WO2019022318A1 - Matériau actif d'anode pour batterie secondaire, et son procédé de préparation - Google Patents

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

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WO2019022318A1
WO2019022318A1 PCT/KR2018/000085 KR2018000085W WO2019022318A1 WO 2019022318 A1 WO2019022318 A1 WO 2019022318A1 KR 2018000085 W KR2018000085 W KR 2018000085W WO 2019022318 A1 WO2019022318 A1 WO 2019022318A1
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silicon
metal alloy
alloy powder
active material
coating layer
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PCT/KR2018/000085
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English (en)
Korean (ko)
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추연이
홍순호
이기강
송진우
박현기
이상한
김용욱
양태영
유재형
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엠케이전자 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • H01M4/62—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 lithium secondary battery has been used as a power source for portable electronic products including mobile phones and notebook computers, as well as being used as a medium and large power source for hybrid electric vehicles (HEV) and plug-in hybrid electric vehicles (plug-in HEV) Applications are rapidly expanding. As the application field is expanded and demand is increased, the external shape and size of the battery are variously changed, and capacity, lifetime, and safety are demanded more than those required in conventional small batteries.
  • HEV hybrid electric vehicles
  • plug-in HEV plug-in hybrid electric vehicles
  • the lithium secondary battery is generally manufactured by using a material capable of intercalating and deintercalating lithium ions as a cathode and an anode, providing a porous separator between the electrodes, and then injecting an electrolyte. And electricity is generated or consumed by the redox reaction by insertion and desorption of lithium ions in the anode.
  • silicon, tin, antimony, and aluminum have the characteristics of increasing / decreasing the volume during charging / discharging through the formation of an electrochemical alloy with lithium.
  • the volume change due to such charging / The electrode cycle characteristics are deteriorated in an electrode in which an active material such as aluminum is introduced.
  • an active material such as aluminum is introduced.
  • such a change in volume causes cracks on the surface of the electrode active material, and continuous crack formation causes undifferentiation of the surface of the electrode, thereby deteriorating cycle characteristics.
  • Patent Document 1 Korean Patent Publication No. 2009-0099922 (Published on September 23, 2009)
  • Patent Document 2 Korean Patent Publication No. 2010-0060613 (Published on Jun. 7, 2010)
  • Patent Document 3 Korean Patent Publication No. 2010-0127990 (Dec. 07, 2010)
  • the present invention provides a negative electrode active material for a secondary battery capable of providing a high capacity and high efficiency of charge / discharge characteristics.
  • a negative active material comprising: a silicon-metal alloy powder; And a conductive nanowire attached on a surface of the silicon-metal alloy powder, wherein the conductive nanowire is attached so that the side surface along the longitudinal axis of the conductive nanowire is in contact with the surface of the silicon-metal alloy powder.
  • the method further comprises a coating layer surrounding at least a portion of the surface of the silicon-metal alloy powder and comprising carbon, wherein the conductive nanowire is formed on the surface of the silicon-metal alloy powder or on the surface of the coating layer Lt; / RTI >
  • the coating layer may comprise amorphous silicon carbide.
  • the anode active material has a first peak exhibited by the silicon carbide in an X-ray diffraction analysis, and the first peak may be a peak of 35.6 +/- 0.5 degrees ([deg.]).
  • ⁇ is the average grain size
  • K is the shape factor
  • ⁇ is the X-ray wavelength
  • ⁇ is the half width
  • ⁇ is the Bragg angle
  • the silicon-metal alloy powder may comprise 60 to 90 at% of silicon, 3 to 20 at% of iron, and 1 to 5 at% of first additive element.
  • the first additive element is selected from the group consisting of boron (B), magnesium (Mg), aluminum (Al), manganese (Mn), cobalt (Co), chromium (Cr), tin Mo may be at least one species selected from the group consisting of niobium (Nb), phosphorus (P), titanium (Ti), nickel (Ni), copper (Cu), zirconium (Zr) .
  • the conductive nanowires may be at least one species selected from the group consisting of carbon nanotubes, carbon fibers, copper nanowires, and silver (Ag) nanowires.
