WO2019108050A1 - Matériau actif d'anode pour batterie rechargeable à électrolyte non aqueux comprenant un composite à base d'oxyde de silicium et son procédé de production - Google Patents

Matériau actif d'anode pour batterie rechargeable à électrolyte non aqueux comprenant un composite à base d'oxyde de silicium et son procédé de production Download PDF

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WO2019108050A1
WO2019108050A1 PCT/KR2018/015213 KR2018015213W WO2019108050A1 WO 2019108050 A1 WO2019108050 A1 WO 2019108050A1 KR 2018015213 W KR2018015213 W KR 2018015213W WO 2019108050 A1 WO2019108050 A1 WO 2019108050A1
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silicon oxide
oxide composite
secondary battery
active material
electrolyte secondary
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PCT/KR2018/015213
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English (en)
Korean (ko)
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오성민
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대주전자재료 주식회사
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Priority to EP18883021.0A priority Critical patent/EP3719881A4/fr
Priority to JP2020529539A priority patent/JP2021504918A/ja
Priority to CN201880077812.2A priority patent/CN111418095A/zh
Priority to US16/768,275 priority patent/US20210184204A1/en
Priority claimed from KR1020180154038A external-priority patent/KR102185490B1/ko
Publication of WO2019108050A1 publication Critical patent/WO2019108050A1/fr

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    • 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
    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • 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
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 nonaqueous electrolyte secondary battery comprising a silicon oxide composite and a method of manufacturing the same.
  • Lithium secondary batteries which have been popular as power sources for portable electronic devices in recent years, exhibit high energy densities that exhibit discharge voltages two times higher than those using conventional alkaline aqueous solutions by using organic electrolytic solutions.
  • an oxide made of a transition metal having a structure capable of intercalating lithium such as LiCoO 2 , LiMn 2 O 4 , LiNi 1 - x Co x O 2 (0 ⁇ x ⁇ 1)
  • various types of carbon-based materials including artificial graphite, natural graphite, and hard carbon capable of inserting and desorbing lithium have been used as the negative electrode active material.
  • Metallic materials such as Si, Sn, Al, and Sb have been studied as novel materials that can replace the carbon-based anode active material.
  • charge / discharge is performed by alloying / non-alloying reaction with Li, and it is known that it exhibits higher capacity than graphite which is a commercial negative electrode active material.
  • Si is known to be the most suitable material for high capacity cathode materials in terms of discharge capacity (4200 mAh / g) and discharge voltage (0.4 V), but it is believed that about 400% Pulverization of the active material occurs due to a large volume expansion, and thus the life characteristics have been drastically reduced.
  • Patent Publication No. 10-2014-0042146 Publication date 2014.04.07 is available.
  • Another object of the present invention is to provide a nonaqueous electrolyte lithium secondary battery containing the negative electrode active material for a nonaqueous electrolyte secondary battery comprising the silicon oxide composite.
  • the negative electrode active material for a nonaqueous electrolyte secondary battery includes a silicon oxide composite containing silicon, silicon oxide (SiO x , 0 ⁇ x? 2) and magnesium silicate and having pores of 50 nm to 300 nm in size .
  • an anode active material for a nonaqueous electrolyte secondary battery according to an embodiment of the present invention is a negative active material comprising a silicon oxide composite, wherein the silicon oxide composite is formed of silicon, silicon oxide (SiO x , 0 ⁇ x ⁇ 2) And magnesium oxide, and pores having a size of 50 nm to 300 nm arranged inside the silicon oxide composite.
  • the pores inside can be displayed by image processing.
  • the pores disposed inside the silicon oxide complex serve to buffer the expansion during the charging process, thereby solving the swelling problem, It can prevent the rapid deterioration of the service life due to shrinkage.
  • the negative electrode active material for a non-aqueous electrolyte secondary battery including the silicon oxide composite according to the present invention can effectively control volume expansion by concentrating the volume expansion and the stress due to charging and discharging of the lithium secondary battery in the internal pores. The lifetime characteristics of the lithium secondary battery can be improved.
  • the pores may be closed pores disposed inside the silicon oxide composite, and some pores of the pores may have an open opening Pores may be included.
  • the pores may be closed pores disposed inside the silicon oxide composite.
