WO2014204095A1 - Matériau actif d'anode pour batterie secondaire au lithium, son procédé de préparation, et batterie secondaire au lithium - Google Patents

Matériau actif d'anode pour batterie secondaire au lithium, son procédé de préparation, et batterie secondaire au lithium Download PDF

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WO2014204095A1
WO2014204095A1 PCT/KR2014/004277 KR2014004277W WO2014204095A1 WO 2014204095 A1 WO2014204095 A1 WO 2014204095A1 KR 2014004277 W KR2014004277 W KR 2014004277W WO 2014204095 A1 WO2014204095 A1 WO 2014204095A1
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carbon
coating layer
based material
silica
active material
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PCT/KR2014/004277
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English (en)
Korean (ko)
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박수진
최남순
최신호
추용철
전상호
이정찬
Original Assignee
국립대학법인 울산과학기술대학교 산학협력단
덕산하이메탈(주)
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Publication of WO2014204095A1 publication Critical patent/WO2014204095A1/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
    • H01M4/38—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/06—Metal silicides
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • 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 negative electrode active material for a lithium secondary battery, a negative electrode for a lithium secondary battery including the same, and a lithium secondary battery including the negative electrode. More specifically, the present invention relates to a negative electrode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery having high capacity, high cycle characteristics, and excellent high rate characteristics.
  • the battery generates power by using a material capable of reacting electrochemically at the positive and negative electrodes.
  • a representative example of such a battery is a recess secondary battery that generates electrical energy by a change in chemical potential when lithium silver is intercalated / deintercalated in a positive electrode and a negative electrode.
  • the lithium secondary battery is prepared by using a material capable of reversible intercalation / deintercalation of lithium ions as a positive electrode and a negative electrode active material, and layering an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
  • a lithium composite metal compound As a cathode active material of a lithium secondary battery, a lithium composite metal compound is used. Examples thereof include a composite of LiCo0 2 , LiMn 2 0 4 , LiNi0 2 , LiNii- x Co x 0 2 (0 ⁇ x ⁇ l), and LiMn0 2 . Metal oxides are being studied.
  • the negative electrode active material of a lithium secondary battery As the negative electrode active material of a lithium secondary battery, an abbreviation or the like capable of inserting / desorbing lithium has been typically applied. However, since the electrode using such abyss has a low charge capacity of 365 mAh / g (theoretical value: 372 mAh / g), there was a limit in providing a lithium secondary battery showing excellent capacity characteristics.
  • the inorganic active material in particular, the silicon-based negative active material has an advantage of implementing a high capacity (3650 mAh / g) when reacting with lithium ions at room temperature.
  • the inorganic negative electrode active material such as silicon has a volume change of more than 300% during insertion / desorption of lithium, that is, a charge / discharge of a battery, and thus the capacity decreases as the contact between the current collector and the active material becomes weak.
  • the low electrical conductivity of silicon makes lithium The charge transfer reaction that occurs during insertion / desorption of does not occur smoothly.
  • previously known inorganic-based negative active material for example, silicon-based negative active material and a lithium secondary battery including the same have a disadvantage of showing a low cycle life characteristics and capacity retention despite the advantages of high charge capacity.
  • carbon-based is known as a material with high electrical conductivity, but the capacity is low, but when nano-sized silicon is coated on the surface, it is necessary to compensate the disadvantages of low-capacity carbon-based lithium secondary battery negative electrode active material, namely , High capacity, high cycle characteristics, and excellent high rate characteristics.
  • One embodiment provides a method of manufacturing a negative active material for a lithium secondary battery having excellent capacity characteristics, cycle characteristics, and high rate characteristics, and a negative electrode active material according thereto. Another embodiment is to provide an electrochemical device including the negative active material for the lithium secondary battery.
  • One embodiment of the present invention comprises the steps of acid-treating a carbon-based material to oxidize the surface of the carbon-based material; Coating the surface of the oxidized carbonaceous material with silica to obtain a carbonaceous material comprising a silica coating layer; Removing only the carbon-based material from the carbon-based material including the silica coating layer to obtain silica nanotubes; And it provides a negative electrode active material for a lithium secondary battery comprising the step of reducing the silica nanotubes to obtain silicon nanotubes.
  • the carbon-based material may be by far abyss, soft carbon, hard carbon, carbon nanotubes, carbon nanofibers, or a combination thereof.
  • the carbon-based material may have a diameter of 10 nm to 1.
  • the step of oxidizing the surface of the carbonaceous material by acid treatment of the carbonaceous material uses a method of impregnating the carbonaceous material in a solution containing a solvent and an acid, wherein the solvent is alcohol, water, DMF, NMP, THF, acetone, or a combination thereof and the acid may be nitric acid, sulfuric acid, or a combination thereof.
  • Obtaining a carbon-based material including the silica coating layer may include reacting the silica precursor and the catalyst with the carbon-based material.
  • the silica precursor may be tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, tetrahydroxysilane, or a combination thereof.