  • the conductive nanowire has a content of 0.1 to 10 weight percent (wt%) based on the total weight of the negative electrode active material, and the coating layer has a content of 1 to 10 wt% with respect to the total weight of the negative electrode active material Lt; / RTI >
  • a method of manufacturing an anode active material including: preparing a first powder including silicon, a second powder including iron, and a third powder including a first additive element Forming a silicon-metal alloy powder including silicon, iron and a first additive element by a first mechanical alloying process; Forming a coating layer on the surface of the silicon-metal alloy powder by a second mechanical alloying process using the negative electrode active material powder and carbon; And forming a negative electrode active material powder having the conductive nanowires on the surface of the silicon-metal alloy powder and the coating layer by a third mechanical alloying process using the silicon-metal alloy powder and the conductive nanowires formed with the coating layer ; ≪ / RTI >
  • the first to third mechanical alloying processes may be performed by a vertical-type milling machine, a horizontal-type milling machine, a ball milling machine, a planetary milling machine, A vibrational milling device, a Spex milling device, or a mechanical alloying process using a high energy milling device.
  • the third mechanical alloying process may be performed after the second mechanical alloying process is performed.
  • the negative electrode active material according to the present invention may include a coating layer containing carbon formed on the surface of the silicon-metal alloy powder and a conductive nanowire adhering to the surface of the silicon-metal alloy powder or the surface of the coating layer.
  • the coating layer may have an amorphous silicon carbide phase, and thus the stress due to the volume change of the silicon-metal alloy powder that may occur during the charging and discharging steps of inserting or removing lithium ions into the silicon-
  • the coating layer can be effectively buffered.
  • the conductive nanowire can promote electron transfer through the silicon-metal alloy powder as the anode active material improves the electrical conductivity of the anode active material.
  • the anode active material exhibits a high capacity retention characteristic and a high- rate characteristic.
  • FIG. 1 shows a schematic cross-sectional view of a negative electrode active material according to exemplary embodiments.
  • FIG. 2 is a flowchart showing a manufacturing process of a negative electrode active material according to exemplary embodiments.
  • FIG. 3 is a flowchart showing a manufacturing process of a negative electrode active material according to another exemplary embodiment.
  • FIG. 6 shows the results of energy dispersive spectroscopy (EDS) analysis of the negative electrode active material according to the exemplary embodiments.
  • EDS energy dispersive spectroscopy
  • FIG. 10 is a graph showing capacity retention characteristics of negative electrode active materials according to exemplary embodiments.
  • At% represents the number of atoms occupied by the component in the total atomic number of the whole alloy as a percentage.
  • the negative electrode active material 100 may include a silicon-metal alloy powder 110, a coating layer 120 including carbon, and conductive nanowires 130.
  • the first additional element may be at least one element selected from the group consisting of boron (B), magnesium (Mg), aluminum (Al), manganese (Mn), cobalt (Co), chromium (Cr), tin (Sn), molybdenum (Mo), niobium At least one species selected from the group consisting of phosphorus (P), titanium (Ti), nickel (Ni), copper (Cu), zirconium (Zr) and zinc (Zn).
  • the silicon-metal alloy powder 110 may comprise about 83.5 at% silicon, about 13.5 at% iron, about 2 at% manganese, and about 1 at% boron.
  • the coating layer 120 may be formed on the surface of the silicon-metal alloy powder 110.
  • the coating layer 120 may be formed on at least a portion of the surface of the silicon-metal alloy powder 110, or may be formed to evenly surround substantially the entire surface of the silicon-metal alloy powder 110.
  • Coating layer 120 may comprise silicon carbide.
  • Coating layer 120 may comprise amorphous silicon carbide or may comprise crystalline silicon carbide having a relatively small grain size.
  • the conductive nanowires 130 may be deposited on the surface of the silicon-metal alloy powder 110 or on the surface of the coating layer 120.
  • the conductive nanowires 130 may have a structure having a minor axis and a major axis (wherein the major axis is referred to as a vertical axis), and a length along the major axis may be substantially greater than a length along the minor axis.
