KR20230115186A - Silicon carbon composite anode materials comprising Ag nanowire, manufacturing method thereof and secondary battery comprising the same - Google Patents

Abstract

The present invention relates to a silicon carbon composite negative electrode active material containing silver nanowires, a manufacturing method thereof, and a secondary battery containing the same. In one embodiment, the method for manufacturing a silicon carbon composite negative electrode active material comprising the silver nanowires comprises the steps of: drying a first mixture including graphite balls, nanosilicon slurry, pitch, flake graphite, and silver nanowires to produce a dried product; firing the dried product to produce a fired product with a hard coating layer including amorphous hard carbon on an outermost layer thereof; mixing a carbon precursor with the fired product and heat-treating the same to form a soft coating layer on the outer peripheral surface of the fired product; forming a carbon nanotube layer on an outer peripheral surface of the soft coating layer; and forming a silver nanowire layer on an outer peripheral surface of the carbon nanotube layer.

Description

Silicon carbon composite anode active material including silver nanowire, manufacturing method thereof, and secondary battery including same

The present invention relates to a silicon carbon composite anode active material including silver nanowires, a manufacturing method thereof, and a secondary battery including the same.

Currently, the problem of greenhouse gas generation such as carbon dioxide and global temperature rise due to the use of fossil energy is a serious situation. Regulations on carbon dioxide emission are being strengthened in countries around the world, and the introduction of electric vehicles using electricity as a power source is rapidly increasing to replace internal combustion locomotives driven by fossil fuels as a power source.

Secondary batteries used to supply electricity to electric vehicles are key parts of electric vehicles that can be used repeatedly through charging, unlike primary batteries that are used once and discarded. In addition, secondary batteries are used in various fields such as notebook PCs, mobile devices, vertical take-off and landing aircraft used as means of urban air mobility (UAM), and electric storage systems in addition to electric vehicles. In recent years, demand for high-capacity, low-weight, and high-efficiency secondary batteries has increased with industrial development, and research on this has been actively conducted.

Representative secondary batteries include lead storage batteries, nickel-cadmium batteries, and lithium ion batteries. Among them, lithium secondary batteries produce electrical energy by the intercalation and deintercalation of lithium ions (Li ⁺ ) during charging and discharging, and are used in various fields such as electric vehicles because of their excellent light weight and high energy density. It is being used.

The lithium secondary battery includes a positive electrode and a negative electrode; an electrolyte disposed between the anode and the cathode; and a separator impregnated with the electrolyte, wherein the positive electrode and the negative electrode each include an active material formed on a current collector. The cathode active material of the lithium secondary battery includes lithium transition metal oxide, etc., and determines the capacity and average voltage of the lithium ion battery as a lithium ion source, and the anode active material stores and releases the lithium ions released from the cathode. while allowing current to flow through the external circuit. The electrolyte serves as a medium for lithium ions to move between the positive and negative electrodes inside the battery.

Conventionally, as an anode active material of a lithium ion battery, a crystalline carbon material or an amorphous carbon material such as natural graphite or artificial graphite has been used.

Recently, silicon (Si) has been attracting attention as an anode active material instead of carbon. While graphite, which is conventionally used as an anode active material, stores 1 lithium ion per 6 carbon atoms, silicon (Si) can store 4.4 lithium ions per 1 atom, which has a higher energy density than conventional graphite and It is attracting attention because it has the advantage of a very fast discharge rate.

However, the silicon negative active material has a problem of low structural stability. As for the anode material, a phenomenon (lithiation) in which the volume of the anode increases in the process of storing lithium ions occurs. Graphite increases in volume by about 10 to 20%, while silicon (Si) has 4.4 lithium ions per silicon. This reaction forms a Li ₂₂ Si ₅ alloy, resulting in a large volume expansion up to 4 to 5 times. In particular, the silicon anode active material has high crystal brittleness, and due to this, pulverization (particle cracking, destruction) of the silicon-based anode active material occurs during repeated charging and discharging of the lithium ion battery, and electrical separation from the current collector (Cu electrode plate) occurs. A rapid capacity decay occurs and the lifetime is shortened.