  • the catalyst may be ammonium hydroxide.
  • the silica coating layer is an amorphous silica coating layer, it may have a thickness of 10 nm to 500 nm.
  • the silica coating layer may also be porous. This minimizes the volume expansion of the silicon.
  • the silica coating layer may be included in 50 to 95 parts by weight based on 100 parts by weight of the carbon-based material including the silica coating layer.
  • Obtaining silica nanotubes by removing only the carbon-based material may include calcining the carbon-based material including the silica coating layer at 500 ° C. to 700 ° C. for 30 to 90 minutes.
  • Reducing the silica nanotubes to obtain silicon nanotubes may include reducing silica to silicon using a metal reducing agent.
  • the metal reducing agent may be magnesium, aluminum, calcium, lithium, or a combination thereof.
  • One embodiment of the present invention may further comprise the step of coating the carbon on the surface of the silicon nanotube after the step of reducing the silicon nanotube to obtain a silicon nanotube.
  • Coating the carbon on the surface of the silicon nano-lube may include coating carbon on the silicon nanotube by pyrolyzing a gas including carbon.
  • the gas containing carbon may be methane gas, ethane gas, propane gas, butane gas, ethylene gas, acetylene gas, or a combination thereof.
  • the pyrolysis temperature is 600 ° C to 900 ° C
  • pyrolysis time may be 5 minutes to 15 minutes.
  • One embodiment of the present invention comprises the steps of acid-treating a carbon-based material to oxidize the surface of the carbon-based material; Coating the surface of the oxidized carbonaceous material with titania to obtain a carbonaceous material including a titania coating layer; Coating a carbon-based material including a titania coating layer with silica to obtain a carbon-based material including a silica coating layer on the titania coating layer; Removing only the carbon-based material from the carbon-based material including the silica coating layer on the titania coating layer to obtain silica nanotubes including the silica coating layer on the titania coating layer; And it provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of reducing the silica nanotubes comprising
  • the carbon-based material is hokyeon, soft carbon, the four possible hard carbon, carbon nanotube, carbon nano-fiber (carbon nano fiber), or a combination thereof.
  • the diameter of the oxidized carbon-based material may be 10 nm to 1.
  • Acid-treating the carbon-based material to oxidize the surface of the carbon-based material using a method of impregnating the carbon-based material in a solution containing a solvent and an acid, wherein the solvent is alcohol, water, or DMF. , MP, THF, acetone, or a combination thereof and the acid may be nitric acid, sulfuric acid, or a combination thereof.
  • Obtaining a carbon-based material including the titania coating layer may include reacting a titania precursor and a catalyst with the carbon-based material.
  • the titania precursor may be titanium (lV) butoxide, titanium oxide, titanium fluoride, or a combination thereof.
  • the catalyst may be 3 ⁇ 40, acetic acid, ammonium hydroxide (NH 4 0H), hydrochloric acid (HC1), or a combination thereof.
  • the titania coating layer may be an amorphous titania coating layer, 1 to
  • the titania coating layer may also be porous. This minimizes the volume expansion of the silicon.
  • the titania coating layer of the carbon-based material 100 including a titania coating layer It may be included in 3 to 5 parts by weight relative to the amount.
  • Between the step of obtaining the system material may further comprise the step of calcining the carbon-based material including the titania coating layer under an argon atmosphere.
  • the calcination temperature is 500 ° C to 700C and the calcination time may be 30 minutes to 90 minutes.
  • the silica coating layer is a carbon-based element comprising a silica coating layer on the titania coating layer 50 to 90 parts by weight based on 100 parts by weight of ash.
  • the thickness of the silica coating layer may be 50 nm to 500 nm.
  • Reducing the silica nanotubes including the silica coating layer on the titania coating layer to obtain silicon nanotubes including titanium may include reducing titania and silica to titanium and silicon, respectively, using a metal reducing agent. have.
  • the metal reducing agent may be magnesium, aluminum, calcium, lithium, or a combination thereof.
  • One embodiment of the present invention may further comprise the step of coating carbon on the surface of the silicon nanotubes containing titanium.
  • Coating carbon on the surface of the silicon nanotubes including titanium may include coating carbon on the silicon nanotubes by pyrolyzing a gas including carbon.
  • the gas containing carbon may be methane gas, ethane gas, propane gas, butane gas ethylene gas, acetylene gas, or a combination thereof.
  • the pyrolysis temperature is 600 ° C to 90 CTC
  • pyrolysis time may be 5 minutes to 15 minutes.
  • Another embodiment of the present invention provides a negative electrode active material prepared according to the negative electrode active material manufacturing method according to the embodiment.
  • Another embodiment of the present invention is a positive electrode including a positive electrode active material; A negative electrode including the negative electrode active material; And electrolytes; It provides an electrochemical device comprising a.
  • the negative electrode active material manufacturing method according to the embodiment by removing the carbon-based material through the calcination process, it is possible to block the formation of silicon carbide or titanium carbide, thereby improving capacity characteristics, cycle characteristics, and high rate characteristics.
