Table 5 below.
  • Example 2-5 2785 88.9 88
  • Example 2-6 2802 88.5
  • Example 2-7 2678 87.2
  • Example 2-8 2843 89.6 79
  • Example 2-9 2821 89.4
  • Example 2-10 2842 89.8
  • Example 2-11 2863 90.1
  • Example 2-12 2763 88.6
  • Example 2-13 1957 83.6 90
  • Example 2-14 2851 90.3 92 Comparative example 1 2762 90.8 28

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Abstract

La présente invention concerne un matériau composite à base de silicium micronique-carbone à structure noyau-enveloppe, comprenant : un noyau formé par du silicium micronique ; et une couche d'enveloppe en carbone déposée sur le noyau, la couche d'enveloppe en carbone comprenant séquentiellement, de l'intérieur vers l'extérieur : une couche de carbone compacte 1, une couche de carbone poreuse et une couche de carbone compacte 2. La présente invention concerne en outre un procédé de préparation pour le matériau composite à base de silicium micronique-carbone à structure noyau-enveloppe, une électrode comprenant le matériau composite à base de silicium micronique-carbone à structure noyau-enveloppe, une batterie comprenant l'électrode, un circuit comprenant la batterie, et un dispositif électrique comprenant le circuit.
PCT/CN2022/135031 2022-06-23 2022-11-29 Matériau composite à base de silicium micronique-carbone à structure noyau-enveloppe et son procédé de préparation, électrode et batterie WO2023245986A1 (fr)

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