WO2015099233A1 - Matériau actif d'anode, batterie secondaire comprenant ledit matériau et procédé de fabrication du matériau actif d'anode - Google Patents

Matériau actif d'anode, batterie secondaire comprenant ledit matériau et procédé de fabrication du matériau actif d'anode Download PDF

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WO2015099233A1
WO2015099233A1 PCT/KR2013/012391 KR2013012391W WO2015099233A1 WO 2015099233 A1 WO2015099233 A1 WO 2015099233A1 KR 2013012391 W KR2013012391 W KR 2013012391W WO 2015099233 A1 WO2015099233 A1 WO 2015099233A1
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active material
negative electrode
secondary battery
electrode active
coating layer
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PCT/KR2013/012391
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English (en)
Korean (ko)
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조종수
안형기
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엠케이전자 주식회사
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Publication of WO2015099233A1 publication Critical patent/WO2015099233A1/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
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/44—Alloys based on cadmium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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 present invention relates to a negative electrode active material, a secondary battery including the same, and a method of manufacturing the negative electrode active material, and more particularly, to a negative electrode active material having excellent lifespan characteristics and electrochemical properties, and a secondary battery and a method of manufacturing the negative electrode active material. will be.
  • lithium secondary batteries are not only used as a power source for portable electronic products such as mobile phones and laptop computers, but also used as medium-large power sources such as hybrid electric vehicles (HEVs) and plug-in HEVs.
  • HEVs hybrid electric vehicles
  • plug-in HEVs plug-in HEVs.
  • the field of application is expanding rapidly. As the application field expands and the demand increases, the appearance and size of the battery are also changed in various ways, and more excellent capacity, life, and safety than the characteristics required in the existing small battery are required.
  • a lithium secondary battery is generally manufactured by using a material capable of intercalation and deintercalation of lithium ions as a cathode and an anode, and installing a porous separator between the electrodes and then injecting an electrolyte solution. And electricity is generated or consumed by a redox reaction by insertion and desorption of lithium ions at the positive electrode.
  • Graphite which is a negative electrode active material widely used in a conventional lithium secondary battery, has a layered structure and thus has very useful characteristics for insertion and desorption of lithium ions.
  • Graphite theoretically has a capacity of 372 mAh / g, but as the demand for high capacity lithium batteries increases recently, a new electrode that can replace graphite is required.
  • active research for commercialization of electrode active materials forming an electrochemical alloy with lithium ions such as silicon (Si), tin (Sn), antimony (Sb), and aluminum (Al) as a high capacity negative electrode active material is actively conducted. It is becoming. However, silicon, tin, antimony, aluminum, etc.
  • transduced active materials such as aluminum, has the problem of degrading electrode cycle characteristics.
  • such a volume change causes cracks on the surface of the electrode active material, and continuous crack formation leads to micronization of the electrode surface, thereby degrading cycle characteristics.
  • the first object of the present invention is to provide a negative active material for a secondary battery having excellent life characteristics and electrochemical characteristics.
  • the second object of the present invention is to provide a secondary battery having excellent life characteristics and electrochemical characteristics.
  • the third object of the present invention is to provide a method for producing a negative active material for a secondary battery having excellent life characteristics and electrochemical characteristics.
  • the present invention to achieve the first object, a silicon single phase; And it has a core comprising an alloy phase, to provide a negative electrode active material for a secondary battery comprising a ceramic coating layer of about 1 nm to about 50 nm thick on the surface of the core.
  • the alloy phase may be an alloy phase of silicon with one or more metal elements selected from the group consisting of titanium, nickel, copper, iron, manganese, aluminum, zirconium, chromium, lanthanum, tin, cerium, cobalt, and zinc.
  • the ceramic coating layer may include aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), or boron oxide (B 2 O 3 ).
  • the thickness of the ceramic coating layer may be about 3 nm to about 25 nm.
  • the ceramic coating layer may be formed conformally on the surface of the core.
  • the ceramic coating layer may be formed by atomic layer deposition (ALD).
  • ALD atomic layer deposition
  • the ratio of the thinnest thickness to the thickest thickness of the ceramic coating layer may be about 0.75 or more.