  • the average diameter of the pores may be 50 nm to 300 nm.
  • the negative electrode active material for a nonaqueous electrolyte secondary battery comprising the silicon oxide composite according to the present invention
  • the average diameter of the pores is less than 50 nm
  • the pore size is too small to accommodate the volumetric expansion of Si upon charging and discharging of the lithium secondary battery
  • the average diameter of the pores is more than 300 nm
  • the energy density can be reduced because there is a large amount of pores remaining to accommodate the volume expansion of Si, and the mechanical strength of the negative electrode active material containing a large amount of pores is reduced .
  • the mechanical strength of the negative electrode active material is lowered, the negative electrode active material may be destroyed during the manufacturing process of the battery such as slurry mixing, coating and rolling.
  • the negative electrode active material for a nonaqueous electrolyte secondary battery comprising the silicon oxide composite according to the present invention can be efficiently charged with lithium ions because the nonaqueous electrolyte is impregnated into the pores and lithium ions can be injected into the silicon oxide complex And the charging and discharging efficiency of the lithium secondary battery can be improved.
  • the anode active material for a nonaqueous electrolyte secondary battery including the silicon oxide composite according to the present invention may have a ratio of the area of the pore portion to the total area of the cross section of 3 to 40%.
  • the area ratio of the pore portion is less than 3%, the volume expansion of the negative electrode active material during charging and discharging of the lithium secondary battery can not be suppressed.
  • the area ratio is more than 40%, the large amount of pores existing in the negative electrode active material causes mechanical strength And the negative electrode active material may be destroyed during the cell manufacturing process (mixing of slurry, rolling after coating, etc.).
  • the silicon may be crystalline or amorphous.
  • the expansion and contraction during charging and discharging are reduced, The battery performance can be improved.
  • the silicon oxide may be silicon dioxide.
  • the silicon oxide is included in an amount of 5 to 45 mol% of the total mols of the silicon oxide complex.
  • the content of the silicon oxide is less than 5 mol% when the negative active material for a non-aqueous electrolyte secondary battery comprising the silicon oxide composite according to the present invention is used, the volume expansion and lifetime characteristics may be deteriorated. When the content exceeds 45 mol% The irreversible reaction is increased and the lifetime of the secondary battery may be reduced.
  • the size of the silicon crystallite calculated from the FWHM may be 1 nm to 20 nm.
  • the ratio of the number of silicon atoms to the number of silicon atoms in the silicon oxide may be 0.5 to 2 (Si / O).
  • the negative electrode active material for a nonaqueous electrolyte secondary battery including the silicon oxide composite according to the present invention since silicon can be dispersed in magnesium silicate, expansion and contraction of silicon are further suppressed, and when used as an anode active material of a secondary battery, Can be further improved.
  • the magnesium silicate may include at least one of MgSiO 3 and Mg 2 SiO 4 .
  • the magnesium silicate may include MgSiO 3 as a main component.
  • the magnesium silicate may be a compound represented by the general formula Mg x SiO y (0.5 ⁇ x ⁇ 2, 2.5 ⁇ y ⁇ 4) .
  • magnesium may be contained in an amount of 2 wt% to 40 wt%, preferably 4 wt% to 30 wt%, based on the total weight of the silicon oxide composite %, More preferably 4 wt% to 20 wt%.
  • the initial charge and discharge efficiency may be decreased.
  • the magnesium content exceeds 40 wt%, the capacity retention ratio and handling stability .
  • the magnesium silicate when used as a negative electrode active material because the magnesium silicate is difficult to react with Li ions, the magnesium silicate is initially irreversible And the lifetime characteristics can be improved by reducing the expansion and contraction amount of the electrode when the Li ion is rapidly increased.
  • the specific gravity of the silicon oxide composite of 1.8 to 3.2, and the average particle diameter of 20 to 0.5 ⁇ m ⁇ m, a specific surface area of 1m 2 / g to 40m 2 / g. If the specific gravity of the silicon oxide composite is less than 1.8, mechanical stability may be deteriorated. If the specific gravity exceeds 3.2, the charge and discharge capacity may be lowered when used as an anode active material of a secondary battery. When the average particle diameter of the silicon oxide composite is less than 0.5 mu m, the bulk density becomes small, so that the charging and discharging capacity per unit volume can be reduced. In the case of the anode active material, dispersion of the slurry may be difficult, .