  • FIG. 1 is a schematic view of a lithium secondary battery according to an embodiment of the present invention.
  • TEM 2 is a transmission electron microscope (TEM) photograph of a silica coating layer prepared using 16 mL and 9 mL of ammonium hydroxide and tetraethoxysilane, respectively.
  • TEM 3 is a transmission electron microscope (TEM) image of a silica coating layer prepared using 8 mL and 9 mL of ammonium hydroxide and tetraethoxysilane, respectively.
  • TEM 4 is a transmission electron microscope (TEM) photograph of a silica coating layer prepared using 12 mL and 12 mL of ammonium hydroxide and tetraespecial silane, respectively.
  • TEM 5 is a transmission electron microscope (TEM) photograph of a silica coating layer prepared using 12 mL and 9 mL of ammonium hydroxide and tetraethoxysilane, respectively.
  • FIG. 6 is a flowchart illustrating a method of manufacturing the negative electrode active material (CNT @ SiC @ Si nanotubes) of Comparative Example 1.
  • FIG. 6 is a flowchart illustrating a method of manufacturing the negative electrode active material (CNT @ SiC @ Si nanotubes) of Comparative Example 1.
  • TEM 7 is a transmission electron microscope (TEM) image of oxidized carbon nanotubes.
  • FIG. 9 is a scanning electron microscope (SEM) photograph of the negative electrode active material (CNT @ SiC @ Si nanotubes) of Comparative Example 1.
  • SEM scanning electron microscope
  • FIG. 10 is a flowchart illustrating a method of manufacturing a negative electrode active material (Si nanotubes) of Example 1.
  • FIG. 11 is a scanning electron microscope (SEM) photograph of silica nanotubes.
  • FIG. 12 is a scanning electron microscope (SEM) photograph of the negative electrode active material (Si nanotubes) of Example 1.
  • SEM scanning electron microscope
  • FIG. 13 is a graph of an X D pattern of a negative electrode active material (Si nano-leuves) of Example 1.
  • FIG. 14 is an XRD pattern graph of a negative electrode active material (CNT @ SiC @ Si nanotubes) of Comparative Example 1.
  • FIG. 13 is a graph of an X D pattern of a negative electrode active material (Si nano-leuves) of Example 1.
  • FIG. 14 is an XRD pattern graph of a negative electrode active material (CNT @ SiC @ Si nanotubes) of Comparative Example 1.
  • FIG. 15 is a graph of an XRD pattern of a negative active material ⁇ /! ⁇ nanotubes of Comparative Example 2.
  • 17 is a graph showing the charge and discharge life characteristics of the coin battery prepared in Comparative Example 3.
  • FIG. 19 is a graph showing charge and discharge life characteristics of the coin battery prepared in Example 3.
  • FIG. 20 is a flowchart illustrating a method of manufacturing a negative electrode active material (Ti x Si y @Si nanotubes) of Example 2.
  • FIG. 20 is a flowchart illustrating a method of manufacturing a negative electrode active material (Ti x Si y @Si nanotubes) of Example 2.
  • FIG. 20 is a flowchart illustrating a method of manufacturing a negative electrode active material (Ti x Si y @Si nanotubes) of Example 2.
  • FIG. 21 is a transmission electron microscope (TEM) photograph of a silica nanotube (Ti0 2 @ Si0 2 nanotubes) including a silica coating layer on a titania coating layer.
  • TEM transmission electron microscope
  • FIG. 22 is a scanning electron microscope (SEM) photograph of the anode active material (Ti x Si y @Si nanotubes) of Example 2.
  • SEM scanning electron microscope
  • FIG. 23 is a graph of an XRD pattern of a negative electrode active material (Ti x Si y @Si nanolyuves) of Example 2.
  • FIG. 24 is a voltage change curve according to the first capacity of the coin battery prepared in Comparative Example 4.
  • 25 is a graph showing the charge and discharge life characteristics of the coin battery prepared in Comparative Example 4.
  • 26 is a voltage change curve according to the first capacity of the coin battery prepared in Example 4.
  • FIG. 27 is a graph showing charge and discharge life characteristics of the coin battery prepared in Example 4.
  • FIG. 28 is a graph showing battery life characteristics according to discharge C-rates of the coin batteries prepared in Examples 3 and 4.
  • FIG. 28 is a graph showing battery life characteristics according to discharge C-rates of the coin batteries prepared in Examples 3 and 4.
  • FIG. 29 is a graph illustrating battery life characteristics according to layer C-rates of the coin batteries prepared in Examples 3 and 4.
  • FIG. 29 is a graph illustrating battery life characteristics according to layer C-rates of the coin batteries prepared in Examples 3 and 4.
  • a @ B means "coated B on A”.
  • '' A @ B @ C '' means that "B is coated on A, and C is further coated on B" 1 .