  • the fraction of the silicon single phase is about 10 wt% to about 60 wt%, and the fraction of the alloy phase is about 40 wt% to the relative content of the silicon single phase and the alloy phase. About 90% by weight.
  • the present invention provides a secondary battery including a positive electrode including a positive electrode active material, a separator, a negative electrode including a negative electrode active material and an electrolyte to achieve the second object.
  • the negative active material may include a ceramic coating layer having a thickness of about 1 nm to about 50 nm on the surface of the core including the silicon single phase and the alloy phase.
  • the alloy phase may be an alloy phase of silicon with one or more metal elements selected from the group consisting of titanium, nickel, copper, iron, manganese, aluminum, zirconium, chromium, lanthanum, tin, cerium, cobalt, and zinc.
  • silicon is mixed with at least one metal element selected from the group consisting of titanium, nickel, copper, iron, manganese, aluminum, zirconium, chromium, lanthanum, tin, cerium, cobalt and zinc. Doing; Grinding the mixture to form a core; And it provides a method for producing a negative electrode active material for a secondary battery comprising the step of forming a ceramic coating layer on the surface of the core by atomic layer deposition (ALD).
  • ALD atomic layer deposition
  • the forming of the ceramic coating layer may include supplying a metal precursor into an ALD reaction chamber in which the core is located to chemisorb the metal precursor to the surface of the core; Purging the ALD reaction chamber to remove excess metal precursor chemisorbed on the surface of the core from the ALD reaction chamber; Supplying an oxidant into the ALD reaction chamber to form a monolayer of metal oxide on the surface of the core; And purging the ALD reaction chamber as one cycle to remove the remaining unreacted oxidant remaining with the metal precursor from the ALD reaction chamber.
  • the forming of the ceramic coating layer may include one to ten cycles of the deposition cycle.
  • the method may further include heat treating the negative active material for the secondary battery after forming the ceramic coating layer.
  • the heat treatment may be performed for about 30 minutes to about 120 minutes at a temperature of about 200 °C to about 500 °C.
  • the content of the metal element is about 10% to about 70% by weight, the content of the silicon is about 30% to about 90% by weight May be%.
  • the negative electrode active material for a secondary battery according to the present invention has an effect having excellent life characteristics and electrochemical characteristics.
  • FIG. 1 is a schematic view showing a cross section of a negative electrode active material for a secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a negative electrode active material for a secondary battery according to an embodiment of the present invention.
  • 3 is a conceptual view for explaining the rapid cooling solidification using a melt spinner.
  • FIG. 4 is a timing diagram illustrating a cycle of forming a ceramic coating layer according to an embodiment of the present invention.
  • FIG. 5 is an exploded perspective view illustrating a rechargeable battery including a negative active material according to an embodiment of the present invention.
  • FIG. 6 is a side cross-sectional view conceptually illustrating a negative electrode included in the rechargeable battery of FIG. 5.
  • FIG. 7 is a side cross-sectional view conceptually illustrating a positive electrode included in the rechargeable battery of FIG. 5.
  • Example 8 is an image of the surface of the negative electrode active material obtained in Example 6 using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • first and second may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • first component may be referred to as the second component, and vice versa, the second component may be referred to as the first component.
  • the present invention is a negative electrode active material for a secondary battery including a silicon single phase and an alloy phase, the secondary coating having a ceramic coating layer of about 1 nm to about 50 nm thick on the surface of the core including the silicon single phase and the alloy phase
  • a battery negative electrode active material Provided is a battery negative electrode active material.
  • FIG. 1 is a schematic view showing a cross-section of a negative electrode active material 100 for a secondary battery according to an embodiment of the present invention.
  • a core 130 including a silicon single phase 110 and an alloy phase 120 is provided, and a ceramic coating layer 140 is provided on a surface of the core 130.
  • the silicon single phase 110 may be particles made of pure silicon (Si), may be single crystalline, may be polycrystalline, or may be amorphous.
  • the alloy phase 120 may be an alloy having a formula of Si-M, and the alloy may form an intermetallic compound and / or a solid solution.