  • the average particle diameter of the silicon oxide composite exceeds 20 mu m, it may be difficult to produce an electrode film, and the negative electrode active material containing the silicon oxide composite may be peeled off from the current collector, and the uniform reaction of lithium and the inside of the negative electrode active material is difficult The life of the secondary battery may be deteriorated.
  • the negative electrode active material for a nonaqueous electrolyte secondary battery comprising the silicon oxide composite according to the present invention may contain 2 wt% to 40 wt% of magnesium based on the total weight of the silicon oxide composite.
  • the negative electrode active material for a nonaqueous electrolyte secondary battery comprising the silicon oxide composite according to the present invention may contain 25 wt% to 40 wt% of oxygen based on the total weight of the silicon oxide composite.
  • the present invention may further comprise a coating layer containing carbon on the surface of the negative electrode active material for a nonaqueous electrolyte secondary battery comprising the silicon oxide composite.
  • the coating layer may be in a proportion of 2 wt% to 20 wt%, more preferably 2 wt% 10 wt%. If the content of the carbon-containing coating layer is less than 2 wt%, sufficient conductivity enhancement effects can not be expected, and the electrode life of the lithium secondary battery may deteriorate. If it exceeds 20 wt%, the discharge capacity may decrease, And the discharge capacity may be lowered.
  • the carbon-containing coating layer may contain at least one selected from the group consisting of amorphous carbon, carbon nanofibers, .
  • the coating layer can provide excellent electrical conductivity between the particles and particles of the silicon oxide composite, thereby further improving the performance of the lithium secondary battery .
  • the carbon-containing coating layer can improve the performance of the lithium secondary battery by suppressing side reactions with the electrolyte.
  • the average thickness of the coating layer containing carbon disposed on the surface of the silicon oxide composite may be 1 nm to 5 m, And more preferably from 10 nm to 1 [mu] m.
  • the conductivity can be improved.
  • the average thickness is 5 m or less, the battery capacity can be suppressed from decreasing when used as a negative electrode active material for a lithium ion battery.
  • the average thickness of the coating layer is less than 1 nm, the synergistic effect of the electric conductivity by the carbon coating is insignificant, and the initial efficiency may be lowered due to high reactivity with the electrolyte when applied to the anode active material. If the average thickness of the coating layer is more than 5 mu m, the resistance of the lithium ions may be increased by interfering with the mobility of lithium ions.
  • the non-aqueous electrolyte secondary battery negative electrode active material comprising silicon oxide composite according to the present invention if it contains a carbon coating layer a specific gravity of 1.8 to 3.2, a mean particle diameter of 20 to 0.5 ⁇ m ⁇ m and a specific surface area of 1m 2 / g to 40m 2 / g Lt; / RTI >
  • the content of magnesium may be 1.5 wt% to 30 wt% with respect to the total weight of the silicon oxide composite containing the coating layer according to the present invention.
  • the content of oxygen may be 15 wt% to 33 wt% with respect to the total weight of the silicon oxide composite containing the coating layer according to the present invention.
  • the nonaqueous electrolyte lithium secondary battery according to an embodiment of the present invention includes the negative electrode active material for the nonaqueous electrolyte secondary battery.
  • a second step of controlling the pressure of the reactor to 0.001 torr to 1 torr;
  • the deposition temperature when the deposition temperature is 1200 ° C or higher, particles of the silicon oxide composite vapor state are densely deposited on the metal plate, , And when the deposition temperature is 500 ⁇ or less, the silicon oxide composite vapor particles are not deposited on the metal plate. In addition, when the deposition temperature is in the range of 700 to 1000 ° C, the silicon oxide composite vapor particles may easily form pores in the metal plate.
  • the deposited lumps can be prepared by pulverizing and classifying with a coarse grinder and a jet mill to adjust the particle size to obtain a silicon oxide composite powder having nanopores.
  • the coating layer containing carbon disposed on the silicon oxide composite may be a gas mixture of carbon dioxide gas, a mixed gas of argon, methane, ethane, propane, butane, water vapor or hydrogen, hydrogen, acetylene, benzene and toluene, Mixed with a carbon source containing the mixture, and reacted at 600 ° C to 1200 ° C.
