WO2014030853A1 - Procédé de préparation de composite carbone/oxyde de silicium pour matériau anodique actif de batterie secondaire au lithium - Google Patents

Procédé de préparation de composite carbone/oxyde de silicium pour matériau anodique actif de batterie secondaire au lithium Download PDF

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WO2014030853A1
WO2014030853A1 PCT/KR2013/006829 KR2013006829W WO2014030853A1 WO 2014030853 A1 WO2014030853 A1 WO 2014030853A1 KR 2013006829 W KR2013006829 W KR 2013006829W WO 2014030853 A1 WO2014030853 A1 WO 2014030853A1
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silicon oxide
secondary battery
carbon composite
active material
lithium secondary
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English (en)
Korean (ko)
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강용묵
송경세
이영민
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동국대학교 산학협력단
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Publication of WO2014030853A1 publication Critical patent/WO2014030853A1/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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/48—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
    • H01M4/58—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for manufacturing a negative electrode active material of a lithium secondary battery, and more particularly, a lithium secondary battery capable of reducing volume expansion during lithium ion insertion and improving ion conductivity and electronic conductivity to maintain high capacity. It relates to a method for producing a silicon oxide (SiO x , 0 ⁇ x ⁇ 2) -carbon composite for a negative electrode active material.
  • Secondary batteries are being used as small-scale, high-performance energy sources for large-capacity power storage batteries such as electric vehicles and battery power storage systems, and portable electronic devices such as mobile phones, camcorders, and notebook computers.
  • power storage batteries such as electric vehicles and battery power storage systems
  • portable electronic devices such as mobile phones, camcorders, and notebook computers.
  • research on weight reduction and low power consumption of components is required, and a secondary battery capable of realizing small size and high capacity is required.
  • the high crystalline carbon-based active material commercialized as a negative electrode active material of the conventional secondary battery has excellent characteristics as an active material of the battery, the theoretical capacity is limited to 372 mAh / g. Development of a non-carbon negative electrode active material is essential.
  • silicon (Si) is known to be the most suitable material as a negative electrode material because it has a very low lithium reaction potential of 0.4 V (Li / Li + ) as well as a high discharge capacity of 4,200 mAh / g.
  • silicon cannot maintain its capacity due to volume expansion of up to 400% upon insertion (charging) of lithium ions, and improvement is necessary for commercialization as a negative electrode active material due to problems such as low electrical conductivity.
  • Patent Document 1 Domestic Registered Patent No. 059596
  • Patent Document 2 Domestic Registered Patent No. 1042009
  • an object of the present invention is to provide a method for producing a silicon oxide-carbon composite for a negative electrode active material of a lithium secondary battery that can continuously maintain high capacity by improving ion conductivity and electron conductivity. It is done.
  • an object of the present invention is to provide a method for producing a silicon oxide-carbon composite for a negative electrode active material of a lithium secondary battery that can improve the electrochemical characteristics of the lithium ion battery.
  • an object of the present invention is to provide a lithium secondary battery electrode of a high capacity, high efficiency and a lithium secondary battery comprising the same.
  • the present invention comprises the steps of preparing a silicon oxide gel by reducing the (S1) silicon oxide precursor through a sol-gel method; (S2) preparing a mixed solution by mixing the silicon oxide gel obtained through the step S1 with a polymer solution in which a polymer material is dissolved in a solvent; (S3) preparing a composite of a one-dimensional structure by electrospinning the mixed solution; And (S4) provides a method for producing a silicon oxide-carbon composite comprising the heat treatment of the composite.
  • silicon oxide precursor silicon chloride (SiCl 4 ), theoose (SiC 8 H 20 O 4 ), silicon acetate (C 8 H 12 O 8 Si), or the like may be used.
  • the step S1 may include (S11) first reducing the silicon oxide precursor by mixing the first solution including the silicon oxide precursor and the second solution including the reducing agent.
  • the step S1, (S12) in the mixed solution obtained in step S11 butyllithium (C 4 H 9 Li), methyl lithium (CH 3 Li), ethyl lithium (C 2 H 5 Li), triethyl aluminum ( Secondary reduction by addition of a secondary reducing agent selected from the group consisting of (C 2 H 5 ) 3 Al), triisobutylaluminum ((C 4 H 9 ) 3 Al) and trimethylaluminum ((CH 3 ) 3 Al) It may be further comprises the step of.
  • the reducing agent is lithium borohydride (LiBH 4 ), sodium borohydride (NaBH 4 ), lithium aluminum hydride (LiAlH 4 ), sodium aluminum hydride (NaAlH 4 ), sodium naphthalide, hydrazine hydrate (N 2 H 4 ), magnesium (Mg), aluminum (Al) and nonstoichiometric aluminum chloride (AlCl x ).