  • M may be an alkali metal, an alkaline earth metal, a group 13-16 element, a transition metal, a rare earth element, or a combination thereof (excluding Si).
  • M is magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr) , Hafnium (Hf), Rutherperdium (Rf), vanadium (V), niobium (Nb), tantalum (Ta), dubnium (Db), chromium (Cr), molybdenum (Mo), tungsten (W), Chevor (Sg), manganese (Mn), technetium (Tc), rhenium (Re), borium (Bh), iron (Fe), lead (Pb), ruthenium (Ru), osmium (Os), hassium (Hs) , Rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd),
  • the alloy phase 120 may be configured to surround the silicon single phase 110, but there may also be a silicon single phase 110a that is not completely surrounded by the alloy phase 120.
  • the ceramic coating layer 140 surrounding the outer surface of the core 130 including the silicon single phase 110 and the alloy phase 120 may have a thickness of about 1 nm to about 50 nm.
  • aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ) or boron oxide (B 2 O 3 ) may be included.
  • the ceramic coating layer 140 may be aluminum oxide, and may have a thickness of about 3 nm to about 25 nm.
  • the ceramic coating layer 140 is formed by atomic layer deposition (ALD), so that hydrothermal synthesis, physical vapor deposition (PVD), or chemical vapor deposition ( higher thickness uniformity than that formed by chemical vapor deposition (CVD).
  • ALD atomic layer deposition
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the ceramic coating layer 140 may be formed on the surface of the core 130 substantially conformally.
  • the thickness uniformity of the ceramic coating layer 140 may be characterized as the ratio of the thinnest thickness to the thickest thickness, the thickness uniformity being less than or equal to 1 in consideration of its definition. It can be seen that it has a value.
  • the ceramic coating layer 140 of the anode active material 100 for secondary batteries of the present invention may have a thickness uniformity of about 0.75 or more.
  • the fraction of the silicon single phase 110 is about 10% to about 60% by weight, the alloy phase 120 The fraction of can be from about 40% to about 90% by weight.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a negative electrode active material for a secondary battery according to an embodiment of the present invention.
  • silicon and a metal element are mixed (S10). Since the metal element has been described in detail above, a detailed description thereof will be omitted.
  • the melting step may be implemented through induction heat generation of silicon and metal elements according to high frequency induction using a high frequency induction furnace.
  • the melt may be formed using an arc melting process or the like.
  • the melt may include, for example, about 30 wt% to about 90 wt% silicon and about 10 wt% to about 70 wt% metal element.
  • other unavoidable impurities may be further included.
  • the molten mixture may be ground to form a core (S20).
  • the melt may be quenched and solidified to form a quenched solidified body.
  • the quench solidification can be performed using a melt spinner apparatus and will be described in detail with reference to FIG. 3.
  • 3 is a conceptual view for explaining the rapid cooling solidification using a melt spinner.
  • the melt spinner 70 includes a cooling roll 72, a high frequency induction coil 74, and a tube 76.
  • the cooling roll 72 may be formed of a metal having high thermal conductivity and thermal shock, and may be formed of, for example, copper or a copper alloy.
  • the cooling roll 72 can be rotated at high speed by a rotating means 71 such as a motor, and can rotate at a speed in the range of 1000 to 5000 rpm (revolution per minute), for example.
  • the high frequency induction coil 74 flows high frequency power by a high frequency induction means (not shown), thereby inducing high frequency to the material charged in the tube 76.
  • a cooling medium flows for cooling.
  • the tube 76 may be formed using a material having low reactivity and high heat resistance with the loaded material, such as quartz or refractory glass.
  • high frequency is induced by the high frequency induction coil 74 and materials (eg, silicon and metal materials) to be melted are charged.
  • the high frequency induction coil 74 is wound around the tube 76 and may melt the material charged in the tube 76 by high frequency induction to form a melt 77 having liquid or fluidity.
  • the tube 76 may then prevent unwanted oxidation of the melt 77 in a vacuum or inert atmosphere.
  • a compressed gas such as an inert gas such as argon or nitrogen
  • the melt 77 is discharged through the nozzle formed on the other side of the tube 76.