  • the carbon source gas may be a mixed gas containing methane, methane and an inert gas, or a mixed gas containing methane and an oxygen-containing gas.
  • the gas mixture may further include a plurality of inert gases selected from the group consisting of nitrogen, helium, and argon in addition to the carbon source gas.
  • the carbon source gas according to one embodiment may be a CH 4 : CO 2 mixed gas and the CH 4 : CO 2 mixed gas may have a molar ratio of about 1: 0.20 to 0.50, and preferably a molar ratio of about 1: 0.25 to 0.45 And more preferably from about 1: 0.30 to 0.40.
  • the carbon source in accordance with one embodiment is CH 4: H 2 O may be a mixed gas: CO 2.
  • the CH 4 : CO 2 : H 2 O mixed gas may be in a molar ratio of about 1: 0.20 to 0.50: 0.01 to 1.45, preferably about 1: 0.25 to 0.45: 0.10 to 1.35, 1: 0.30 to 0.40: 0.50 to 1.0.
  • the carbon source according to one embodiment may be carbon monoxide (CO) or carbon dioxide (CO 2 ).
  • the carbon source according to an embodiment may be a mixed gas of CH 4 and N 2 .
  • the CH 4: N 2 gas mixture is about 1: may be a molar ratio of 0.30 to 0.40: 0.20, and may be about 0.50 molar, preferably from about 1: and the molar ratio of the number of days of 0.25 to 0.45, more preferably from about 1 .
  • the silicon oxide composite in which the coating layer is disposed on the surface can exhibit high conductivity by the coating layer when the gas mixture contains water vapor.
  • the water vapor content in the gas mixture is not limited, and the preferred water vapor content may be from 0.01 to 10% by volume based on 100% by volume of the total carbon source gas.
  • the nonaqueous electrolyte lithium secondary battery according to an embodiment of the present invention includes the negative electrode active material for the nonaqueous electrolyte secondary battery.
  • the nonaqueous electrolyte secondary battery using the silicon oxide composite as a negative electrode may have excellent capacity retention and initial efficiency.
  • the silicon oxide composite may include a negative electrode active material for a nonaqueous electrolyte secondary battery, a positive electrode active material, a binder, and a conductive material.
  • the negative electrode active material is capable of intercalating and deintercalating lithium ions.
  • the negative electrode active material for a nonaqueous electrolyte secondary battery according to the present invention includes a silicon oxide composite and includes pores having a size of 50 nm to 300 nm in the interior of the secondary battery including the negative active material of the present invention, And the capacity characteristic is improved while preventing rapid deterioration of the lifetime due to shrinkage.
  • FIG. 1 is an image taken by a scanning electron microscope (FE-SEM) with the surface of the silicon oxide composite according to Example 1 being 30000 times.
  • FE-SEM scanning electron microscope
  • Example 2 is an image obtained by scanning electron microscope (FE-SEM) with the surface of the silicon oxide composite according to Example 1 being 100000 times.
  • Example 3 is an image taken by a scanning electron microscope (FE-SEM) with the surface of the silicon oxide composite according to Example 2 being 20,000 times.
  • FE-SEM scanning electron microscope
  • Example 4 is an image taken by a scanning electron microscope (FE-SEM) with the surface of the silicon oxide composite according to Example 2 being 100000 times.
  • Example 5 is an image obtained by scanning electron microscope (FE-SEM) with the surface of the silicon oxide composite according to Example 3 being 20,000 times.
  • Example 6 is an image obtained by scanning electron microscope (FE-SEM) with the surface of the silicon oxide composite according to Example 3 being 100000 times.
  • the silicon oxide composite powder containing magnesium recovered in order to form a coating layer containing carbon was subjected to CVD (chemical vapor deposition) under a mixed gas of argon (Ar) and methane (CH 4 ) using a tube- To prepare a silicon oxide composite (sample 1) containing 9 wt% of magnesium in which a carbon coating layer having a carbon content of 5 wt% was formed.
  • the silicon oxide composite material (sample 1) containing magnesium had a BET specific surface area of 5.5 m 2 / g, a specific gravity of 2.3 g / cm 3, and an average particle diameter (D50) of 6.3 ⁇ , It was confirmed that the crystallite size was 8 nm
  • a silicon oxide composite (sample 2) containing magnesium in an amount of 9 wt% was prepared in the same manner as in Example 1 except for cooling at 800 DEG C to precipitate a silicon oxide composite having a carbon coating layer having a carbon content of 5 wt% Powder.
