WO2019112325A1 - Matériau actif d'électrode négative pour batterie secondaire à électrolyte non aqueux et procédé de production correspondant - Google Patents

Matériau actif d'électrode négative pour batterie secondaire à électrolyte non aqueux et procédé de production correspondant Download PDF

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WO2019112325A1
WO2019112325A1 PCT/KR2018/015351 KR2018015351W WO2019112325A1 WO 2019112325 A1 WO2019112325 A1 WO 2019112325A1 KR 2018015351 W KR2018015351 W KR 2018015351W WO 2019112325 A1 WO2019112325 A1 WO 2019112325A1
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active material
secondary battery
silicon oxide
negative electrode
electrolyte secondary
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PCT/KR2018/015351
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Korean (ko)
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오성민
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대주전자재료 주식회사
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Priority to JP2020530303A priority Critical patent/JP2021506059A/ja
Priority to CN201880078427.XA priority patent/CN111433949A/zh
Priority to EP18885241.2A priority patent/EP3723171A4/fr
Priority to US16/769,320 priority patent/US20200295352A1/en
Priority claimed from KR1020180155595A external-priority patent/KR102236365B1/ko
Publication of WO2019112325A1 publication Critical patent/WO2019112325A1/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
    • H01M4/38—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
    • 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 an anode active material for a non-aqueous electrolyte secondary cell and a method of manufacturing the same, and more particularly, to a method for producing a silicon oxide composite by reacting silicon, silicon dioxide and magnesium by a gas phase reaction,
  • the present invention also relates to a negative electrode active material for a nonaqueous electrolyte secondary battery and a method for manufacturing the negative electrode active material, which exhibits a stable structure with respect to volume change due to lithium intercalation / deintercalation, thereby greatly improving lifetime characteristics and capacity efficiency characteristics.
  • the lithium secondary battery which has been popular as a power source for portable electronic devices and electric vehicles in recent years, is a battery exhibiting a high energy density exhibiting a discharge voltage two times higher than that of a conventional battery using an alkaline aqueous solution by using an organic electrolytic solution.
  • 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.
  • charging / discharging is performed by alloying / non-alloying reaction with Li, and it is known that it exhibits a higher capacity than graphite, which is a commercial negative electrode active material (Patent Document 1).
  • 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.
  • Silicon oxide (SiO x ) has a capacity several times higher (about 1500 mAh / g) than the capacity of a carbonaceous anode (about 350 mAh / g), which has a smaller capacity than silicon, and silicon nanocrystals uniformly
  • the dispersed structure is in the spotlight as a material having significantly improved volume expansion rate and lifetime (capacity retention rate) characteristics as compared with other silicon-based materials.
  • lithium oxide and silicon oxide react with each other at the initial charging to produce lithium oxide (lithium oxide and lithium silicate), and the generated lithium oxide does not return to the anode reversibly upon discharge.
  • silicon oxide (SiO x ) has a capacity several times higher (about 1500 mAh / g) than the carbon-based anode capacity (about 350 mAh / g)
  • the uniformly dispersed structure is in the spotlight as a material having significantly improved volume expansion rate and lifetime (capacity retention rate) characteristics as compared with other silicon-based materials.
  • the present invention has been extensively studied on the structure of the surface and the stability of the volume change due to lithium intercalation and deintercalation.
  • silicon microcrystals or fine particles The present inventors have found that the above problems can be solved and a large capacity charge / discharge capacity can be stably achieved and the charge / discharge cycle characteristics and efficiency can be greatly improved by coating carbon to disperse in silicon and to impart conductivity to at least a part of the surface.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2012-033317
  • An object of the present invention is to provide a negative electrode active material for a non-aqueous electrolyte lithium secondary battery improved in charging and discharging capacity, initial charging and discharging efficiency and capacity retention rate to solve the problems of the conventional secondary battery negative electrode active material.
  • the preferable ratio of I Si (111) and I MgSiO 3 (610) may be 0.15 ⁇ I MgSiO 3 (610) / I Si (111) ⁇ 0.3.
  • the silicon oxide composite according to the present invention is characterized in that the MgSiO 3 -type magnesium silicate phase contains at least a part of the magnesium silicate phase.
  • the silicon oxide composite may be homogeneously dispersed with silicon fine particles in a matrix containing silicon oxide and crystalline MgSiO 3 . Since MgSiO 3 is difficult to react with Li ions, it is possible to improve cycle characteristics and initial charge and discharge efficiency by reducing the amount of expansion of the electrode when Li ions are occluded when the electrode is used as an electrode.