  • Solvents used in the preparation of the first and second solutions are tetrahydrofuran (THF; (CH 2 ) 4O ), triglyme (C 8 H 18 O 4 ), tetraglyme (TEGDME; C 10 H 22 O) and polyglyme (CH 3 O (C 2 H 4 O) nCH 3 ).
  • the polymer material is polyacrylonitrile (PAN), polyvinyl alcohol (polyvinylalcohol, PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyvinylidene fluoride (Polyvinylidene) Fluoride, PVDF), polymethyl methacrylate (PMMA), polyacrylic acid, polyurethane, and the like can be used.
  • the organic solvent may be ethanol, methanol, propanol, butanol, isopropyl alcohol (IPA), dimethylformamide (DMF), acetone, tetrahydrofuran (THF) and toluene.
  • IPA isopropyl alcohol
  • DMF dimethylformamide
  • THF tetrahydrofuran
  • the electrospinning is preferably performed at a humidity of 36% or less and a temperature of 34 ° C or less.
  • the electrospinning is preferably made using a nozzle of 17 gauge to 25 gauge.
  • the electrospinning is preferably made by applying a voltage of 0.5 kV / cm to 3.0 kV / cm.
  • the heat treatment is preferably the first heat treatment for 1 to 10 hours at a temperature of 230 to 350 °C, the second heat treatment for 1 to 7 hours at a temperature of 500 to 900 °C.
  • the secondary heat treatment is preferably performed under a mixed gas atmosphere of an inert gas and a reducing gas.
  • the present invention also provides a negative electrode and a lithium secondary battery of a lithium secondary battery comprising the silicon oxide-carbon composite.
  • the manufacturing method of the silicon oxide-carbon composite for a negative electrode active material of the lithium secondary battery of the present invention through the control of the oxidation number of silicon by heat treatment and complexing with carbon, it is possible to reduce the volume expansion during lithium ion insertion, ion conductivity and The electronic conductivity can be improved to maintain high capacity continuously.
  • the present invention is to produce a one-dimensional structure of silicon oxide (SiO x ) -carbon composites using an electrospinning method to have a larger specific surface area to improve the lithium ion conductivity and electrical conductivity to effectively improve the performance of the silicon oxide-carbon composites It can be improved.
  • the capacity and the life of the silicon oxide may be appropriately adjusted through the control of the oxidation number of silicon oxide.
  • Example 1 is a graph showing the results of X-ray diffraction analysis of the silicon oxide-carbon composite prepared according to Example 1.
  • Figure 2 is a graph of the electrochemical characteristics evaluation results of the silicon oxide-carbon composite prepared according to Example 1.
  • a silicon oxide gel is prepared by reducing the (S1) silicon oxide precursor through a sol-gel method. step; (S2) preparing a mixed solution by mixing the silicon oxide gel obtained through the step S1 with a polymer solution in which a polymer material is dissolved in a solvent; (S3) preparing a composite of a one-dimensional structure by electrospinning the mixed solution; And (S4) heat treating the composite.
  • the silicon oxide precursor is reduced by the sol-gel method to prepare a silicon oxide gel (S1).
  • the silicon oxide precursor is, for example, silicon chloride (SiCl 4 ), trimethylchlorosilane (CH 3 SiCl 3 ), trisilane (Si 3 H 8 ), teos (SiC 8 H 20 O 4 ) and silicon acetate (C 8 H 12 O 8 Si) can be used.
  • the step S1 may include (S11) first reducing the silicon oxide precursor by mixing the first solution including the silicon oxide precursor and the second solution including the reducing agent.
  • step S1 butyllithium (C 4 H 9 Li), methyl lithium (CH 3 Li), ethyl lithium (C 2 H 5 Li), triethyl aluminum ( Secondary reduction by addition of a secondary reducing agent selected from the group consisting of (C 2 H 5 ) 3 Al), triisobutylaluminum ((C 4 H 9 ) 3 Al) and trimethylaluminum ((CH 3 ) 3 Al) It may be further comprises the step of.
  • the alkyl group terminates the dangling bond on the Si surface, thereby preventing reoxidation after completion of the reaction.
  • the reducing agent is, for example, lithium borohydride (LiBH 4 ), sodium borohydride (NaBH 4 ), lithium aluminum hydride (LiAlH 4 ), sodium aluminum hydride (NaAlH 4 ), sodium naphthalide (NaC10H 8 ), hydrazine hydrate (N 2 H 4 ), magnesium (Mg), aluminum (Al) or nonstoichiometric aluminum chloride (AlCl x ) can be used.