  • One embodiment of the present invention comprises the steps of acid-treating a carbon-based material to oxidize the surface of the carbon-based material; Coating the surface of the oxidized carbonaceous material with silica to obtain a carbonaceous material comprising a silica coating layer; Removing only the carbon-based material from the carbon-based material including the silica coating layer to obtain silica nanotubes; And it provides a negative electrode active material for a lithium secondary battery comprising the step of reducing the silica nanotubes to obtain silicon nanotubes.
  • the negative electrode active material prepared by the above method does not include silicon carbide (SiC) or titanium carbide nc), thereby improving capacity characteristics, cycle characteristics, and high rate characteristics.
  • the carbonaceous material may be by far the soft carbon, the hard carbon, carbon nanotubes, or It can be a combination of these.
  • the carbon-based material may be carbon nanotubes, multi-walled carbon nanotubes (Mult i-walled CNTs, MWCNT).
  • the carbon-based material may have a diameter of about 10 nm to about 1.
  • the diameter of the carbonaceous material may be about 10 nm to 20 nm.
  • the carbon-based material may have a length of about 1 mm 3 to about 50 mm.
  • the carbon-based material may have a length of about 1 urn to about 10.
  • the silicon may be in the form of nanotubes or porous silicon.
  • bulky silicon is used in a silicon negative electrode active material, and the silicon negative active material reacts with lithium ions during charging and discharging so that the active material is detached from the current collector during the expansion of the volume, thereby deteriorating cycle characteristics. do.
  • tube-type silicones or porous silicones provide space during shrinkage after volume expansion, thereby preventing cracks from forming. Therefore, when the silicon structure is in the form of a rib or porous silicon, it may have excellent cycle characteristics by alleviating the volume change occurring during the reaction with the lithium ions.
  • Carbonaceous materials have a hydrophobic surface and do not readily react with most inorganic precursors such as silica precursors and titania precursors. Accordingly, the carbonaceous material surface can be oxidized using a strong acid and a catalyst to improve the reaction between the carbonaceous material surface and inorganic precursors such as a silica precursor or a titania precursor.
  • the surface of the carbon-based material may be oxidized by impregnating the carbon-based material in a solution containing a solvent and an acid.
  • the solvent may be alcohol, water, DMF, NMP, THF, acetone, or a combination thereof
  • the acid may be nitric acid, sulfuric acid, or a combination thereof.
  • the concentration of nitric acid and sulfuric acid may be 10 to 20%, respectively, and a mixed acid in which nitric acid and sulfuric acid are mixed may be used.
  • a functional group such as -C00H, -0H, or -C (0)-is formed on the surface of the carbon-based material, and the surface of the carbon-based material is activated. Or titania coating layer can be easily formed.
  • a step of obtaining a carbon-based material including a silica coating layer by coating the surface of the oxidized carbon-based material with silica will be described.
  • the surface of the oxidized carbon-based material may be reacted with a silica precursor and a catalyst to obtain a carbon-based material including a silica coating layer.
  • the silica precursor may be tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, tetrahydroxysilane, or a combination thereof.
  • the catalyst may be ammonium hydroxide (NH 4 0H).
  • a silica precursor such as tetraespecial silane
  • tetraespecial silane there is an effect of promoting the hydrolysis reaction or the polycondensation reaction of the silica precursor represented by the following reaction formula.
  • the silica precursor may be used in about 5 to 15 mL. When the amount of the silica precursor used is within the above range, the silica coating layer may be evenly formed on the surface of the carbon-based material. '
  • the silica coating layer is an amorphous silica coating layer, and may have a thickness of about 10 nm to 500 nm, for example, about 10 to 100 nm.
  • the thickness of the silica coating bug can be adjusted by changing the amount of the catalyst and the silica precursor used.
  • the silica coating layer may also be porous. This minimizes the volume expansion of the silicon ⁇
  • the silica coating layer may be included in about 50 to 95 parts by weight based on 100 parts by weight of the carbon-based material including the silica coating layer. In this case, the density of the final material can be improved by increasing the content of silicon.
  • silica tends to coagulate with each other, carbon-based materials including a silica coating layer may gather together to form an assembly.
  • a step of obtaining the silica nanotubes by removing only the carbon-based material from the carbon-based material including the silica coating layer will be described.
  • the carbon-based material including the silica coating insect may be calcined in an air environment for about 30 to 90 minutes at about 500 ° C to 700 ° C, to remove the carbon-based material.
  • FIG. 6 is a flowchart illustrating a method of manufacturing a negative electrode active material in which the calcination process of Comparative Example 1 is omitted. If the carbon-based material 1 including the silica coating layer is reduced without the calcination process, silicon carbide (SiC) is formed between the carbon-based material and silicon according to the following reaction formula:
  • FIG. 14 is an XRD pattern graph of a negative active material prepared according to FIG. 6. In FIG. 14, it can be confirmed that silicon carbide (SiC) is present.
  • FIG. 10 is a flow chart of the manufacturing method of the negative electrode active material including the calcination process of Example 1.