In addition, the silicon anode active material has a problem in that the efficiency is rapidly reduced due to a change in the interface state between the anode material (negative electrode active material), the electrolyte, and the electrode. This is because when the silicon particles are broken due to the expansion of the anode material during battery charging, numerous lithium traps are generated. In more detail, the SEI (Solid Electrolyte Interphase) layer is easily destroyed by mechanical stress when the silicon particles expand. When the process of destruction and regeneration of the SEI layer is repeated during charging and discharging, a large amount of SEI layer is formed on the surface of the silicon, forming a gap between the particles. Since the gap between the particles is reduced, the electrical contact between the particles is weakened and the lithium trap phenomenon occurs. The SEI layer is a protective film formed on the surface of the active material when the electrolyte reacts with the active material of the electrode, and is a passage through which lithium ions move between the electrolyte and the negative electrode material due to its low electron mobility but high lithium ion conductivity. Graphite has a small volume change, so there is no problem with the SEI layer, but silicon expands to the extent of destroying the SEI layer during charging, so lithium is consumed by lithiation of silicon particles and gas is generated, and the SEI layer gradually hardens and becomes thicker. Ions do not have access to the electrode, which limits the oxidation-reduction reaction of lithium, resulting in a problem that shortens battery life.

Therefore, studies are being actively conducted to improve the structural stability of the silicon anode active material to prevent cracking of the anode active material during charging and discharging of the secondary battery and to prevent energy capacity reduction.

Background art related to the present invention is disclosed in Republic of Korea Patent Registration No. 10-2185490 (2020.12.02. Notice, title of the invention: negative electrode active material for non-aqueous electrolyte secondary battery containing silicon oxide composite and manufacturing method thereof).

An object of the present invention is to provide a method for preparing a silicon-carbon composite anode active material including silver nanowires having excellent electrical conductivity, durability and structural stability.

Another object of the present invention is to minimize the increase in volume due to lithium ion insertion during charging and discharging, thereby minimizing the destruction of the negative electrode active material and the decrease in energy capacity. will be.

Another object of the present invention is to provide a method for manufacturing a silicon-carbon composite negative electrode active material including silver nanowires having high capacity, high output, and long lifespan characteristics and excellent initial efficiency.

Another object of the present invention is to provide a method for manufacturing a silicon-carbon composite negative electrode active material including silver nanowires having excellent productivity and economic efficiency.

Another object of the present invention is to provide a silicon carbon composite anode active material containing silver nanowires prepared by the method for preparing a silicon carbon composite anode active material containing silver nanowires.

Another object of the present invention is to provide a secondary battery including the silicon carbon composite anode active material including the silver nanowires.

One aspect of the present invention relates to a method for manufacturing a silicon-carbon composite anode active material including silver nanowires. In one embodiment, the negative electrode active material manufacturing method includes preparing a dry product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires; Calcining the dried product to produce a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost portion; forming a soft coating layer on an outer circumferential surface of the fired object by mixing a carbon precursor with the fired object and performing heat treatment; forming a carbon nanotube layer on an outer circumferential surface of the soft coating layer; and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

In another embodiment, the negative electrode active material manufacturing method includes preparing a dried product by drying a first mixture including graphite balls, nano-silicon slurry, flake graphite, and silver nanowires; preparing a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost layer, by mixing and firing the dried product and the pitch; preparing an intermediate by mixing a carbon precursor with the fired product and heat-treating to form a first soft coating layer and a second soft coating layer on the inner and outer circumferential surfaces of the hard coating layer, respectively; forming a carbon nanotube layer on an outer circumferential surface of the second soft coating layer; and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

In another embodiment, the negative electrode active material manufacturing method includes preparing a dry product by drying a first mixture including graphite balls and nano-silicon slurry; Calcining the dried product to produce a fired product having a hard coating layer formed thereon, including amorphous hard carbon on the outermost layer; preparing an intermediate body by mixing a carbon precursor and silver nanowires with the fired product and performing a first heat treatment to form a first soft coating layer on an outer circumferential surface of the hard coating layer; and forming a second soft coating layer on an outer circumferential surface of the first soft coating layer by mixing the intermediate, the carbon precursor, the carbon nanotubes, and the silver nanowires and performing secondary heat treatment.

In another embodiment, the negative electrode active material manufacturing method includes preparing a dry product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires; Preparing a first fired product having a first hard coating layer comprising amorphous hard carbon on an outermost layer by mixing the dried product and the pitch and performing primary firing; preparing a second fired product having a second hard coating layer formed on an outer circumferential surface of the first hard coating layer by mixing the first fired product and pitch and second fired; forming a carbon nanotube layer on an outer circumferential surface of the second hard coating layer; and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

In another embodiment, the negative electrode active material manufacturing method includes preparing a dried product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, and flake graphite; Preparing a first fired product on which a first hard coating layer containing amorphous hard carbon is formed on an outermost layer by performing primary firing on the dried product; preparing an intermediate body in which a soft coating layer is formed on an outer circumferential surface of the first hard coating layer by mixing a carbon precursor with the first fired product and performing heat treatment; Preparing a secondary firing product by mixing pitch with the intermediate body and performing secondary firing; forming a carbon nanotube layer on an outer circumferential surface of the second fired product; and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer. and a second hard coating layer including amorphous hard carbon is sequentially formed.