  • the melt 77 discharged from the tube 76 contacts the rotating cooling roll 72 and is rapidly cooled by the cooling roll 72 to form a quench solidified body 78.
  • the quench coagulation body 78 may have a shape of a ribbon, flake, powder, or the like.
  • the melt 77 can be cooled at a high rate, for example, at a cooling rate of 10 3 ° C / sec to 10 7 ° C / sec.
  • the cooling rate may vary depending on the rotational speed, material, temperature, and the like of the cooling roll 72.
  • the silicon single phase when the quench solidified body is formed using a melt spinner, since the silicon single phase is rapidly precipitated in the melt, the silicon single phase forms an interface with the silicon-metal alloy phase and the silicon-metal alloy phase in the quenched solidified body. It can be uniformly dispersed inside.
  • the present invention is not limited thereto. In other words, it will be understood by those skilled in the art that the quench solidification can be carried out via a method other than the melt spinner, for example, an atomizer or the like.
  • the quench coagulation body may optionally be heat treated.
  • the heat treatment may be performed in a vacuum atmosphere or in an inert atmosphere including nitrogen, argon, helium, or mixtures thereof, or in a reducing atmosphere including hydrogen and the like.
  • the heat treatment may be implemented by using an inert gas such as vacuum or nitrogen, argon, helium in a circulating manner.
  • the heat treatment may be performed at a temperature in the range of 400 ° C. to 800 ° C. for a period of 1 minute to 60 minutes.
  • the cooling rate after performing the heat treatment step may be in the range of 4 °C / min to 20 °C / min.
  • the heat treatment temperature may be heat treated at a temperature lower than about 200 °C compared to the melting temperature of the quench solidified body. By the heat treatment, the microstructure of the quench solidified body may change.
  • the negative electrode active material pulverized may be a powder having a diameter of several hundreds of micrometers.
  • the powder may have a diameter in the range of 1 ⁇ m to 10 ⁇ m, for example a diameter in the range of 2 ⁇ m to 4 ⁇ m.
  • the grinding process may be performed using known methods for grinding the alloy into powder alloy, such as milling process, ball milling process, jet milling process.
  • the size of the ground powder may be adjusted by adjusting the ball milling process time.
  • the core of the negative electrode active material may be formed into a powder having a particle diameter of several micrometers by ball milling the quenched solidified body for about 20 hours to about 50 hours.
  • a ceramic coating layer may be formed on the surface of the core by atomic layer deposition (S30).
  • FIG. 4 is a timing diagram illustrating a cycle of forming a ceramic coating layer according to an embodiment of the present invention.
  • For a third time t 3 and purging the reaction chamber for a fourth time t 4 to remove residual unreacted oxidant remaining with the metal precursor from the reaction chamber.
  • the deposition cycle (s) comprising the steps may be performed.
  • the deposition cycle may be performed one or more times, and may be performed until a ceramic coating layer having a desired thickness is obtained.
  • the deposition cycle may be performed from 1 cycle to 10 cycles.
  • the thickness of the ceramic coating layer may be about 1 nm to about 50 nm, and more preferably about 3 nm to about 25 nm, as described above.
  • the metal precursor may be, for example, an aluminum precursor, a silicon precursor, a zirconium precursor, or a boron precursor.
  • the aluminum precursor is, for example, trimethylaluminum (Al (CH 3 ) 3 ), triethylaluminum (Al (C 2 H 5 ) 3 ), hexakis (dimethylamino) aluminum (Al 2 (N (CH 3 ) 2 ) 6 ), aluminum trichloride (AlCl 3 ), tritertarybutyl aluminum (TTBA), triisobutyl aluminum, or tris (dimethylamido) aluminum.