  • the conductive nanowires 130 may be attached so that sidewalls extending along their longitudinal axes adhere to the surface of the silicon-metal alloy powder 110 or the surface of the coating layer 120.
  • the conductive nanowire 130 may include a carbon nanotube, a carbon fiber, a copper nanowire, or a silver (Ag) nanowire.
  • conductive nanowire 130 may have a length along its longitudinal axis of about 2 nm to about 30 nm.
  • the negative electrode active material has a first peak of silicon carbide represented by the coating layer 120 in an X-ray diffraction analysis, and the first peak may have a peak of 35.6 +/- 0.5 degrees ([deg.]). Also, the average grain size calculated from equation (1) below from the first peak may be from about 8 nm to about 20 nm,
  • K is the shape factor,? Is the wavelength of the X-ray,? Is the half width, and? Is the Bragg angle).
  • the coating layer 120 may comprise amorphous silicon carbide, or may include silicon carbide having a relatively low grain size and a low degree of crystallinity.
  • the negative electrode active material 100 having the coating layer 120 containing amorphous silicon carbide may have a significantly better capacity retention characteristic than the negative electrode active material not having the coating layer 120.
  • the coating layer 120 may be formed on the surface of the silicon-metal alloy powder 110 by a mechanical alloying process.
  • the coating layer 120 acts as a buffer to effectively buffer the volume expansion during charging and discharging of the silicon-metal alloy powder 110 or to facilitate the rapid transfer of electrons generated within the silicon- By acting as an electrical pathway, the negative electrode active material 100 can have improved electrochemical properties (e.g., discharge capacity or cycle performance).
  • the thickness of the coating layer 120 is too thin (for example, the content of carbon contained in the negative electrode active material 100 is less than 1 at%), the function of the buffer or the electric path described above may not be sufficiently performed, If the thickness of the coating layer 120 is too large (for example, the content of carbon contained in the negative electrode active material 100 is greater than 10 at%), the content of the silicon single phase that can act as an active region in the negative electrode active material 100 So that the discharge capacity can be reduced.
  • the conductive nanowires 130 may comprise a material having a high electrical conductivity and may be deposited on the surface of the silicon-metal alloy powder 110 or on the surface of the coating layer 120 .
  • the conductive nanowire 130 may be attached to the surface of the silicon-metal alloy powder 110 or the surface of the coating layer 120 so that the side wall extending along the longitudinal axis thereof may adhere to the surface of the silicon- A relatively large contact area can be ensured between the surfaces of the powder 110 so that the electrical path between adjacent silicon-metal alloy powders 110 can be provided through the conductive nanowires 130.
  • the negative electrode active material 100 has improved electrochemical properties (e.g., Discharge capacity or cycle performance). If the content of the conductive nanowires 130 included in the negative electrode active material 100 is too small, the function of the electrical path described above may not be sufficiently performed, and if the content of the conductive nanowires 130 contained in the negative electrode active material 100 If the content is too large, the content of the silicon single phase that can act as an active region in the negative electrode active material 100 may be too small, or the specific surface area may be greatly increased, and side reactions may occur.
  • electrochemical properties e.g., Discharge capacity or cycle performance
  • the negative electrode active material 100 may include the silicon single phase having an average crystal grain size of 100 nanometers (nm) or less.
  • the silicon single phase is uniformly distributed within the silicon-metal alloy phase in a fine size, the silicon-metal alloy as a matrix acts as a buffer layer for buffering the volume change of the single phase of silicon due to the insertion / And cracks and damage of the negative electrode active material 100 due to such volume change can be prevented. Therefore, the negative electrode active material 100 can have excellent capacity retention characteristics.
  • FIG. 2 is a flowchart showing a manufacturing process of a negative electrode active material according to exemplary embodiments.
  • a silicon-metal alloy powder including silicon, iron, and a first additive element may be formed by a first mechanical alloying process (step S10).
  • Iron, and a first additive element by a first mechanical alloying process using a third powder comprising, for example, a first powder comprising silicon, a second powder comprising iron, and a first additive element, Silicon-metal alloy powder can be formed.