  • the negative electrode active material prepared by the manufacturing method of FIG. 10 may block the formation of silicon carbide (SiC) by removing carbonaceous materials such as carbon nanotubes through the calcination process, thereby realizing a lithium secondary battery having excellent capacity characteristics.
  • FIG. 13 is an XRD pattern graph of a negative active material prepared according to FIG. 10. FIG. It can be seen from FIG. 13 that silicon carbide (SiC) does not exist.
  • the silica nanotubes may be reduced by using a reducing agent.
  • the reducing agent may reduce the silica of the silica nano-lube to silicon.
  • the reduction reaction is as follows.
  • the metal reducing agent may be magnesium, aluminum, kale, lithium, or a combination thereof.
  • the silica nanotubes may be reduced to silicon nanonubs using magnesium thermal reduction (magnesiothermic reduction).
  • One embodiment of the present invention may further comprise the step of coating the carbon on the surface of the silicon nanotube after the step of reducing the silicon nanotube to obtain a silicon nanotube.
  • the step of coating carbon on the surface of silicon nanotubes will be described.
  • the gas containing carbon may be pyrolyzed to coat carbon on the silicon nanotubes.
  • SEI solid electrolyte surface interface
  • the gas containing carbon may be methane gas, ethane gas, propane gas, butane gas, ethylene gas, acetylene gas, or a combination thereof.
  • the gas containing carbon may be an acetylene gas.
  • the pyrolysis temperature may be about 600 ° C. to 90 CTC, and the pyrolysis time may be about 5 to 15 minutes.
  • the pyrolysis temperature may be about 700 ° C to 800 ° C.
  • One embodiment of the present invention comprises the steps of acid-treating a carbon-based material to oxidize the surface of the carbon-based material; Coating the surface of the oxidized carbonaceous material with titania to obtain a carbonaceous material including a titania coating layer; Coating a carbon-based material including a titania coating layer with silica to obtain a carbon-based material including a silica coating layer on the titania coating layer; Removing only the carbon-based material from the carbon-based material including the silica coating layer on the titania coating layer to obtain silica nanotubes including the silica coating layer on the titania coating layer; It provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of reducing the silica nanotubes including the silica coating layer on the tinania coating layer to obtain a silicon nanotube containing titanium.
  • the carbon-based material may be graphite, soft carbon, hard carbon, carbon nanotubes, carbon or nofiber, or a
  • the diameter of the oxidized carbonaceous material may be about 10 nm to 1 ⁇ , for example about 10 nm to 20 nm.
  • the surface of the oxidized carbonaceous material may be reacted with a titania precursor and a catalyst to obtain a carbonaceous material including a titania coating layer.
  • the titania precursor may be titanium butoxide (T anium (lV) but o ide), titanium oxide (Titanium (4) oxide), titanium fluoride (Titanium (IV) fluoride), or a combination thereof.
  • the catalyst may be 3 ⁇ 40, acetic acid, ammonium hydroxide (NH 4 0H), hydrochloric acid (HC1), or a combination thereof.
  • water and titanium tetrabutoxide are added to the mixed solution of ethylene glycol and ethanol on the surface of the oxidized carbon-based material, and about 7 (rc to 9 (about
  • the titania coating layer is an amorphous titania coating layer and may have a thickness of about 1 nm to 10 nm.
  • the titania coating layer may have a thickness of about 2 nm to 5 nm.
  • the thickness of the titania coating layer can be adjusted by changing the amount of the catalyst and the titania precursor.
  • the titania coating layer may also be porous. This minimizes the volume expansion of the silicon.
  • the silica coating layer may be included in about 50 to 90 parts by weight based on 100 parts by weight of the carbon-based material including the silica coating layer. In this case, the density of the final material can be improved by increasing the content of silicon.
  • One embodiment of the present invention comprises the steps of coating the oxidized carbon-based material surface with titania to obtain a carbon-based material comprising a titania coating layer; And coating a carbon-based material including the titania coating layer with silica to obtain a carbon-based material including a silica coating layer on the titania coating layer. And calcining the carbonaceous material including the titania coating layer in an argon atmosphere therebetween. can do.
  • the titania coating layer and the silica coating layer may be separated to form a silica coating layer on the titania coating layer.
  • the titania and silica may be mixed and the titania coating layer and the silica coating layer may not be separated.
  • the silica coating layer may be included in about 50 to 90 parts by weight based on 100 parts by weight of the carbon-based material including the silica coating layer on the tinania coating layer.
  • the thickness of the silica coating layer may be about 50 nm to 500 nm, such as about 200 nm to 400 nm.
  • carbon-based materials including a silica coating layer on the thin tinania coating layer may be gathered together to form an assembly.
  • a step of obtaining silica nanotubes including a silica coating layer on the titania coating layer by removing only the carbon-based material from the carbon-based material including the silica coating layer on the titania coating layer.