  • the silicon precursor is, for example, silane (SiH 4 ), disilane (Si 2 H 6 ), trisilane (Si 3 H 8 ), tetrasilane (Si 4 H 10 ), methylsilane ((CH 3 ) SiH 3 ), dimethylsilane ((CH 3 ) 2 SiH 2 ), ethylsilane ((C 2 H 5 ) SiH 3 ), methyldisilane ((CH 3 ) Si 2 H 5 ), dimethyldisilane ((CH 3 ) 2 Si 2 H 4 ), hexamethylsilane ((CH 3 ) 6 Si 2 ), tris (dimethylamino) silane (TDMAS), tris (tertiary-butoxy) silanol ((C 4 H 9 O) 3 Si -OH), tris (tertiary-pentoxy) silanol ((C 5 H 11 O) 3 Si-OH), di (tertiary-butoxy) silanediol
  • zirconium precursor examples include tetrakisethyl methyl amido zirconium (Zr (NEtMe) 4 , TEMAZ), tetrakis (dimethyl amido) zirconium (TDMAZ), tetrakis (diethyl amido) zirconium (TDEAZ).
  • the boron precursor may be, for example, diborane (B 2 H 6 ), triborane (B 3 H 8 ), tetraborane (B 4 H 10 ), trimethylboraine ((CH 3 ) 3 B), Triethylborane ((C 2 H 5 ) 3 B), borazine (B 3 N 3 H 6 ), alkyl-substituted derivatives of borazine, or BCl 3 .
  • the aluminum, silicon, zirconium and boron precursors are not limited thereto.
  • An inert gas such as helium (He), neon (Ne), argon (Ar), or a low active gas such as nitrogen (N 2 ) may be used to purge the reaction chamber.
  • helium He
  • neon Ne
  • argon Ar
  • nitrogen N 2
  • Water vapor (H 2 O (g)), O 2 , O 3 , N 2 O, NO, CO, CO 2 , CH 3 OH, or C 2 H 5 OH may be used as an oxidizing agent for oxidizing the metal precursor. . However, it is not limited to this.
  • heat treatment may be performed on the negative electrode active material having the ceramic coating layer formed on the core surface (S40).
  • the heat treatment may be performed for about 30 minutes to about 120 minutes at a temperature of about 200 °C to about 500 °C. If the temperature of the heat treatment is too low or the time is too short, the initial efficiency of the prepared negative electrode active material may deteriorate. On the contrary, if the temperature of the heat treatment is too high or the time is too long, the material of the Si alloy core may be recrystallized to reduce the life during charging and discharging, which may cause a problem of a sharp decrease in capacity.
  • the heat treatment may be performed in an atmosphere, or may be performed in an inert atmosphere in which nitrogen gas, argon gas, helium gas, krypton gas, or xenon gas is present.
  • the negative electrode active material for the secondary battery obtained by the above method is not only excellent in initial capacity and initial efficiency as compared with the conventional negative electrode active material, it can also greatly improve the life.
  • FIG. 5 is an exploded perspective view illustrating the rechargeable battery 1 including the negative active material according to the exemplary embodiment.
  • 6 and 7 are side cross-sectional views conceptually illustrating a negative electrode 10 and a positive electrode 20 included in the secondary battery 1 of FIG. 5, respectively.
  • the secondary battery 1 includes a negative electrode 10, a positive electrode 20, and a separator 30, a battery container 40, and a sealing member 50 interposed between the negative electrode 10 and the positive electrode 20. ) May be included.
  • the secondary battery 1 may further include an electrolyte impregnated in the negative electrode 10, the positive electrode 20, and the separator 30.
  • the negative electrode 10, the positive electrode 20, and the separator 30 may be sequentially stacked and accommodated in the battery container 40 in a spirally wound state.
  • the battery container 40 may be sealed by the sealing member 50.
  • the secondary battery 1 may be a lithium secondary battery using lithium as a medium, and may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the separator 30 and the type of electrolyte.
  • the secondary battery 1 may be classified into a coin, a button, a sheet, a cylinder, a flat, a square, and the like according to a shape, and may be classified into a bulk type and a thin film type according to the size.
  • the secondary battery 1 illustrated in FIG. 5 exemplarily shows a cylindrical secondary battery, and the technical spirit of the present invention is not limited thereto.
  • the negative electrode 10 includes a negative electrode current collector 11 and a negative electrode active material layer 12 positioned on the negative electrode current collector 11.
  • the negative electrode active material layer 12 includes a negative electrode binder 14 for attaching the negative electrode active material 13 and the negative electrode active material 13 to each other.