  • lithium borohydride LiBH 4
  • sodium borohydride NaBH 4
  • lithium aluminum hydride LiAlH 4
  • sodium aluminum hydride NaAlH 4
  • sodium naphthalide NaC10H 8
  • hydrazine hydrate N 2 H 4
  • AlCl x nonstoichiometric aluminum chloride
  • Solvents used in the preparation of the first and second solutions are, for example, tetrahydrofuran (THF; (CH 2 ) 4O ), glyme (C 4 H 10 O 2 ), triglyme (C 8 H 18 O 4 ), tetraglyme (TEGDME; C 10 H 22 O) or polyglyme (CH 3 O (C 2 H 4 O) nCH 3 ) can be used.
  • Step S1 may further include removing byproducts after the production of the silicon oxide gel.
  • the silicon oxide gel obtained through the step S1 is mixed with a polymer solution in which a polymer material is dissolved in a solvent to prepare a mixed solution (S2).
  • the polymer material is a precursor for providing carbon in the silicon oxide-carbon composite, and is not particularly limited as long as it is a material capable of providing carbon by carbonization.
  • the polymer material may be polyacrylonitrile (PAN), polyvinylalcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyfluorinated Polyvinylidene Fluoride (PVDF), polymethyl methacrylate (PMMA), polyacrylic acid, polyurethane, etc. may be used, and it is particularly preferable to use polyacrylonitrile.
  • the polymer material has a limited solvent which can be dissolved according to the intrinsic properties of the polymer such as hydrophilicity and hydrophobicity, and it is preferable to combine it with an appropriate solvent.
  • the polymer material is preferably included in an amount of 3 to 20 parts by weight based on 100 parts by weight of the solvent. If the content is less than 3 parts by weight, a kind of agglomeration of bead is formed for each structure due to the low viscosity during electrospinning, so that uniform fibers of a certain thickness cannot be produced.
  • the agglomeration of silicon particles with each other prevents the carbon from properly controlling the volume expansion of the silicon particles, and the polymer materials are agglomerated in part, resulting in beads and non-uniform thicknesses.
  • the solvent for preparing the mixed solution is ethanol, methanol, propanol, butanol, butanol, isopropyl alcohol (IPA), dimethylformamide (DMF), acetone ), Tetrahydrofuran (THF), toluene or distilled water (H 2 O).
  • the solvent has a boiling point of up to about 120 degrees and is used according to the hydrophilicity or hydrophobicity of the polymer material.
  • water H 2 O, distilled water
  • a homogeneous solution can be obtained by stirring the mixed solution at a temperature of 25 to 80 ° C.
  • the melting temperature is different according to the characteristics of the polymer material, and if the melting is not performed at an appropriate temperature, an even fiber structure is not produced and electrospinning is not continuously performed.
  • polyacrylonitrile is most preferably dissolved at about 60 ° C. when dissolved in dimethylformamide.
  • the silicon oxide precursor is preferably included in 10 to 40 parts by weight based on 100 parts by weight of the polymer material. If the content is less than 10 parts by weight, the amount of silicon contained in the final manufactured silicon-carbon composite may be low, and the energy density as an electrode may be reduced. If the content exceeds 40 parts by weight, amorphous silica (SiO 2 ) may be present on the surface. Due to the high surface energy of the silicon particles in the production of the coated silicon-carbon composites, the carbon particles produced by carbonization due to carbonization of the polymer material due to agglomeration in many parts of the silicon material are not evenly distributed, thereby preventing effective volume expansion.
  • the composite solution is electrospun to prepare a composite having a one-dimensional structure (S3).
  • the prepared mixed solution is prepared into a composite having a one-dimensional structure by using an electrospinning method.
  • the electrospinning method may be carried out using a conventional electrospinning device, for example, a feeder for supplying a conventional solution, a spinneret for spinning a solution supplied through the feeder, and a fiber spun through the spinneret And an electrospinning device including a collector and a voltage generator for applying a voltage between the spinneret and the collector.
  • the mixed solution prepared in the previous step is supplied through the feeder of the electrospinning apparatus, and the mixed solution supplied through the feeder is transported and spun through the spinning nozzle, a positive voltage applied from the voltage generator to the nozzle The mixed solution is radiated and collected by a relatively negative collector.
  • Electrospinning causes the solvent to be volatilized by positive voltage, and at the same time, the polymer chain is stretched while the polymer material is wrapped in the silicon oxide contained in the solution. .
