WO2022000589A1 - Procédé destiné à préparer un matériau d'électrode négative composite à base de silicium - Google Patents

Procédé destiné à préparer un matériau d'électrode négative composite à base de silicium Download PDF

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WO2022000589A1
WO2022000589A1 PCT/CN2020/102976 CN2020102976W WO2022000589A1 WO 2022000589 A1 WO2022000589 A1 WO 2022000589A1 CN 2020102976 W CN2020102976 W CN 2020102976W WO 2022000589 A1 WO2022000589 A1 WO 2022000589A1
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silicon
nano
negative electrode
electrode material
particles
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PCT/CN2020/102976
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Chinese (zh)
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张健
赵前进
徐斌
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瑞声声学科技(深圳)有限公司
瑞声科技（南京）有限公司
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Publication of WO2022000589A1 publication Critical patent/WO2022000589A1/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
    • H01M4/36—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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a silicon-based composite negative electrode material.
  • silicon anode As an anode material for next-generation lithium-ion batteries, silicon anode has the advantages of high capacity (4200 mAh g-1), high abundance, low operating voltage platform and low price, attracting the attention of many researchers, but the volume of silicon-based anode materials Large swelling (300%) and poor electrical conductivity lead to poor cycle performance and rate performance of batteries based on it.
  • the purpose of the present invention is to provide a preparation method of a silicon-based composite negative electrode material, which can improve the silicon negative electrode by using the shell structure, buffer its volume expansion, improve its electrical conductivity, and improve the cycle performance and rate performance of the silicon-based negative electrode material.
  • a preparation method of a silicon-based composite negative electrode material comprising:
  • the conductive nano-silicon-based particles as the core and the polymer material as the outer shell, build a shell structure that enables the conductive nano-silicon-based particles to change in volume in the shell, and the shell structure is The silicon-based composite negative electrode material.
  • the nano-silicon-based particles include one or more of nano-silicon particles, nano-silicon oxide particles, and nano-silicon-silicon oxide composite particles, and the particle size of the nano-silicon-based particles is less than or equal to 150 nm.
  • the shell structure includes one or more of hollow nanosphere structure, nanotube structure, porous nanofiber structure, coaxial nanowire structure, and porous nanotube structure.
  • the conductive nano-silicon-based particles are used as the inner core and the polymer material is used as the outer shell to build a shell structure that enables the conductive nano-silicon-based particles to change in volume in the outer shell.
  • the method is one of electrospinning method, vapor deposition method, spray drying method, electrospray method, microfluidic method and solution method.
  • the conductive nano-silicon-based particles are used as the inner core and the polymer material is used as the outer shell to build a shell structure that enables the conductive nano-silicon-based particles to change in volume in the outer shell.
  • the method is electrospinning, including:
  • the spinning mixture is cured at a high temperature to obtain a cured mixture, wherein the curing temperature is 250-500° C. and the curing time is 1-4 h;
  • the cured mixture is sintered at high temperature to obtain the shell structure, that is, the silicon-based composite negative electrode material, wherein the sintering temperature is 600-1500° C. and the sintering time is 1-10 h.
  • the first solution includes several kinds of water, glycerol, N,N dimethylformamide, acetone, acetonitrile and ethanol;
  • the pore-forming agent includes sodium carbonate, potassium carbonate, calcium carbonate, ammonium bicarbonate and several kinds of polymethyl methacrylate;
  • the polymer material includes several kinds of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral and polyvinylidene fluoride;
  • the second organic Solvents include several of glycerol, N,N dimethylformamide, acetone, and acetonitrile.
  • the electrospinning includes one of needle spinning, drum spinning and solution spinning.
  • the conductive nano-silicon-based particles are subjected to conductive treatment to obtain conductive nano-silicon-based particles, and the method used is one of a doping method, a coating method and an alloying method.
  • the method used is a doping method
  • the doped elements include B, Al, Na, Mg, Ca, Ba, Ti , one or more of Mn, Fe, Co, Ni, Cu, Zn, Zr, Li, Mo, Ge, Sn.