  • the negative electrode active material layer 12 may further include a negative electrode conductor 15 selectively.
  • the negative electrode active material layer 12 may further include an additive such as a filler or a dispersant.
  • a negative electrode active material 13, a negative electrode binder 14, and / or a negative electrode conductor 15 may be mixed in a solvent to prepare a negative electrode active material composition, and the negative electrode active material composition may be disposed on the negative electrode current collector 11. It can be formed as an inclusion in the.
  • the negative electrode current collector 11 may include a conductive material and may be a thin conductive foil.
  • the negative electrode current collector 11 may include, for example, copper, gold, nickel, stainless steel, titanium, or an alloy thereof.
  • the negative electrode current collector 11 may be made of a polymer including a conductive metal.
  • the negative electrode current collector 11 may be formed by compressing the negative electrode active material.
  • the negative electrode active material 13 may use, for example, a negative electrode active material for a lithium secondary battery, and may include a material capable of reversibly intercalating / deintercalating lithium ions. As described in detail above, the negative electrode active material 13 may be a negative electrode active material having a ceramic coating layer formed on a surface of a core made of a single silicon phase and an alloy phase.
  • the negative electrode binder 14 attaches the particles of the negative electrode active material 13 to each other, and also serves to attach the negative electrode active material 13 to the negative electrode current collector 11.
  • the negative electrode binder 14 may be, for example, a polymer, for example polyimide, polyamideimide, polybenzimidazole, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, polyvinylchloride, carboxylation Polyvinylchloride, polyvinylfluoride, ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene, acrylated styrene-butadiene, Epoxy resins and the like.
  • the negative electrode conductor 15 may further provide conductivity to the negative electrode 10 and may be a conductive material that does not cause chemical change in the secondary battery 1, and may be, for example, graphite, carbon black, acetylene black, carbon fiber, or the like. It may include a conductive material containing a carbon-based material, a metal-based material such as copper, nickel, aluminum, silver, conductive polymer materials such as polyphenylene derivatives or mixtures thereof.
  • the positive electrode 20 includes a positive electrode current collector 21 and a positive electrode active material layer 22 positioned on the positive electrode current collector 21.
  • the positive electrode active material layer 22 includes a positive electrode active material 23 and a positive electrode binder 24 for adhering the positive electrode active material 23.
  • the positive electrode active material layer 22 may further include a positive electrode conductor 25 selectively.
  • the positive electrode active material layer 22 may further include an additive such as a filler or a dispersant.
  • the positive electrode 20 is prepared by mixing a positive electrode active material 23, a positive electrode binder 24, and / or a positive electrode conductor 25 in a solvent to prepare a positive electrode active material composition, the positive electrode active material composition on the positive electrode current collector 21 It can be formed by applying to.
  • the positive electrode current collector 21 may be a thin conductive foil, and may include, for example, a conductive material.
  • the positive electrode current collector 21 may include, for example, aluminum, nickel, or an alloy thereof.
  • the positive electrode current collector 21 may be made of a polymer including a conductive metal.
  • the positive electrode current collector 21 may be formed by compressing the negative electrode active material.
  • the positive electrode active material 23 may use, for example, a positive electrode active material for a lithium secondary battery, and may include a material capable of reversibly inserting / desorbing lithium ions.
  • the positive electrode binder 24 attaches the particles of the positive electrode active material 23 to each other, and also serves to attach the positive electrode active material 23 to the positive electrode current collector 21.
  • the positive electrode binder 24 may be, for example, a polymer, for example polyimide, polyamideimide, polybenzimidazole, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, polyvinylchloride, carboxylation Polyvinylchloride, polyvinylfluoride, ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene, acrylated styrene-butadiene, Epoxy resins and the like.
  • the positive electrode conductor 25 may further provide conductivity to the positive electrode 20, and may be a conductive material that does not cause chemical change in the secondary battery 1, and may be, for example, graphite, carbon black, acetylene black, carbon fiber, or the like. It may include a conductive material containing a carbon-based material, a metal-based material such as copper, nickel, aluminum, silver, conductive polymer materials such as polyphenylene derivatives or mixtures thereof.