  • the I MgSiO3 (610) / I Si (111) satisfies the range of 0.1 to 0.5, whereby the deterioration of the battery characteristics can be suppressed by the presence of the magnesium silicate salt, It is easy to insert and detach. In addition, the initial efficiency can be further improved.
  • the silicon oxide composite according to the present invention when the content of I MgSiO3 (610) / I Si (111) exceeds 0.5, crystals of MgSiO 3 type are excessively formed, and initial charging and discharging capacity become small.
  • the I MgSiO3 (610) / I si (111) a low amount of the magnesium silicate MgSiO 3 type is less than 0.1, whereby the effect of improving the cycle characteristics of charge and discharge test is reduced accordingly.
  • the reason why the initial charge and discharge capacities are reduced is that MgSiO 3 , which is included in SiO x and is difficult to react with Li atoms due to reaction of Si atoms originally alloyed with Li atoms and added Mg atoms, may be formed in an excessive amount.
  • Cu-K ⁇ X-ray diffraction
  • the silicon oxide composite may include magnesium in an amount of 2 to 30 parts by weight per 100 parts by weight of the total amount.
  • the magnesium silicate is Mg 2 SiO 4
  • Magnesium silicate is an oxide having a negative Gibbs free energy thermodynamically than silicon oxide, and may be preferable because it plays a role of suppressing the occurrence of the initial irreversible reaction stably in the amorphous state.
  • the magnesium silicate represents a compound represented by the general formula Mg x SiO y (0.5? X ? 2, 2.5? Y ? 4).
  • the magnesium silicate preferably contains MgSiO 3 (enstatite) crystal as a main component.
  • MgSiO 3 (enstatite) crystals exhibit peaks attributed to silicon crystals in the range of diffraction angles 28 ° ⁇ 2 ⁇ ⁇ 29 ° when analyzed by X-ray diffraction patterns, and MgSiO 3 crystals in the range of diffraction angles 30.5 ° ⁇ 2 ⁇ ⁇ 31.5 ° It is preferable that an attributed peak appears. Further, it is preferable to include Mg 2 SiO 4 (forsterite) crystals.
  • the silicon oxide composite is a negative electrode active material for a nonaqueous electrolyte secondary battery having a ratio (Si / O) of the number of silicon atoms to oxygen atoms of 0.5 to 2.
  • the silicon oxide composite further includes a coating layer containing carbon on the surface.
  • the coating layer is 2 to 20 parts by weight per 100 parts by weight of the total of the silicon oxide composite.
  • the covering amount of the carbon coating layer is 2 parts by mass or less, sufficient conductivity improving effect can not be obtained.
  • the covering amount is 20 parts by mass or more, Does not appear.
  • the average thickness of the carbon coating may be 1 nm to 2 ⁇ , preferably 5 nm to 1 ⁇ , and more preferably 10 nm to 0.8 ⁇ .
  • the average thickness of the carbon coating is less than 1 nm, improvement in conductivity can not be obtained. If the average thickness is more than 2 ⁇ , improvement in conductivity due to addition of carbon material can not be obtained.
  • the covering layer containing carbon may be selected from the group consisting of amorphous carbon, carbon nanofiber, carbon nanotube, graphite, graphene, oxidized graphene and reduced oxidized graphene And at least one of the plurality of light emitting devices.
  • the average particle diameter of the carbon-coated silicon composite may be 0.5 to 20 ⁇ .
  • the average particle diameter is a value measured by weight average D 50 (i.e., particle diameter or median diameter when the cumulative weight becomes 50%) in the particle size distribution measurement by the laser diffraction method.
  • weight average D 50 i.e., particle diameter or median diameter when the cumulative weight becomes 50%
  • the average particle diameter of the silicon-coated carbon composite is too small, the bulk density becomes small, so that the charge / discharge capacity per unit volume decreases. On the contrary, It is difficult to produce an electrode film, and there is a fear of peeling off from the current collector.
  • the specific surface area of the carbon-coated silicon composite is preferably 1 to 40 m 2 / g. In the negative electrode active material for a non-aqueous electrolyte secondary cell according to the present invention, the specific surface area of the carbon-coated silicon composite is more preferably 1 m 2 / g to 20 m 2 / g. In the negative electrode active material for a nonaqueous electrolyte secondary battery according to the present invention, when the specific surface area of the composite oxide is less than 1 m 2 / g, the charging / discharging characteristics deteriorate and it is not preferable. When the specific surface area exceeds 40 m 2 / g, And the decomposition reaction of the electrolytic solution is promoted to cause a side reaction, which is not preferable.