  • the silicon oxide composite material (sample 2) containing magnesium had a BET specific surface area of 6.2 m 2 / g, a specific gravity of 2.3 g / cm 3 and an average particle diameter (D 50) of 6.5 ⁇ m, It was confirmed that the crystal size was 8 nm.
  • a silicon oxide composite (sample 3) containing 4 wt% of magnesium was prepared in the same manner as in Example 1 except for cooling at 900 DEG C to precipitate a silicon oxide composite having a carbon coating layer having a carbon content of 10 wt% Powder.
  • the silicon oxide composite material (sample 3) containing magnesium had a BET specific surface area of 6.3 m 2 / g, a specific gravity of 2.4 g / cm 3 and an average particle diameter (D50) of 6.2 ⁇ , It was confirmed that the crystal size was 11 nm.
  • a silicon oxide composite (sample 4) containing magnesium in an amount of 12 wt% was prepared in the same manner as in Example 1, except that the titanium oxide was precipitated by cooling at 1000 ⁇ , and a silicon oxide composite Powder.
  • the silicon oxide composite (sample 4) containing magnesium had a BET specific surface area of 5.8 m 2 / g, a specific gravity of 2.3 g / cm 3 and an average particle diameter (D50) of 6.8 ⁇ m, It was confirmed that the crystal size was 13 nm.
  • a silicon oxide composite (sample 5) containing 16 wt% of magnesium was prepared in the same manner as in Example 1 except that the silicon oxide was precipitated by cooling at 1100 ⁇ and a silicon oxide composite Powder.
  • the silicon oxide composite (sample 5) containing magnesium had a BET specific surface area of 6.7 m 2 / g, a specific gravity of 2.4 g / cm 3, and an average particle diameter (D50) of 6.7 ⁇ , It was confirmed that the size of the crystal was 14 nm.
  • a silicon oxide composite (sample 6) containing 15 wt% of magnesium was prepared in the same manner as in Example 1 except for cooling at 800 DEG C to precipitate a silicon oxide composite having a carbon coating layer having a carbon content of 5 wt% Powder.
  • the silicon oxide composite material (sample 6) containing magnesium had a BET specific surface area of 5.2 m 2 / g, a specific gravity of 2.3 g / cm 3 and an average particle diameter (D50) of 6.6 ⁇ , It was confirmed that the size of the crystal was 14 nm.
  • the silicon oxide composite material (sample 7) containing magnesium had a BET specific surface area of 7.2 m 2 / g, a specific gravity of 2.0 g / cm 3 and an average particle diameter (D50) of 6.5 ⁇ , It was confirmed that the crystal size was 12 nm.
  • a silicon oxide composite (sample 8) containing 1 wt% of magnesium in which a carbon coating layer having a carbon content of 5 wt% was formed was prepared in the same manner as in Example 1 except for the precipitation by natural cooling
  • the silicon oxide composite material (sample 8) containing magnesium had a BET specific surface area of 5 m 2 / g, a specific gravity of 2.2 g / cm 3 and an average particle diameter (D 50) of 6.5 ⁇ m, It was confirmed that the crystal size was 8 nm.
  • a silicon oxide composite (sample 9) having a carbon coating layer having a carbon content of 5 wt% was prepared in the same manner as in Example 1, except that magnesium was not added.
  • the silicon oxide composite (sample 9) had a BET specific surface area of 6.5 m 2 / g, a specific gravity of 2.0 g / cm 3, an average particle diameter (D50) of 6.0 ⁇ m and a silicon crystal size measured by X- 5 nm.
  • a negative electrode for a lithium secondary battery and a battery (coin cell) including the silicon oxide composite powder prepared according to the above Examples and Comparative Examples as an electrode active material were prepared.
  • SUPER-P and polyacrylic acid were mixed with the active material and the conductive material so as to have a weight ratio of 80:10:10 to prepare an anode slurry.
  • An electrode having a thickness of 70 mu m was prepared by coating the above composition on a copper foil having a thickness of 18 mu m and drying.