  • the separator 30 may have a porosity, and may consist of a single membrane or multiple layers of two or more layers.
  • the separator 30 may include a polymer material, and may include, for example, at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyolefin, and the like.
  • the electrolyte (not shown) impregnated in the cathode 10, the anode 20, and the separator 30 may include a non-aqueous solvent and an electrolyte salt.
  • the non-aqueous solvent is not particularly limited as long as it is used as a conventional non-aqueous solvent for non-aqueous electrolyte, and for example, carbonate solvent, ester solvent, ether solvent, ketone solvent, alcohol solvent or aprotic It may include a solvent.
  • the non-aqueous solvent may be used alone or in mixture of one or more, and the mixing ratio in the case of mixing one or more may be appropriately adjusted according to the desired battery performance.
  • the electrolyte salt is not particularly limited as long as it is used as a conventional electrolyte salt for a nonaqueous electrolyte, and may be, for example, a salt having a structural formula of A + B ⁇ .
  • a + may be an ion including an alkali metal cation such as Li + , Na + , K + or a combination thereof.
  • B - is PF 6 -, BF 4 -, Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, Or an ion such as C (CF 2 SO 2 ) 3 ⁇ , or a combination thereof.
  • the electrolyte salt may be a lithium salt, for example LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (SO 2 C 2 F 5 ) 2 , Li (CF 3 SO 2 ) 2 N, LiN (SO 3 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ), where , x and y may be a natural number), LiCl, LiI and LiB (C 2 O 4 ) 2 It may include one or two or more selected from the group consisting of. These electrolyte salts may be used alone or in combination of two or more thereof.
  • the melt was first formed by melting using an arc melting process and a high frequency induction heating process to have 70% by weight of silicon and 15% by weight of nickel and titanium.
  • the melt solidified rapidly to form a rapid solidified body.
  • the rapid solidification process was performed using the melt spinner equipment.
  • the rapid solidified body was crushed again using a ball milling process, and the cores obtained therein were charged into an ALD reactor and a ceramic coating layer was formed on the surface using ALD.
  • Trimethylaluminum (Al (CH 3 ) 3 ) was used as a precursor to form a ceramic coating layer on the surface of the core, and water vapor was used as the oxidant.
  • the negative electrode active material was obtained by repeating ALD deposition cycle 2 cycles.
  • An anode active material was prepared in the same manner as in Example 1 except that the ALD deposition cycle was repeated 4 cycles instead of 2 cycles.
  • An anode active material was prepared in the same manner as in Example 1 except that the ALD deposition cycle was repeated 8 cycles instead of 2 cycles.
  • a negative electrode active material was prepared in the same manner as in Example 1 except that the heat treatment was performed at 350 ° C. for 60 minutes after the ceramic coating layer was formed.
  • a negative electrode active material was prepared in the same manner as in Example 2 except that the heat treatment was performed at 350 ° C. for 60 minutes after the ceramic coating layer was formed.
  • a negative electrode active material was prepared in the same manner as in Example 3 except that the heat treatment was performed at 350 ° C. for 60 minutes after the ceramic coating layer was formed.
  • Example 1 It was used as a negative electrode active material without forming a ceramic coating layer on the surface of the core obtained in Example 1.
  • Aluminum oxide was coated on the surface of the core obtained in Example 1 by using hydrothermal synthesis.
  • LiPON was coated on the surface of the core obtained in Example 1 by hydrothermal synthesis.
  • Example 6 In order to confirm that the ceramic coating layer was well formed on the surface of the negative electrode active material obtained in Example 6, a negative electrode active material was photographed using a transmission electron microscope (TEM). As a result, as shown in FIG. 8, it was found that the ceramic coating layer was formed on the surface of the particles with a uniform thickness of about 8 nm.
  • TEM transmission electron microscope
  • a coin cell was prepared using a metal lithium as a reference electrode and a negative electrode formed by adding a binder and a conductive material to the negative electrode active materials obtained in Examples 1 to 6 and Comparative Examples 1 to 3 as measurement electrodes. .