  • the carbon-based material comprising a silica coating layer on the tinania coating layer is calcined in an air environment for about 30 to 90 minutes at about 500 ° C to 70 (C, to remove the carbon-based material have.
  • FIG. 15 is an XRD pattern graph of a negative electrode active material prepared according to Comparative Example 2. to be. It can be seen from FIG. 15 that titanium carbide (TiC) is present.
  • FIG. 20 is a flowchart illustrating a method of manufacturing a negative electrode active material including the calcining process of Example 2; By removing the carbon-based material such as carbon nano-lube through it to block the formation of titanium carbide (TiC), it is possible to implement a lithium secondary battery with excellent capacity characteristics.
  • FIG. 23 is an XRD pattern graph of a negative active material prepared according to Example 2. FIG. It can be seen from FIG. 23 that titanium carbide (TiC) does not exist.
  • the silica nanotubes including the silica coating layer on the tinania coating layer may be reduced by using a reducing agent.
  • the reducing agent may reduce titania and silica of the silica nanotubes to titanium and silicon, respectively.
  • the metal reducing agent may be magnesium aluminum, calcium, lithium, or a combination thereof.
  • the silica nanotubes may be reduced to silicon nanonueves using magnesium thermal reduction (magnesiothermic reduction).
  • the surface of the silicon nanotubes including titanium is coated with carbon. It may further comprise a step to make.
  • Another embodiment of the present invention provides a negative electrode active material for a lithium secondary battery manufactured by the manufacturing method according to the embodiment.
  • the anode active material does not include silicon carbide (SiC) or titanium carbide (Ti'C), and has a form of silicon nanotubes by removing carbon nanotubes located at the center of the anode active material through a calcination process, and the surface of the silicon nanotubes.
  • SiC silicon carbide
  • Ti'C titanium carbide
  • Another embodiment of the present invention provides an electrochemical device including the negative electrode, the positive electrode, and the electrolyte including the negative electrode active material.
  • the electrochemical device may be a battery, a capacitor, or the like, and specifically, may be a lithium secondary battery.
  • a lithium secondary battery according to one embodiment is described with reference to FIG. 1.
  • 1 is a schematic view showing a rechargeable lithium battery according to one embodiment.
  • a lithium secondary battery 100 according to an embodiment is disposed between a positive electrode 114, a negative electrode 112 facing the positive electrode 114, a positive electrode 114, and a negative electrode 112.
  • An electrode assembly including a separator 113 and an electrolyte solution (not shown) that impregnates the anode 114, the cathode 112, and the separator 113, a battery container 120 containing the electrode assembly, and the battery And a sealing member 140 for sealing the container 120.
  • the negative electrode 112 includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode active material is as described above.
  • the negative electrode active material layer may optionally further include a binder and / or a conductive material.
  • the binder adheres the anode active material particles to each other well, and also serves to adhere the anode active material to the current collector.
  • the binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose and polyvinyl chloride. Carboxylated polyvinylchloride, polyvinylfluoride, polymers containing ethylene oxide, polyvinylpyridone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene- Butadiene rubber, acrylic styrene—butadiene rubber, epoxy resin, nylon, etc. may be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and may be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • natural alum, artificial graphite, carbon black, acetylene black, ke Carbon-based materials such as chen black and carbon fiber;
  • Metal materials such as metal powder or metal fibers such as copper, nickel, aluminum, and silver; conductive polymers such as polyphenylene derivatives; Or an electroconductive material containing these mixture can be used.
  • the current collector may be copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam (foam), copper foam, a polymer substrate coated with a conductive metal, or a combination thereof.
  • the positive electrode 114 includes a current collector and a positive electrode active material layer formed on the current collector, and the positive electrode active material layer includes a positive electrode active material.
  • a compound (lithiated intercalation compound) capable of reversible intercalation and deintercalation of lithium may be used.
  • one or more of complex oxides of metal and lithium of cobalt, manganese, nickel or a combination thereof may be used, and specific examples thereof may be a compound represented by any one of the following chemical formulas. Li a / — b R b D 2 (wherein 0.90 ⁇ a
  • Li a Ni b Co c Mn d Ge 0 2 (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.5 and 0.001 ⁇ e ⁇ 0.1); Li a NiG b 0 2 (wherein 0.90 ⁇ a ⁇ 1.8 and 0.001 ⁇ b ⁇ 0.1 J; Li a CoG b 0 2 (wherein 0.90 ⁇ a ⁇ 1.8 and 0.001 ⁇ b ⁇ 0.1); a MnG b 0 2 (wherein 90 ⁇ a ⁇ 1.8 and 0.001 ⁇ b ⁇ 0.1); Li a Mn 2 G b 0 4 (wherein 0.90 ⁇ a ⁇ 1.8 and 0.001 ⁇ b ⁇ 0.1) J ; Q0 2 ; QS 2 ; LiQS 2 ; V 2 0 5 ; LiV 2 0 5 ; LiT0 2 ; LiN
  • A is Ni, Co, Mn or a combination thereof;
  • R is A1, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or combinations thereof;
  • D is 0, F, S, P or a combination thereof;
  • E is Co, Mn or a combination thereof;
  • Z is F, S, P or Is a combination of these;
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or a combination thereof;
  • Q is Ti, Mo, Mn or a combination thereof;
  • T is Cr, V, Fe, Sc, Y or a combination thereof;
  • J is V, Cr, Mn, Co, Ni, Cu or a combination thereof.