  • the present invention also provides a negative electrode comprising a negative electrode active material comprising the silicon oxide composite according to the present invention.
  • the negative electrode according to the present invention is a negative electrode having at least one or more selected from the group consisting of graphite, conductive carbon black, soft carbon, hard carbon, carbon nanofiber, carbon nanotube, graphene, reduced oxidation graphene, In an amount of 30 wt% to 95 wt% with respect to the total weight of the negative electrode active material. That is, in addition to the silicon oxide composite, the negative electrode according to the present invention can be applied to a negative electrode material used as a conventional negative electrode, specifically, graphite, conductive carbon black, soft carbon, hard carbon, carbon nanofiber, carbon nanotube, A pin, and a graphene nanoflake may be further included. In addition to the silicon oxide composite according to the present invention, the material contained in the negative electrode is preferably contained in a proportion of 30 wt% to 95 wt% with respect to the total weight of the negative electrode active material.
  • the present invention also provides a nonaqueous electrolyte lithium secondary battery comprising the negative electrode active material for a nonaqueous electrolyte secondary battery according to the present invention.
  • the present invention also relates to
  • a second step of controlling the pressure of the reactor to 0.000001 torr to 1 torr;
  • the negative electrode active material for a nonaqueous electrolyte secondary battery according to the present invention includes the negative electrode active material.
  • Si / SiO 2 raw material powder in a homogeneous gas phase reaction of honhapchegwa heating with magnesium to Si / SiO 2 raw material powder honhapchegwa magnesium particles are silicon complexes are synthesized, the conventional solid-phase reaction It is possible to prevent the silicon from being abruptly grown due to an excessive excessively mixed exothermic reaction of Mg as a result, and as a result, the capacity retention ratio of the silicon oxide composite can be improved.
  • the negative electrode active material for a non-aqueous electrolyte secondary battery according to the present invention reacts in the vapor phase in this way, the volume change of Li ions during occlusion and discharge is small because each of Si, SiO 2 , and magnesium is bonded at the atomic level, It is difficult for cracks to occur in the electrode active material. Therefore, even if the number of cycles is large, the capacity is hardly lowered.
  • the cycle characteristics are excellent because there is no rapid capacity decrease in the same cycle as the conventional one.
  • This silicon composite is characterized in that each phase is in a bonded state at atomic level, thereby facilitating the desorption of Li ions during discharging, good balance between Li ion charging and discharging, and high charging / discharging efficiency.
  • the method for producing a negative electrode active material for a nonaqueous electrolyte secondary battery according to the present invention comprises supplying the silicon oxide composite and the carbon source in the fifth step and reacting at 600 to 1200 ° C to form a coating layer containing carbon disposed on the surface of the silicon oxide composite
  • the method comprising the steps of:
  • the silicon used as the raw material has an average particle size of 2 to 20 ⁇ and an average particle size of 10 to 300 nm .
  • the carbon source is at least one selected from the group consisting of methane, propane, butane, acetylene, benzene and toluene.
  • the silicon composite oxide and the carbon source are charged, and at least one selected from the group consisting of nitrogen, helium, argon, carbon dioxide gas, hydrogen, .
  • the negative electrode active material for a nonaqueous electrolyte secondary battery according to the present invention comprises carbonaceous material for reacting silicon and silicon dioxide with magnesium by a gas phase reaction and coating carbon to impart conductivity to the surface, It is possible to improve not only the conductivity of the lithium secondary battery but also a stable structure due to the volume change due to the insertion and discharge of lithium, thereby improving the life characteristics, charging and discharging capacity, initial charging and discharging efficiency, and capacity retention rate. Accordingly, a stable and high performance nonaqueous electrolyte lithium secondary battery including the negative electrode active material according to the present invention can be provided.
  • FIGS. 1 to 4 show XRD measurement results of the carbon-coated silicon oxide composite prepared in one embodiment of the present invention and a comparative example.
  • 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 6.2 wt% of magnesium in which a carbon coating layer having a carbon content of 5 wt% was formed.
  • a silicon oxide composite 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 prepare a silicon oxide composite powder having a carbon coating layer having a carbon content of 5 wt% .
  • the specimen was found to have a BET specific surface area of 6.3 m 2 / g, a specific gravity of 2.3 g / cm 3 , and an average particle diameter (D 50 ) of 6.2 ⁇ for the silicon oxide composite containing magnesium (Sample 2) And that the size of the silicon crystal measured by this method was 8 nm.