  • the electrospun fibrous material is collected by the electric field towards the collector with a relatively negative charge.
  • the positive and negative voltages during electrospinning are changed by the polymer and the solvent.
  • the thickness control and the quality of the fiber produced are determined by the applied voltage per distance (kV / cm), the injection amount of the solution (ml / min, ml / h, l / h) and the nozzle (nozzle, needle) during electrospinning.
  • the positive applied voltage during electrospinning is controlled by the distance between the collector and the jet as well as the inherent properties of the polymer material.
  • the solution injection amount the rapid injection requires a higher amount of applied voltage and the production amount can be adjusted over time.
  • 17 gauge (inner diameter of about 1.05 mm) to 25 gauge (inner diameter of about 0.25 mm) are suitable, and the uniformity and thickness of the fabric produced is determined by the choice of the nozzle.
  • the composite having a one-dimensional structure prepared by the electrospinning method may be prepared by partially oxidizing silicon oxide through QHS heat treatment and simultaneously complexing by carbonizing a polymer material.
  • the heat treatment is the first heat treatment for 1 to 10 hours at a temperature of 230 to 350 °C under an air atmosphere, the second heat treatment for 1 to 7 hours at a temperature of 500 to 900 °C under a mixed atmosphere of an inert gas and a reducing gas desirable. More preferably, the heat treatment of the mixed solution is a first heat treatment for 5 hours at 280 °C, then a second heat treatment for 1 hour at 700 °C.
  • the temperature is less than 230 °C during the first heat treatment, the solvent and water in which the polymer and the silicon particles are dissolved do not evaporate sufficiently, so that the state cannot be obtained in powder form after heat treatment or structurally unstable during the second heat treatment. If it is in a state where the temperature exceeds 350 ° C., it is not preferable because there is a problem in that the structure is not maintained because it is partially carbonized in a state where the solvent and the moisture cannot evaporate.
  • the temperature during the second heat treatment is less than 500 °C there is a problem that the polymer material is not sufficiently carbonized, if it exceeds 900 °C silicon particles are too much oxidized so that the amount of Si having an electrochemically high energy density It is not desirable to have too few problems.
  • helium (He), nitrogen (N 2 ), argon (Ar), neon (Ne), xenon (Xe), etc. may be used as the inert gas, and hydrogen (H 2 ) may be added as a reducing gas.
  • H 2 hydrogen
  • the lithium oxide (SiO x ) -carbon composite having a one-dimensional structure is prepared by using an electrospinning method to improve lithium ion conductivity and electrical conductivity by having a larger specific surface area. Can be.
  • the oxidation number of the silicon oxide in the silicon oxide-carbon composite obtained as a final product depends on the electrospinning and heat treatment conditions and the materials used.
  • the oxidation number (x) in silicon oxide is low, that is, when the content of amorphous silica (SiO 2 ) is low, volume expansion can be reduced during lithium ion insertion, while the capacity is low, and when the oxidation number (x) is high, that is, amorphous
  • the content of silica (SiO 2 ) is large, the capacity is increased while the effect of reducing volume expansion is low.
  • Sodium and naphthalene were added to the solution in a molar ratio of 1: 8 to 80 mL of glyme, and a mixed solution of sodium naphthalide as a reducing agent was prepared by stirring for 24 hours.
  • a solution of silicon tetrachloride (SiCl 4 ) dispersed by stirring in 100 mL of glyme was prepared.
  • sodium and silicon tetrachloride (SiCl 4 ) is prepared to be 5: 1 in a molar ratio.
  • the gel is obtained by heating and maintaining at 10-1 torr pressure and temperature of 80 ° C for 30 minutes using a rotary concentrator to remove the solvent, glyme, and further at 6 ° C at 120 ° C 10-2 torr pressure to remove naphthalene. Keep up the time. Subsequently, an excess of hexane was added to disperse and then water was added to dissolve by-products such as sodium, lithium, sodium chloride, and lithium chloride, and only hexane solution was obtained using a separatory funnel. Finally, a silicon oxide (SiO x ) gel was prepared by maintaining a rotary concentrator at 120 ° C. and a pressure of 10-1 torr for 2 hours.
  • SiO x silicon oxide
  • polyacrylonitrile and dimetalformamide were dissolved at a mass ratio of 11:89 by heating at a temperature of 60 ° C., and then the prepared silicon oxide gel was added at a ratio of 2: 8 to polyacrylonitrile and stirred. A homogeneous mixed solution was obtained.