  • the negative electrode active material powder to be formed in step S10 contains 60 to 90 atomic percent (at%) silicon, 3 to 20 at% iron, and 0 to 5 at%
  • the mass of the first to third powders may be weighed so as to include one additional element.
  • the first mechanical alloying process may be a vertical milling machine, a horizontal milling machine, a ball milling machine, a planetary milling machine, a vibration milling machine, a speckle milling machine, Or by a milling device such as a milling device.
  • the first mechanical alloying process can be performed using a ball milling device with a diameter of 1 m and a chrome steel ball with a diameter of 25.4 mm.
  • the first powder, the second powder, and the third powder may be injected into the milling apparatus in powder form and the first mechanical alloying process may be performed, in which case the active material is heated at a high temperature After melting and rapidly cooling to form a primary alloy (for example, a ribbon alloy), the rapid cooling method of pulverizing the primary alloy to form the negative electrode active material powder may not be used.
  • a primary alloy for example, a ribbon alloy
  • the rapid cooling method of pulverizing the primary alloy to form the negative electrode active material powder may not be used.
  • an anode active material comprising 83.5 at% of silicon, 13.5 at% of iron, 2 at% of manganese and 1 at% of boron, 21.85 kg of silicon, 7.02 kg of iron, 1.02 kg of manganese, 0.1 kg of boron are prepared and they can be injected into the ball milling apparatus.
  • anode active material comprising 86 at% silicon, 11 at% iron, 2 at% manganese and 1 at% boron, 20.34 kg of ferrosilicon, 1.49 kg of silicon manganese, (Fe-B) of 0.64 kg, and 7.52 kg of silicon are prepared and they can be injected into the ball milling apparatus.
  • the silicon single phase may be uniformly distributed in the silicon-metal alloy phase, and the first additive element may be substituted or interstitially contained within the silicon-metal alloy phase, It may be present at the interface between the alloy phase and the silicon single phase.
  • the silicon single phase formed in the powder can be changed into a fine silicon single phase, and a fine silicon single phase can evenly be distributed using the silicon-metal alloy phase as a matrix.
  • the negative electrode active material powder formed by the pulverization and alloying process may uniformly distribute the particle size of the single phase of silicon within 100 nm or less.
  • a coating layer containing carbon may be formed on the surface of the silicon-metal alloy powder by a second mechanical alloying process using the silicon-metal alloy powder and carbon (step S20).
  • Metal alloy powder is formed on the silicon-metal alloy powder by pulverizing and finely grinding the silicon-metal alloy powder and the carbon using the second mechanical alloying process so as to surround the surface of the silicon-metal alloy powder and having a thickness of about 50 nm to about 200 nm < / RTI > may be formed.
  • the starting material of carbon used in the second mechanical alloying process may include artificial graphite such as plate-like graphite.
  • the second mechanical alloying process may be a vertical milling machine, a horizontal milling machine, a ball milling machine, a planetary milling machine, a vibration milling machine, a speckle milling machine, Or by a milling device such as a milling device.
  • the second mechanical alloying process may be performed using a chromium steel ball having a diameter of 25.4 mm by injecting the silicon-metal alloy powder and artificial graphite obtained by the first mechanical alloying process into a ball milling machine have.
  • the anode active material powder to which the conductive nanowires are adhered can be formed on the surface of the silicon-metal alloy powder or on the surface of the coating layer by a third mechanical alloying process using the silicon-metal alloy powder and the conductive nanowire (S30 step).
  • the conductive nanowires may be attached on the surface of the silicon-metal alloy powder or on the surface of the coating layer by pulverizing and refining the silicon-metal alloy powder and the conductive nanowires using the third mechanical alloying process.
  • the third mechanical alloying process may be performed so that the conductive nanowires are relatively uniformly dispersed and adhered on the surface of the silicon-metal alloy powder.
  • the third mechanical alloying process may be a vertical-type milling apparatus, a horizontal-type milling apparatus, a ball milling apparatus, a planetary milling apparatus, a vibration milling apparatus, Or by a milling device such as a milling device.
  • a milling device such as a milling device.