  • Example 1 Initial capacity (mAh / g) Initial Efficiency (%) Coulomb Efficiency (%) Capacity retention rate after 50 cycles (%)
  • Example 1 813 84.2 99.4 92.2
  • Example 2 812 84.3 99.4 92.7
  • Example 3 812 84.9 99.5 92.9
  • Example 4 813 87.2 99.8 94.6
  • Example 5 813 87.6 99.8 94.8
  • Example 6 813 88.3 99.9 95.2 Comparative Example 1 813 82.3 99 87.1 Comparative Example 2 757 83.5 99.2 88.5 Comparative Example 3 763 82.8 99.1 88.3
  • the negative electrode active materials of Examples 1 to 6 can be seen that the initial capacity is further improved compared to when the surface layer is formed on the surface by using hydrothermal synthesis. Furthermore, it was found that the initial capacity was more disadvantageous than when the surface layer was formed on the surface of the negative electrode active material by the hydrothermal synthesis method (Comparative Example 2, Comparative Example 3) rather than when the surface layer was not formed (Comparative Example 1).
  • the negative electrode active materials prepared in Examples 1 to 6 not only improved initial efficiency and coulombic efficiency than the negative electrode active materials prepared in Comparative Examples 1 to 3, but also the negative electrode active materials of Examples 4 to 6, which were subjected to heat treatment, to Example 1 It was found that the initial efficiency and the coulombic efficiency were significantly improved than the negative electrode active material of the third to third.
  • the negative electrode active materials prepared in Examples 1 to 6 showed remarkably superior characteristics compared to the negative electrode active materials prepared in Comparative Examples 1 to 3, and particularly in the negative electrode active materials of Examples 4 to 6 subjected to heat treatment. It was confirmed to have a better capacity retention rate.
  • the present invention can be usefully used in the secondary battery industry.

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Abstract

La présente invention concerne un matériau actif d'anode, une batterie secondaire comprenant ledit matériau et un procédé de fabrication du matériau actif d'anode et, plus particulièrement : un matériau actif d'anode pour une batterie secondaire, comprenant une couche de revêtement en céramique ayant une épaisseur d'environ 1 nm à environ 50 nm sur la surface d'un noyau comprenant une monophase de silicium et une phase d'alliage ; la batterie secondaire comprenant ledit matériau ; et un procédé de fabrication du matériau actif d'anode. Le matériau actif d'anode pour la batterie secondaire selon la présente invention offre une durée de vie prolongée et d'excellentes caractéristiques électrochimiques.
PCT/KR2013/012391 2013-12-27 2013-12-30 Matériau actif d'anode, batterie secondaire comprenant ledit matériau et procédé de fabrication du matériau actif d'anode WO2015099233A1 (fr)

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WO2023043603A1 (fr) * 2021-09-15 2023-03-23 Nanograf Corporation Matériau d'électrode comprenant des particules d'oxyde de silicium à surface modifiée
WO2023200985A1 (fr) * 2022-04-13 2023-10-19 Hunt Energy Enterprises, L.L.C. Matériaux d'oxyde métallique revêtus et procédé, leur procédé et leur appareil de fabrication

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KR20190115022A (ko) * 2017-02-27 2019-10-10 엠케이전자 주식회사 음극 활물질, 이를 포함하는 이차 전지 및 음극 활물질의 제조 방법
KR102148511B1 (ko) 2017-09-01 2020-08-27 주식회사 엘지화학 음극 활물질의 제조방법 및 이를 이용한 음극 활물질 및 리튬 이차전지
WO2019045408A1 (fr) 2017-09-01 2019-03-07 주식회사 엘지화학 Procédé de fabrication de matériau actif négatif, matériau actif négatif et batterie secondaire au lithium le comprenant
KR20230155213A (ko) * 2022-05-03 2023-11-10 주식회사 엘지에너지솔루션 리튬 이차 전지용 음극, 리튬 이차 전지용 음극의 제조 방법 및 음극을 포함하는 리튬 이차 전지

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WO2023200985A1 (fr) * 2022-04-13 2023-10-19 Hunt Energy Enterprises, L.L.C. Matériaux d'oxyde métallique revêtus et procédé, leur procédé et leur appareil de fabrication

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