  • the prepared mixed solution is supplied through a feeder of an electrospinning apparatus, and a positive voltage of 0.7 kV / cm or more is applied when spinning the conveyed mixed solution through a spinning nozzle, so that the spun fiber is relatively accumulated.
  • a fibrous mixture having a one-dimensional structure was obtained by electrospinning collected through a negative voltage collector.
  • the prepared fibrous mixture was first heat-treated at 280 ° C. for 5 hours in an air atmosphere, and then at 700 ° C. under argon / hydrogen mixed gas (Ar / H 2 5%) atmosphere in which an inert gas and a reducing gas were mixed. Secondary heat treatment was performed for 1 hour to prepare a silicon oxide-carbon composite having a one-dimensional structure.
  • Electrochemical analysis of the silicon oxide-carbon composite of Example 1 is shown in FIG. Referring to FIG. 2, it can be seen that the potential flat surface near 0.1V corresponding to the formation of an intermediate compound of silicon and lithium during the charging reaction shows an initial capacity of 1300mAh / g and an initial irreversible capacity of 52%. As a result, it was confirmed that an excellent silicon oxide-carbon composite could be prepared by replacing the precursor with the silicon oxide gel obtained from the sol-gel method, mixing with the polymer solution, and electrospinning and heat treating.

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Abstract

La présente invention se rapporte à un procédé destiné à préparer un composite carbone/oxyde de silicium pour un matériau anodique actif d'une batterie secondaire au lithium. Le procédé de la présente invention destiné à préparer un composite carbone/oxyde de silicium pour un matériau anodique actif d'une batterie secondaire au lithium comprend les étapes consistant à : (S1) préparer un gel d'oxyde de silicium par la réduction d'un précurseur de l'oxyde de silicium par l'intermédiaire d'un procédé sol-gel ; (S2) préparer une solution de mélange grâce au mélange du gel d'oxyde de silicium obtenu à l'étape S1 avec une solution polymère préparée par la dissolution d'un matériau polymère dans un solvant ; (S3) préparer un composite présentant une structure unidimensionnelle par électrofilage de la solution mélangée ; et (S4) traiter thermiquement le composite. Selon le procédé de la présente invention destiné à préparer le composite carbone/oxyde de silicium pour un matériau actif anodique d'une batterie secondaire au lithium, l'expansion volumétrique au cours de l'introduction d'ions lithium peut être réduite par la complexation avec du carbone et par l'ajustement de l'état oxydant du silicium par le traitement thermique, et une capacité élevée peut être également maintenue de façon continue par l'amélioration de la conductivité ionique et la conductivité électrique. De plus, la capacité et la durée de vie peuvent être ajustées de façon appropriée si besoin par la modification des conditions du processus de préparation, ce qui permet d'ajuster l'état oxydant de l'oxyde de silicium.
PCT/KR2013/006829 2012-08-22 2013-07-30 Procédé de préparation de composite carbone/oxyde de silicium pour matériau anodique actif de batterie secondaire au lithium WO2014030853A1 (fr)

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EP3254321A4 (fr) * 2015-02-04 2018-07-18 Axium IP, LLC Composites nanostructurés silicium-carbone
CN110416523A (zh) * 2019-08-05 2019-11-05 北方奥钛纳米技术有限公司 一种Si-O-C复合材料及其制备方法、硅碳复合材料
CN110571409A (zh) * 2018-06-05 2019-12-13 微宏动力系统（湖州）有限公司 一种负极材料的制备方法、负极材料及锂电池
CN111584859A (zh) * 2020-05-22 2020-08-25 合肥国轩高科动力能源有限公司 中空硅微球-氮掺杂碳纳米线硅负极材料及其制法和应用
CN112289983A (zh) * 2020-09-18 2021-01-29 合肥国轩高科动力能源有限公司 一种SiOx-MWCNTs/C核壳复合负极材料及其制备方法、应用
CN113422009A (zh) * 2021-06-01 2021-09-21 广东工业大学 一种锂离子电池负极材料及其制备方法与应用
CN113809307A (zh) * 2021-09-18 2021-12-17 西北大学 一种基于硅/碳微纳米球不同维度的硅基复合材料的制备方法及应用

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CN113422009A (zh) * 2021-06-01 2021-09-21 广东工业大学 一种锂离子电池负极材料及其制备方法与应用
CN113422009B (zh) * 2021-06-01 2022-03-18 广东工业大学 一种锂离子电池负极材料及其制备方法与应用
CN113809307A (zh) * 2021-09-18 2021-12-17 西北大学 一种基于硅/碳微纳米球不同维度的硅基复合材料的制备方法及应用

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