  • a silicon oxide composite containing magnesium in an amount of 11.7 wt% was prepared in the same manner as in Example 1 except for cooling at 900 DEG C to precipitate a silicon oxide composite powder having a carbon coating layer having a carbon content of 10 wt% 3).
  • the specimen was found to have a BET specific surface area of 5.8 m 2 / g, a specific gravity of 2.4 g / cm 3 and an average particle diameter (D 50 ) of 6.7 ⁇ m with respect to the magnesium oxide-containing silicon oxide composite (sample 3) It was confirmed that the size of the silicon crystal measured was 11 nm.
  • a silicon oxide composite containing 4.6 wt% of magnesium was prepared in the same manner as in Example 1 except for cooling at 1000 ⁇ to precipitate a silicon oxide composite powder having a carbon coating layer having a carbon content of 7 wt% 4).
  • the specimen was found to have a BET specific surface area of 7.3 m 2 / g, a specific gravity of 2.3 g / cm 3 , and an average particle diameter (D 50 ) of 6.2 ⁇ based on the magnesium-containing silicon oxide composite (sample 4) It was confirmed that the size of the measured silicon crystal was 7 nm.
  • the silicon oxide composite containing magnesium in an amount of 16.6 wt% was prepared in the same manner as in Example 1 except for cooling at 1100 ⁇ to precipitate a silicon oxide composite powder having a carbon coating layer having a carbon content of 4 wt% 5).
  • the silicon oxide composite material (sample 5) containing magnesium had a BET specific surface area of 6.8 m 2 / g, a specific gravity of 2.4 g / cm 3 and an average particle diameter (D 50 ) of 7.1 ⁇ and was measured by X- It was confirmed that the measured size of the silicon crystal was 14 nm.
  • a silicon oxide composite containing magnesium in an amount of 3 wt% was prepared in the same manner as in Example 1 except for cooling at 800 DEG C to precipitate a silicon oxide composite powder having a carbon coating layer having a carbon content of 5 wt% ).
  • a silicon oxide composite (Sample 7) 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 7) had a BET specific surface area of 6.5 m 2 / g, a specific gravity of 2.0 g / cm 3 and an average particle diameter (D 50 ) of 6.0 ⁇ and a silicon crystal Of 5 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 that it was precipitated 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 ⁇ and was measured by X-ray diffraction analysis It was confirmed that the size of the silicon crystal measured was 8 nm.
  • Example 1 The average particle diameter, specific surface area, and magnesium content of the silicon oxide composites (Samples 1 to 8) prepared by Examples 1 to 6 and Comparative Examples 1 and 2 were analyzed and shown in Table 1 below.
  • Example 6 Comparative Example 1 Comparative Example 2 D 50 ( ⁇ ⁇ ) 6.3 6.2 6.7 6.2 7.1 5.9 6.0 6.5 BET (m < 2 > / g) 6.2 6.3 5.8 7.3 6.8 6.3 6.5 5.0 Mg content (wt%) 6.2 9.0 11.7 4.6 16.6 3.0 0 One Si C, S (nm) 8 8 11 7 14 6 5 8
  • the XRD was measured for the magnesium-containing silicon composites (Samples 1 to 8) prepared in Examples 1, 2 and 6, and the results are shown in Table 2 and FIG. 1 to FIG.
  • Intensity Si (111) The height from the center to the peak point was defined as Intensity Si (111), and the peak of MgSiO 3 (610) was also determined by X-ray diffraction analysis (CuK ⁇ ) Intensity MgSiO 3 (610) was set in the same manner as Si (111).
  • the Si crystal size was also calculated by the following Scherrer's equation (Scherrer's equation).
  • the intensity I MgSiO3 of the peak I MgSiO3 (610) / I Si (111) was more than 0.1 and less than 0.5 in Examples 1 to 6 of the present invention, whereas in the comparative example, MgSiO 3 peak was not detected Or less than 0.1.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Si (111) 2? ( O ) 28.5056 28.5056 28.5476 28.4796 28.5836 28.5606 28.5216 28.4762 Si (111) FWHM ( o ) 1.02 1.03 0.75 1.16 0.59 1.37 1.65 1.03 FWHM (radians) 0.0178 0.0180 0.0131 0.0202 0.0103 0.0239 0.0287 0.0179 IntensityMgSiO3 (610) 147.22 154.11 181.97 150.03 140.87 147.51 - 21.5 IntensitySi (111) 715.94 712.22 828.42 755.37 840.81 618.33 317.85 551.50 MgSiO3 (610) / Si (111) 0.21 0.22 0.22 0.20 0.17 0.24 - 0.04
  • 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 ⁇ was prepared by coating the above composition on a copper foil having a thickness of 18 ⁇ and drying it.