  • the nano-silicon-based particles are subjected to conductive treatment to obtain conductive nano-silicon-based particles
  • the method used is an alloying method
  • the alloy includes Fe-Si alloy, Au-Si alloy, Sn- One or more of Si alloy, V-Si alloy, C-Si alloy and B-Si alloy.
  • the nano-silicon-based particles are subjected to conductive treatment to obtain conductive nano-silicon-based particles, and the method used is a coating method, and the coating includes carbon coating, oxide coating, and polymer coating.
  • the number of coating layers is one or more layers.
  • the carbon-coated carbon source includes graphite, pitch, graphene, sucrose, glucose, polyacrylic acid, polyacrylonitrile, polyvinyl alcohol, polymethyl cellulose methyl ester, polymethyl methacrylate, polymethyl methacrylate One or more of vinylidene tetrafluoroethylene and various biomass carbons;
  • the oxide-coated oxide is a metal oxide, including one or more of Al2O3, Fe2O3, Co3O4 and WO3;
  • the The polymer-coated polymer is a structural conductive polymer, including one or more of polyacetylene, linear polyphenylene, polyketonephthalein, and surface-type high polymer.
  • the silicon-based raw material is processed to obtain nano-silicon-based particles, and the method used is one of grinding method, ball milling method, gas phase synthesis method, solid phase synthesis method and sand milling method.
  • the beneficial effect of the present invention is that: the silicon-based composite negative electrode material of the present invention is sequentially constructed by nano-processing, conductive processing and shell structure, so that the volume change of the conductive nano-silicon-based particles in the inner space of the shell can be realized, thereby improving the Its cycle performance makes the silicon-based composite material have good rate performance and cycle stability.
  • Fig. 1 is the schematic flow chart of the preparation method of the silicon-based composite negative electrode material of the present invention
  • Fig. 2 is the scanning electron microscope picture before and after nano-processing of silicon material
  • Fig. 3 is the optical picture before and after the conductive treatment of nano-silicon powder
  • Figure 4 is the half-cell charge-discharge curve of the material obtained by coaxial needle spinning
  • Figure 5 is the half-cell cycle performance curve of the material obtained by coaxial needle spinning
  • Figure 6 is the half-cell charge-discharge curve of the material obtained by coaxial non-needle spinning
  • Figure 7 is the half-cell cycle performance curve of the material obtained by coaxial non-needle spinning
  • Figure 8 is the half-cell charge-discharge curve of the material obtained by uniaxial needle spinning
  • Figure 9 is the cycle performance curve of the half-cell obtained by uniaxial needle spinning
  • Figure 10 shows the full battery charge-discharge curve of the special structure silicon anode material
  • Figure 11 is the cycle performance curve of the full battery of the special structure silicon anode material
  • FIG. 12 is a schematic structural diagram of a silicon-based composite negative electrode material.
  • a preparation method of a silicon-based composite negative electrode material of the present invention includes:
  • S100 nano-processing: processing silicon-based raw materials to obtain nano-silicon-based particles;
  • the main purpose of nano-processing is to solve the problem of pulverization of silicon particles during charging and discharging, and the methods used are grinding, ball milling, gas phase synthesis, solid phase synthesis and sand milling.
  • the present invention preferably adopts a grinding method and a gas phase synthesis method, wherein the grinding method is simple and practical, and has a wide range of applications, and can use low-cost raw materials such as micron silicon powder and semiconductor industry waste. The requirements are strict, but the product has high uniformity, small particle size and good performance.
  • the present invention is specifically described as follows by taking the grinding method as an example:
  • This example provides a simple nano-processing method, including:
  • S120 Disperse 5g of micron silicon powder into the above-mentioned grinding jar, and grind it.
  • the grinder used is a horizontal grinder, the rotational speed is 200rpm, and the grinding time is 5h;
  • the left picture of Figure 2 shows the silicon powder before nano-treatment, with a particle size of more than 5 ⁇ m, mixed with random particles of about 200 nm; as shown in the right picture of Figure 2, the material can be optimized to a particle size of Uniform particles below 150 nm.
  • the nano-silicon-based particles after nano-processing are 150 nm and below, thereby improving the pulverization problem of silicon particles during the charging and discharging process.
  • the nano-silicon-based particles are nano-silicon particles, nano-silicon monoxide particles, and nano-silicon-silica composite one or more of the particles.