  • the copper foil coated with the electrode was punched into a circle having a diameter of 14 mm to prepare a coin cell negative electrode.
  • a metal lithium foil were used.
  • a porous polyethylene sheet having a thickness of 0.1 mm was used as a separator, and 1 M LiPF6 was dissolved in a solution of ethylene carbonate (EC) and diethylene carbonate (DEC) at a volume ratio of 1: 1 as an electrolyte.
  • EC ethylene carbonate
  • DEC diethylene carbonate
  • 2032 type coin cell (battery) having a thickness of 2 mm and a diameter of 32 mm was manufactured by applying the constituent elements of FIG.
  • the coin cell manufactured in the above production example was charged at a constant current of 0.1 C when the voltage became 0.005 V and discharged until the voltage became 2.0 V at a constant current of 0.1 C to obtain a charging capacity (mAh / g) and a discharging capacity mAh / g) and the initial charge / discharge efficiency (%) were determined.
  • the results are shown in Table 1 above.
  • the coin cell prepared for each sample was charged and discharged one time, and then charged and discharged from the second time until the voltage reached 0.005 V at a constant current of 0.5 C, and the voltage Was discharged until 2.0 V was reached, and cycle characteristics (capacity retention rate of 50 times) were determined.
  • cycle characteristics capacity retention rate of 50 times

Abstract

La présente invention concerne un matériau actif d'anode pour une batterie rechargeable à électrolyte non aqueux. Un matériau actif d'anode pour une batterie rechargeable à électrolyte non aqueux, selon un mode de réalisation de l'invention, comprend un composite à base d'oxyde de silicium comprenant du silicium, de l'oxyde de silicium (SiOx, 0 < x ≤ 2), et du silicate de magnésium, le composite d'oxyde de silicium comprenant des pores ayant une taille de 50 nm à 300 nm à l'intérieur de celui-ci. Le matériau actif d'anode pour une batterie rechargeable à électrolyte non aqueux comprenant le composite à base d'oxyde de silicium selon l'invention résout un problème d'expansion du fait que les pores internes servent à amortir l'expansion pendant un processus de charge, et permet de concentrer les contraintes exercées par l'expansion et la contraction pendant les processus de charge et de décharge dans les pores internes de telle sorte que l'expansion volumique est contrôlée de manière efficace, et par conséquent, les caractéristiques de durée de vie d'une batterie rechargeable au lithium peuvent être améliorées.
PCT/KR2018/015213 2017-12-01 2018-12-03 Matériau actif d'anode pour batterie rechargeable à électrolyte non aqueux comprenant un composite à base d'oxyde de silicium et son procédé de production WO2019108050A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18883021.0A EP3719881A4 (fr) 2017-12-01 2018-12-03 Matériau actif d'anode pour batterie rechargeable à électrolyte non aqueux comprenant un composite à base d'oxyde de silicium et son procédé de production
JP2020529539A JP2021504918A (ja) 2017-12-01 2018-12-03 ケイ素酸化物複合体を含む非水電解質二次電池用負極活物質、及びその製造方法
CN201880077812.2A CN111418095A (zh) 2017-12-01 2018-12-03 包含氧化硅复合物的用于非水电解质二次电池的负极活性物质及其制备方法
US16/768,275 US20210184204A1 (en) 2017-12-01 2018-12-03 Negative electrode active material for non-aqueous electrolyte secondary battery comprising silicon oxide composite and manufacturing method thereof

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KR10-2017-0164207 2017-12-01
KR20170164207 2017-12-01
KR10-2018-0154038 2018-12-03
KR1020180154038A KR102185490B1 (ko) 2017-12-01 2018-12-03 규소산화물복합체를 포함하는 비수전해질 이차전지용 음극활물질 및 이의 제조방법

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112563476A (zh) * 2019-09-26 2021-03-26 贝特瑞新材料集团股份有限公司 一种硅复合物负极材料及其制备方法和锂离子电池
WO2022059340A1 (fr) * 2020-09-18 2022-03-24 株式会社村田製作所 Matériau actif d'électrode négative pour batteries secondaires, électrode négative pour batteries secondaires et batterie secondaire
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CN116732482B (zh) * 2023-05-16 2024-01-26 河南固锂电技术有限公司 一种复合多层镁离子电池正极材料及制备方法

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