  • the coating layer may include an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • the compounds that make up these coating layers may be amorphous or crystalline.
  • the coating element included in the coating layer Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr or a combination thereof may be used.
  • the coating layer forming process is a method that does not adversely affect the physical properties of the positive electrode active material by using these elements in the compound (for example, any coating method may be used as long as it can be coated by spray coating, dipping, etc.) This will be well understood by those skilled in the art, so a detailed description thereof will be omitted.
  • the positive electrode active material layer may also include a binder and a conductive material.
  • the binder adheres the positive electrode active material particles to each other well, and also serves to adhere the positive electrode active material to the current collector.
  • the binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl salose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers including ethylene oxide, poly Vinylpyridone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. no.
  • the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical changes in the battery.
  • natural alum, artificial alum, carbon black, acetylene black, Metal powders such as ketjen black, carbon fiber, copper, nickel, aluminum, silver, metal fibers and the like can be used, and one or more kinds of conductive materials such as polyphenylene derivatives can be used in combination.
  • A1 may be used as the current collector, but is not limited thereto.
  • the negative electrode and the positive electrode are each prepared by mixing an active material, a binder, and a conductive material in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • N-methylpyrrolidone may be used as the solvent, but is not limited thereto.
  • the electrolyte solution contains a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the cell can move.
  • the non-aqueous organic solvent may be a carbonate, ester, ether, ketone, alcohol or aprotic solvent.
  • the carbonate solvent is dimethyl .
  • the ester solvent may be methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate methyl propionate, ethyl propionate, gamma- Butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone and the like can be used.
  • the ether solvent dibutyl ether, tetraglyme, diglyme, dimethoxy ethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be used.
  • the ketone solvent cyclonucleanone may be used. Can be used.
  • ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol solvent, and as aprotic solvent, R ⁇ CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, Amides such as nitrile dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolane, etc. may be used.
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more in combination can be appropriately adjusted according to the desired battery performance, which is widely used by those skilled in the art. Can be understood.
  • the carbonate solvent it is preferable to use a cyclic carbonate and a chain carbonate in combination.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the non-aqueous organic solvent may further include the aromatic hydrocarbon organic solvent in the carbonate solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of about 1: 1 to about 30: 1.
  • the non-aqueous electrolyte may further include vinylene carbonate or ethylene carbonate-based compound to improve battery life.
  • ethylene carbonate compounds include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyano ethylene carbonate, fluoroethylene carbonate, Vinylene ethylene carbonate, and the like.
  • the vinylene carbonate or the ethylene carbonate-based compound is further used, the amount thereof may be appropriately adjusted to improve life.
  • the lithium salt is dissolved in the non-aqueous organic solvent, and serves as a source of lithium ions in the battery to enable the operation of the basic lithium secondary battery, and to promote the movement of lithium ions between the positive electrode and the negative electrode. It is a substance.
  • lithium salt examples include LiPF 6) LiBF 4 , LiSbF 6 , LiAsF 6) LiC 4 F 9 S0 3 , LiC10 4) LiA10 2 LiAlCU, LiN (C x F 2x + 1 S0 2 ) (C y F 2y + 1 S0 2 ), where x and y are natural numbers, LiCl, Li I, LiB (C 2 0 4 ) 2 (lithium bis (oxalato) borate (LiBOB) or combinations thereof
  • the lithium salt may be used within the range of 0.1 to 2.0 M. If the concentration of the lithium salt is in the above range, the electrolyte may have an appropriate conductivity and viscosity. Therefore, it can exhibit excellent electrolyte performance, and lithium can move effectively.
  • the separator separates the negative electrode from the positive electrode and provides a passage for moving lithium ions, and any separator can be used as long as it is commonly used in lithium batteries.
  • a low resistance to the subsequent movement of the electrolyte and excellent in the electrolyte solution moistening ability can be used.
  • it is selected from glass fiber, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or a combination thereof, and may be in the form of a nonwoven fabric or a woven fabric.
  • a polyolefin-based polymer separator such as polyethylene or polypropylene is mainly used for a lithium ion battery, and a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength. Or it can be used in a multilayer structure.
  • 0.2 g of multi-walled carbon nanotubes with an average diameter of 15 mm was added to the aqueous sulfuric acid solution to activate the surface of the carbon nano-leave.
  • a mixed solution of ammonium hydroxide (12 mL, 25.0 to 28.0 wt%) and ethanol (200 mL) was dispersed for about 20 to 40 minutes in ultrasonically activated carbon nanotubes, and then about 10 minutes.