  • conductive treatment conducting conductive treatment on the nano-silicon-based particles to obtain conductive nano-silicon-based particles
  • the main purpose of conductive treatment is to improve the rate performance of silicon-based materials.
  • Silicon is a typical semiconductor material with low intrinsic conductivity.
  • the rate performance is poor, and certain improvements are required to meet battery performance. magnification requirement. Modification methods include, but are not limited to, doping, cladding, and alloying.
  • the doping element includes one of B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Li, Mo, Ge, Sn or more.
  • the alloy includes one or more of Fe-Si alloy, Au-Si alloy, Sn-Si alloy, V-Si alloy, C-Si alloy and B-Si alloy.
  • a coating method it can be one or more of carbon coating, oxide coating, and polymer coating, and the number of coating layers can be one or more layers; specifically, the carbon coating layer
  • the carbon sources include graphite, pitch, graphene, sucrose, glucose, polyacrylic acid, polyacrylonitrile, polyvinyl alcohol, polymethyl cellulose methyl ester, polymethyl methacrylate, polyvinylidene fluoride and various raw materials.
  • the oxide coating layer includes but is not limited to Al2O3, Fe2O3, Co3O4 and WO3 and other metal oxides with good rigidity and high strength;
  • the polymer coating source includes but not limited to Polyacetylene, linear polyphenylene, polyketone phthalocyanine, surface polymer and other structural conductive polymers.
  • a coating method is used to conduct conductive treatment, and the coating method includes but is not limited to solution method, vapor deposition, spray drying, microfluidics, and electrospray.
  • the solution coating method and the gas phase coating method as an example, the description is as follows:
  • the solution coating method includes:
  • the nano-silicon-based particles are uniformly dispersed in a mixed solution of sulfuric acid and hydrogen peroxide, wherein the volume ratio of sulfuric acid and hydrogen peroxide ranges between 3:1 and 1:2 to form a dispersion;
  • vapor cladding methods includes:
  • the surface of the silicon particles changed from brown to black.
  • the shell structure is the silicon-based composite negative electrode material.
  • the biggest problem of silicon-based anode materials is that the volume expansion is too large during the charging and discharging process, resulting in poor cycle performance of lithium-ion batteries. Therefore, material structure design is extremely important in the development of silicon-based materials.
  • the present invention designs hollow structures, nanowires, porous nanomaterials
  • the silicon anode material is modified by tube and concentric circle structure, etc., in order to achieve the effect of improving the cycle stability.
  • various special structures are not used singly, but interspersed with various structures, and a material includes at least one special structure.
  • the realization methods of the shell structure include, but are not limited to, electrospinning, vapor deposition, spray drying, electrospray, microfluidics, and solution methods.
  • the present invention adopts electrospinning or microfluidic control method, wherein electrospinning includes but is not limited to needle spinning, drum spinning, solution spinning, etc.
  • electrospinning includes but is not limited to needle spinning, drum spinning, solution spinning, etc.
  • the needle spinning has high precision, uniform and stable products, but relatively low productivity. Low, drum spinning product uniformity is poor, but can greatly improve the production capacity.
  • the electrospinning includes several kinds of needle spinning, drum spinning and solution spinning.
  • a method for preparing a silicon anode material by a coaxial needle electrospinning method which includes the following steps:
  • the obtained nanofiber precursor into an air furnace for curing treatment, the curing temperature is 280°C, and the time is 1 h to obtain a cured body;
  • the sintering temperature is 1000° C. and the sintering time is 5 hours, and the corresponding silicon-based negative electrode material can be obtained.
  • a non-aqueous electrolyte lithium ion half-cell can be prepared from the above-mentioned silicon-based negative electrode material.
  • a non-aqueous electrolyte lithium ion half-cell prepared by using the above-mentioned silicon-based negative electrode material as the positive electrode active material, the lithium sheet as the negative electrode, the polyethylene separator, and the lithium hexafluorophosphate as the electrolyte salt; it should be noted that the material is characterized in the half-cell Therefore, the silicon-based anode material is the cathode active material in the half-cell.