  • the negative electrode for a coin cell was produced by punching the copper foil coated with the electrode with a circular shape having a diameter of 14 mm. A metal lithium foil was used.
  • a porous polyethylene sheet having a thickness of 0.1 mm was used as a separator, and 1 M LiPF 6 was dissolved in a mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) at a volume ratio of 1: 1 as an electrolyte.
  • EC ethylene carbonate
  • DEC diethylene carbonate
  • a coin cell (battery) having a thickness of 2 mm and a diameter of 32 mm was produced by applying the above-described components.
  • the coin cell manufactured in the above production example was charged at a constant current of 0.1 C until the voltage became 0.005 V and discharged until the voltage reached 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 3 below.
  • 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 became 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 (50 times capacity retention rate) were determined.
  • the results are shown in Table 3 below.

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Abstract

La présente invention concerne un matériau actif d'électrode négative pour une batterie secondaire à électrolyte non aqueux et un procédé de production correspondant, et plus particulièrement un matériau actif d'électrode négative pour une batterie secondaire à électrolyte non aqueux et un procédé de production correspondant caractérisés en ce que le matériau actif d'électrode négative, par réaction de silicium, de dioxyde de silicium et de magnésium lors d'une réaction en phase gazeuse et par application d'un revêtement de carbone sur une surface pour lui conférer une conductivité, présente une structure stable vis-à-vis d'un changement de volume dû à une occlusion et à une libération de lithium, ainsi qu'une conductivité, ce qui permet d'obtenir un effet d'amélioration significative des caractéristiques de durée de vie et de capacité.
PCT/KR2018/015351 2017-12-05 2018-12-05 Matériau actif d'électrode négative pour batterie secondaire à électrolyte non aqueux et procédé de production correspondant WO2019112325A1 (fr)

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JP2020530303A JP2021506059A (ja) 2017-12-05 2018-12-05 非水電解質二次電池用負極活物質、及びその製造方法
CN201880078427.XA CN111433949A (zh) 2017-12-05 2018-12-05 用于非水电解质二次电池的负极活性物质及其制备方法
EP18885241.2A EP3723171A4 (fr) 2017-12-05 2018-12-05 Matériau actif d'électrode négative pour batterie secondaire à électrolyte non aqueux et procédé de production correspondant
US16/769,320 US20200295352A1 (en) 2017-12-05 2018-12-05 Negative electrode active material for non-aqueous electrolyte secondary battery and manufacturing method thereof

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* Cited by examiner, † Cited by third party
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CN111342031A (zh) * 2020-03-28 2020-06-26 兰溪致德新能源材料有限公司 一种多元梯度复合高首效锂电池负极材料及其制备方法
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
WO2022015803A1 (fr) * 2020-07-14 2022-01-20 Nanograf Corporation Matériau d'électrode comprenant de l'oxyde de silicium et des nanotubes de carbone monoparois
CN114744167A (zh) * 2022-03-10 2022-07-12 合盛科技(宁波)有限公司 一种氧化亚硅/膨胀石墨/碳复合材料及其制备方法
EP4120388A1 (fr) * 2021-07-15 2023-01-18 Tera Technos Co., Ltd. Matériau d'électrode négative pour batterie secondaire

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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
CN111342031A (zh) * 2020-03-28 2020-06-26 兰溪致德新能源材料有限公司 一种多元梯度复合高首效锂电池负极材料及其制备方法
WO2022015803A1 (fr) * 2020-07-14 2022-01-20 Nanograf Corporation Matériau d'électrode comprenant de l'oxyde de silicium et des nanotubes de carbone monoparois
EP4120388A1 (fr) * 2021-07-15 2023-01-18 Tera Technos Co., Ltd. Matériau d'électrode négative pour batterie secondaire
US20230025959A1 (en) * 2021-07-15 2023-01-26 Tera Technos Co., Ltd Negative electrode material for secondary battery
CN114744167A (zh) * 2022-03-10 2022-07-12 合盛科技(宁波)有限公司 一种氧化亚硅/膨胀石墨/碳复合材料及其制备方法
CN114744167B (zh) * 2022-03-10 2024-02-27 合盛科技(宁波)有限公司 一种氧化亚硅/膨胀石墨/碳复合材料及其制备方法

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