  • tetraethoxysilane (9 mL) was added and mixed at room temperature for 6 hours. Thereafter, the suspension added with tetraethoxysilane was centrifuged at a speed of 3500 rpm to form a silica coating layer on the carbon nanotubes.
  • the carbon nanotubes including the silica coating layer were calcined at 450 ° C. for 1 hour to remove the carbon nanotubes, thereby obtaining silica nanotubes. (Si0 2 nanotubes)
  • Silicon nanotubes were obtained by reducing the silica nanotubes at 70 (C for 3 hours using magnesium thermal reduction method. (Si nanotubes)
  • Example 2 the step was performed in the same manner as in Example 1 to remove the carbon nanotubes (Ti0 2 @ Si0 2 nanotubes), and in the same manner as in Example 1, the silicon nano-rubber containing titanium (TixSiy @ Si nano-lube) , 0 ⁇ x ⁇ 5, 0 ⁇ y ⁇ 4).
  • a negative electrode active material was prepared in the same manner as in Example 1, except that the carbon nanotubes including the silica coating layer were calcined at 60 CTC for 1 hour to remove the carbon nanotubes. (Carbon coated CNT @ SiC @ Si nanotubes)
  • a negative electrode active material was prepared in the same manner as in Example 2 except that the carbon nanotubes including the silica coating layer on the titania coating layer were calcined at 60 CTC for 1 hour to remove the carbon nanotubes. Prepared. (Carbon coated CNT @ TiC / TixSiy @ Si nanotubes, 0 ⁇ x ⁇ 5, 0 ⁇ y ⁇ 4)
  • a coin battery was manufactured in the same manner as in Example 3, except that the negative electrode active material prepared in Example 2 was used instead of the negative electrode active material prepared in Example 1.
  • a coin battery was manufactured in the same manner as in Example 3, except that the negative electrode active material prepared in Comparative Example 1 was used instead of the negative electrode active material prepared in Example 1.
  • a coin battery was manufactured in the same manner as in Example 3, except that the negative electrode active material prepared in Comparative Example 2 was used instead of the negative electrode active material prepared in Example 1.
  • the coin cells prepared in Examples 3, 4, Comparative Example 3, and Comparative Example 4 were subjected to constant current experiments using a layer discharger capable of constant current / potential control at 25 ° C. 19 and FIGS. 24 to 27.
  • FIG. 18 and "19 for the coin battery of Comparative Example 3 is an evaluation of the coin battery of Example 3.
  • a constant current corresponding to C / 5 (lithiation)-C / 5 (Delithiation) rate of each coin cell was applied, and the discharge end voltage was 1.2 V (vs. Li / Li). +), The termination voltage was fixed at 0.01 V (vs. Li / Li + ), respectively.
  • FIGS. 16 and 18 are voltage change curves according to one cycle capacity
  • FIGS. 17 and 19 are capacity change curves when layer discharge is performed up to 50 times. 16 to 19, it can be seen that the life characteristics of Example 3 are significantly superior to those of Comparative Example 3.
  • 24 and 25 show evaluation results of the coin battery of Comparative Example 4
  • FIGS. 26 and 27 show evaluation results of the coin battery of Example 4.
  • 24 and 26 are voltage change curves according to one cycle capacity
  • FIGS. 25 and 27 are capacity change curves when charge and discharge are performed up to 50 or 80 times. 24 to 27, it can be seen that the life characteristics of Example 4 are significantly superior to those of Comparative Example 4.
  • the experimental conditions were changed to 0.5-0.7 ⁇ 1-1.5-2-3-5-0.2 C-rate based on the capacity of each coin cell to apply constant current, and the discharge end voltage was 1.2 V (vs. Li / Li +), the end-of-layer (1 ithiat ion) end voltage was fixed to 0.01V (vs. Li / Li + ), respectively.
  • lithium secondary battery o

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Abstract

La présente invention concerne un procédé de préparation d'un matériau actif d'anode destiné à une batterie secondaire au lithium, un matériau actif d'anode préparé au moyen dudit procédé de préparation et une batterie secondaire au lithium le comprenant. Ledit procédé de préparation de matériau actif d'anode destiné à une batterie secondaire au lithium comprend les étapes consistant à : soumettre un matériau à base de carbone à un traitement acide en vue d'oxyder la surface du matériau à base de carbone; revêtir la surface du matériau à base de carbone oxydé avec de la silice en vue d'obtenir un matériau à base de carbone comprenant une couche de revêtement en silice; éliminer uniquement le matériau à base de carbone contenu dans le matériau à base de carbone comprenant la couche de revêtement en silice en vue d'obtenir un nanotube de silice; et faire réduire le nanotube de silice en vue d'obtenir un nanotube de silicium.
PCT/KR2014/004277 2013-06-20 2014-05-13 Matériau actif d'anode pour batterie secondaire au lithium, son procédé de préparation, et batterie secondaire au lithium WO2014204095A1 (fr)

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