  • the above-mentioned non-aqueous electrolyte lithium-ion half-cell was charged and discharged in the voltage range of 0.01 ⁇ 1V, the first discharge capacity could reach 1200mAh/g, and the first Coulomb efficiency was 60%, as shown in Figure 4; the reversible capacity at 0.1 C rate Reaching 800mAh/g, the stable cycle is 2800 cycles, while other untreated Si/C materials have poor cycle performance.
  • the cycle number of the non-aqueous electrolyte lithium-ion half-cell based on the black thick line is the same as
  • the schematic curve of specific capacity, the other curves are the schematic curves of cycle number and specific capacity of untreated Si powder material, Si/Graph blended material and commercial SiO/C material, it is obvious that the non-water The electrolyte lithium-ion half-cell has strong cyclability and good stability.
  • the above-mentioned silicon-based negative electrode material can also be used as the negative electrode active material, 4.35V high-voltage lithium cobalt oxide, polyethylene separator, and lithium hexafluorophosphate as the non-aqueous electrolyte lithium ion half-cell prepared by the electrolyte salt;
  • the charge-discharge test was carried out in the voltage range of 2.75 ⁇ 4.35V.
  • the first charge capacity of the anode material in the full battery can reach 1200 mAh/g (calculated based on silicon), as shown in Figure 10, the reversible capacity at 0.1 C rate It reaches 1000mAh/g and is stable for 50 cycles, as shown in Figure 11.
  • a method for preparing a silicon anode material by a coaxial needle electrospinning method which includes the following steps:
  • the obtained nanofiber precursor into an air furnace for curing treatment, the curing temperature is 300 °C, and the time is 2 h to obtain a cured body;
  • the sintering temperature is 800° C.
  • the sintering time is 4 hours, and the corresponding coaxial nanowire silicon-based negative electrode material can be obtained.
  • the non-aqueous electrolyte lithium ion half-cell can be prepared by the above-mentioned silicon-based negative electrode material.
  • the above-mentioned silicon-based negative electrode material is used as a positive electrode active material
  • a lithium sheet is used as a negative electrode
  • a polyethylene separator is used
  • lithium hexafluorophosphate is used as a non-aqueous electrolyte lithium phosphate prepared as an electrolyte salt.
  • a method for preparing a silicon anode material by a coaxial drum electrospinning method which includes the following steps:
  • the obtained nanofiber precursor into an air furnace for curing treatment, the curing temperature is 300°C, and the time is 2 h to obtain a cured body;
  • the sintering temperature is 900°C
  • the sintering time is 4 hours, and then the silicon-based negative electrode material with the corresponding coaxial nanofiber structure can be obtained.
  • the non-aqueous electrolyte lithium ion half-cell can be prepared by the above-mentioned silicon-based negative electrode material. Specifically, the silicon-based material obtained by the above-mentioned coaxial needle spinning is used as the negative electrode active material, 4.45V high-voltage lithium cobalt oxide, polyethylene diaphragm, and lithium hexafluorophosphate are The non-aqueous electrolyte lithium-ion half-cell prepared from the electrolyte salt; the above-mentioned non-aqueous electrolyte lithium-ion half-cell is charged and discharged in the voltage range of 2.75 ⁇ 4.45V, and the negative electrode material can reach 1000 mAh in the first charging capacity /g at 0.1 The reversible capacity reaches 950mAh/g at C rate, and the stable cycle is 80 cycles.
  • a method for preparing a silicon anode material by a coaxial drum electrospinning method which includes the following steps:
  • the obtained nanofiber precursor into an air furnace for curing treatment, the curing temperature is 300°C, and the time is 2 h to obtain a cured body;
  • the sintering temperature is 900° C.
  • the sintering time is 4 hours, and the corresponding coaxial nanowire silicon-based negative electrode material can be obtained.
  • a method for preparing a silicon anode material by a uniaxial needle electrospinning method comprises the following steps:
  • the obtained nanofiber precursor into an air furnace for curing treatment, the curing temperature is 300°C, and the time is 2 h to obtain a cured body;
  • the sintering temperature is 900°C
  • the sintering time is 4 hours, and the corresponding porous nanofiber silicon-based negative electrode material can be obtained.