  • the silicon-metal alloy powder and the carbon nanotube obtained by the second mechanical alloying process are injected into a ball milling device, and the third mechanical alloying process is performed using a chromium steel ball having a diameter of 25.4 mm .
  • the powders of silicon, iron, and the first additive element can be made finer or alloyed by the first mechanical alloying process, thereby facilitating the manufacturing process.
  • a silicon-metal alloy powder in which a fine silicon single phase is uniformly distributed in the silicon-metal alloy phase can be provided.
  • Metal alloy powder surface by the second mechanical alloying process and the third mechanical alloying process; and a conductive layer which is uniformly dispersed and attached on the surface of the silicon-metal alloy powder and / An anode active material powder containing nanowires can be produced.
  • FIG. 3 is a flowchart showing a manufacturing process of a negative electrode active material according to another exemplary embodiment.
  • the anode active material powder to which the conductive nanowires are adhered can be formed on the surface of the silicon-metal alloy powder by the third mechanical alloying process using the silicon-metal alloy powder and the conductive nanowire (step S30A).
  • the conductive nanowires may be attached such that the sidewalls along their longitudinal axes contact the surface of the silicon-metal alloy powder. Meanwhile, the conductive nanowires may be formed to cover about 20% to about 80% of the surface of the silicon-alloy powder.
  • a coating layer containing carbon may be formed on the silicon-metal alloy powder to which the conductive nanowires are attached by a second mechanical alloying process (step S20A).
  • a coating layer comprising carbon can be formed on the surface of the silicon-alloy powder or on the surface of the conductive nanowire.
  • FIG. 4 is a flowchart showing a manufacturing process of a negative electrode active material according to another exemplary embodiment.
  • a silicon-metal alloy powder including silicon, iron, and a first additive element may be formed by a first mechanical alloying process (step S10).
  • the second and third mechanical alloying processes may be used to form a coating layer comprising carbon on the silicon-metal alloy powder while the conductive nanowires may be deposited on or on the surface of the silicon-alloy powder . Further, a conductive nanowire may be first attached to the surface of the silicon-alloy powder, and a coating layer including carbon may be formed to cover both the silicon-alloy powder and the conductive nanowire.
  • the silicon-metal alloy powder and the carbon nanotube (CNT) were injected into a ball milling device having a diameter of 1 m, and the third mechanical alloying process was performed using a chrome steel ball having a diameter of 25.4 mm.
  • the classification process was then carried out by means of a jet mill.
  • SEM scanning electron microscopy
  • FIG. 6 is a result of energy dispersive spectroscopy (EDS) analysis of the negative electrode active material according to the exemplary embodiments.
  • FIG. 7 is a graph showing the results of analysis of energy dispersive spectroscopy (EDS) , Carbon (C), and manganese (Mn) components.
  • the anode active material powder has a shape in which substantially spherical or elliptical particles are aggregated.
  • 5 (d) it is observed that the carbon nanotubes extending in one direction (for example, the longitudinal axis thereof) are uniformly dispersed and adhered to the surfaces of the negative electrode active material particles.
  • the EDS analysis results of the anode active material particles it is confirmed that silicon, iron, and manganese are uniformly distributed in the anode active material particle and a coating layer containing carbon is formed on the surface of the anode active material to a thickness of about 100 nm .
  • the X-ray diffraction patterns of Experimental Example 1 (EX1) and Experimental Example 5 (EX5) each had a first peak shown by silicon carbide.
  • the first peak may be a peak of about 35.6 +/- 0.5 degrees ( ⁇ ), and may be a peak represented by a (111) plane of cubic system silicon carbide (crystal group: T 2 d -F43m).
  • the first peaks of Experimental Example 1 (EX1) and Experimental Example 5 (EX5) had an average grain size of about 10.4 nm and 15.5 nm, respectively, according to the following Equation 1 (i.e., Scherrer equation).
  • the first peak of Experimental Example 1 (EX1) and Experimental Example 5 (EX5) shows a slightly broader profile, so that the coating layer includes silicon carbide having an amorphous crystal structure.
  • the average grain size of Experimental Example 1 (EX1) and Experimental Example 5 (EX5) is considerably small, it can be understood that the coating layer contains silicon carbide which is polycrystalline with a very low degree of crystallinity.