  • the non-aqueous electrolyte lithium ion half-cell can be prepared by the above-mentioned silicon-based negative electrode material. Specifically, the silicon-based material obtained by the above-mentioned uniaxial needle spinning is used as the positive electrode active material, the lithium sheet is the negative electrode, the polyethylene separator is used, and the lithium hexafluorophosphate is used as the electrolyte salt.
  • the prepared non-aqueous electrolyte lithium-ion half-cell the above-mentioned non-aqueous electrolyte lithium-ion half-cell is charged and discharged in the voltage range of 0.01 ⁇ 2V, the first discharge capacity can reach 1200 mAh/g, and the first Coulomb efficiency is 73%, such as As shown in Figure 8; the reversible capacity reaches 970mAh/g at a rate of 0.1 C, and the stable cycle is 80 cycles, as shown in Figure 9.
  • the above electrospinning method can solve the problem of poor cycle stability of the silicon-based negative electrode material, and the solution spinning and drum spinning greatly improve the spinning efficiency. , solves the problem of low production capacity of traditional spinning, and this solution is beneficial to subsequent industrial production.
  • the present invention also discloses a silicon-based composite negative electrode material, prepared by the above-mentioned method, comprising an inner core of conductive nano-silicon-based particles and an outer shell of a polymer material, the inner core and all The shell is built to form a shell structure, and a, b, and c in FIG. 12 are respectively exemplary structural forms of different shell structures.
  • the silicon-based composite negative electrode material prepared by the present invention includes, but is not limited to, one or more of a core-shell structure, a concentric circle structure, a hollow structure, a nanowire structure and a nanotube structure.
  • the content of conductive nano-silicon-based particles is 5 ⁇ 50%
  • the capacity of the negative electrode material for lithium ion batteries is 500 ⁇ 1500mAh/g, and the cycle performance meets the needs of commercial batteries.

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Abstract

L'invention concerne un procédé destiné à préparer un matériau d'électrode négative composite à base de silicium. Le procédé consiste : à traiter une matière première à base de silicium pour obtenir une nanoparticule à base de silicium ; à procéder à un traitement conducteur sur la nanoparticule à base de silicium pour obtenir une nanoparticule conductrice à base de silicium ; et à prendre la nanoparticule conductrice à base de silicium en tant que cœur intérieur et à utiliser une matière macromoléculaire en tant qu'écorce pour construire une structure cœur-écorce permettant à la nanoparticule conductrice à base de silicium de changer de volume à l'intérieur de l'écorce. La structure cœur-écorce est le matériau d'électrode négative composite à base de silicium. Le matériau d'électrode négative composite à base de silicium selon la présente invention permet d'obtenir un changement de volume de la nanoparticule conductrice à base de silicium dans l'espace intérieur de l'écorce au moyen d'un nanotraitement, d'un traitement conducteur, et d'une construction de structure cœur-écorce dans cet ordre, améliorant ainsi sa performance de circulation, de sorte que le matériau composite à base de silicium a une bonne performance de débit et une bonne stabilité de circulation.
PCT/CN2020/102976 2020-06-29 2020-07-20 Procédé destiné à préparer un matériau d'électrode négative composite à base de silicium WO2022000589A1 (fr)

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CN114843461A (zh) * 2022-04-18 2022-08-02 晖阳(贵州)新能源材料有限公司 一种低膨胀硅基复合材料的制备方法
CN115818647A (zh) * 2022-11-18 2023-03-21 浙江新安化工集团股份有限公司 一种多孔碳负载纳米硅材料及其制备方法和应用
WO2023169552A1 (fr) * 2022-03-10 2023-09-14 比亚迪股份有限公司 Matériau d'électrode négative composite, son procédé de préparation, pièce d'électrode négative, batterie et dispositif électrique

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CN113594438A (zh) * 2021-07-27 2021-11-02 上海纳米技术及应用国家工程研究中心有限公司 用作锂离子电池负极材料的蜂窝结构微/纳米尺寸硅/碳复合材料的制备及产品和应用
CN113903892A (zh) * 2021-09-13 2022-01-07 惠州市贝特瑞新材料科技有限公司 氧化亚硅复合负极材料及其制备方法
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