  • the average grain size of Experimental Example 5 (EX5) in which the coating layer contains 5 wt% of carbon was larger than the average grain size of Experimental Example 1 (EX1) in which the coating layer contained 3 wt% of carbon, (Or as the thickness of the coating layer is increased), the crystallinity of the silicon carbide tends to increase.
  • FIG 9 is a graph showing the electrical conductivity of the negative electrode active material according to the exemplary embodiments.
  • FIG. 10 is a graph showing capacity retention characteristics of a negative electrode active material according to exemplary embodiments. Specifically, FIG. 10 shows the capacity retention rate (%) (ie, the ratio of 300 discharge capacities to the initial discharge capacity) in the 300 cycles of Comparative Example (CO) and Experimental Examples 1 to 8 (EX1 to EX8) .
  • Experimental Example 2 (EX2) and Experimental Example 3 (EX3) comprising a coating layer containing 3 wt% of carbon and 1 to 5 wt% of carbon nanotubes (or conductive nanowires)
  • Capacity maintenance characteristics This is because the carbon-containing coating layer contains amorphous silicon carbide, effectively buffering the stress caused by the volume change occurring during charging and discharging of the silicon-metal alloy powder, and also allowing the carbon nanotube to provide electrical conductivity to the silicon- It can be considered that it exhibits excellent capacity retention characteristics.
  • the silicon-metal alloy powder contains 1 to 5 wt% of carbon nanotubes (for example, Experiments 2, 3, 6 and 7 (EX2, EX3, EX6, EX7) And thus exhibits excellent capacity retention characteristics.
  • the content of the silicon-metal alloy powder capable of acting as an active region in the negative electrode active material is too small (for example, in the case of Experiments 4 and 8 (EX4, EX8)) containing 10 wt% of carbon nanotubes Or the specific surface area is greatly increased, side reaction may occur, so that it can be inferred that the capacity retention characteristic is somewhat lowered.
  • the content of the coating layer containing carbon is 5 wt% or more when the content of the coating layer containing carbon is 3 wt% or more (for example, in the case of Experiments 1 to 4 (EX1, EX2, EX3, EX4) (For example, in the case of Experiments 5 to 8 (EX5, EX6, EX7, EX8)).
  • EX1, EX2, EX3, EX4 Experiments 1 to 4
  • Experiments 5 to 8 EX5, EX6, EX7, EX8
  • the carbon content of the coating layer is 5 wt%, the degree of crystallization of the silicon carbide is somewhat increased.
  • the carbon content of the coating layer is 3 wt%, the crystallinity is low or the amorphous silicon carbide is formed. It can be presumed that the stress due to the volume change occurring during charging and discharging of the silicon-metal alloy powder can be most effectively buffered or suppressed by the coating layer containing silicon carbide.

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Abstract

La présente invention concerne un matériau actif d'anode pour une batterie secondaire, pouvant fournir des caractéristiques de charge/décharge hautement efficaces et à haute capacité. Le matériau actif d'anode comprend : une poudre d'alliage de silicium-métal; une couche de revêtement comprenant au moins une partie de la surface de la poudre d'alliage de silicium-métal, et comprenant du carbone; et un nanofil conducteur fixé à la surface de la poudre d'alliage de silicium-métal ou à la surface de la couche de revêtement, le nanofil conducteur étant fixé de telle sorte que le côté latéral le long de l'axe longitudinal du nanofil conducteur entre en contact avec la surface de la poudre d'alliage de silicium-métal ou la surface de la couche de revêtement.
PCT/KR2018/000085 2017-07-24 2018-01-03 Matériau actif d'anode pour batterie secondaire, et son procédé de préparation WO2019022318A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113707862A (zh) * 2021-08-26 2021-11-26 厦门大学 一种铜纳米线缠绕硅碳复合材料及其制备方法和应用
US11891523B2 (en) 2019-09-30 2024-02-06 Lg Energy Solution, Ltd. Composite negative electrode active material, method of manufacturing the same, and negative electrode including the same

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