In one embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to a first solvent and dispersing to prepare a dispersion; and pulverizing the dispersion, wherein the graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; In addition, it may be prepared by including; pulverizing the calcined graphite mixture.

In one embodiment, the first solvent includes at least one of water, ethanol, isopropyl alcohol, and potassium hydroxide (KOH), and the graphite mixture is at least one of N-methylpyrrolidone (NMP), ethanol, and water. 2 may further contain a solvent.

In one embodiment, the carbon precursor includes at least one of polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, polyvinylidene fluoride, styrene butadiene rubber, and sucrose can do.

In one embodiment, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.01 to 5:2 to 8:1 to 25:5 to 70.

In one embodiment, the silver nanowire layer is prepared by applying a silver (Ag) nanowire dispersion to an outer circumferential surface of the carbon nanotube layer and heat-treating it at 80 to 150° C., wherein the silver nanowire dispersion is made of silver nanowires. It includes a wire, a binder, and a dispersing solvent, and the dispersing solvent may include at least one of water and an organic solvent.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a first dispersant, and water, and the first dispersant includes at least one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. can do.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride.

In one embodiment, the silver nanowire layer may be formed by chemical vapor deposition (CVD) of silver (Ag) nanowires on the outer circumferential surface of the carbon nanotube layer.

Another aspect of the present invention relates to a silicon carbon composite negative electrode active material including silver nanowires prepared by the method for manufacturing a silicon carbon composite negative electrode active material including silver nanowires. In one embodiment, the anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver (Ag) nanowires and flake graphite dispersed in the porous matrix; a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; a soft coating layer formed on an outer circumferential surface of the hard coating layer; a carbon nanotube layer formed on an outer circumferential surface of the soft coating layer; and a silver (Ag) nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 1 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. , 0.1 to 5% by weight of the soft coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

In one embodiment, the negative active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the soft coating layer has a thickness of 0.05 to 15 μm. 5 μm, the hard coating layer may have a thickness of 0.05 μm to 5 μm, the carbon nanotube layer may have a thickness of 0.01 μm to 10 μm, and the silver nanowire layer may have a thickness of 0.01 μm to 10 μm.

In another embodiment, the anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver nanowires and flake graphite dispersed in the porous matrix; a first soft coating layer formed on an outer circumferential surface of the core; a hard coating layer formed on an outer circumferential surface of the first soft coating layer and containing amorphous hard carbon; a second soft coating layer formed on an outer circumferential surface of the hard coating layer; a carbon nanotube layer formed on an outer circumferential surface of the second soft coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. , 0.1 to 15 wt% of the first soft coating layer, 0.1 to 15 wt% of the second soft coating layer, 0.01 to 10 wt% of the carbon nanotube layer, and 0.01 to 10 wt% of the silver nanowire layer.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the first soft coating layer has a thickness 0.05 to 5 μm, the second soft coating layer has a thickness of 0.5 to 10 μm, the hard coating layer has a thickness of 0.05 to 5 μm, the carbon nanotube layer has a thickness of 0.01 to 10 μm, and the The silver nanowire layer may have a thickness of 0.01 to 10 μm.

In another embodiment, the anode active material includes a core including a porous matrix including nano-silicon (Si) and amorphous hard carbon; a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; a first soft coating layer formed on an outer circumferential surface of the hard coating layer and including soft carbon and silver nanowires; and a second soft coating layer formed on an outer circumferential surface of the first soft coating layer and including soft carbon, carbon nanotubes, and silver nanowires.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 5 to 50% by weight of amorphous hard carbon, 0.1 to 15% by weight of a hard coating layer, 0.1 to 15% by weight of a first soft coating layer, and 0.1 to 15% by weight of a second soft coating layer. 0.1 to 15% by weight, wherein the first soft coating layer includes the silver nanowires and soft carbon in a weight ratio of 1:0.5 to 1:20, and the second soft coating layer includes the silver nanowires and the carbon nanowires The tube and soft carbon may be included in a weight ratio of 1:0.01 to 5:0.5 to 20.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the hard coating layer has a thickness of 0.05 to 5 μm, and the first soft coating layer has a thickness of 0.05 ~ 5㎛, and the second soft coating layer may have a thickness of 0.5 ~ 10㎛.

In another embodiment, the anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing flake graphite and silver nanowires dispersed in the porous matrix; a first hard coating layer and a second hard coating layer sequentially formed on an outer circumferential surface of the core and each containing amorphous hard carbon; a carbon nanotube layer formed on an outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 35% by weight of a first hard coating layer. % by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the first hard coating layer has a thickness 0.05 to 10 μm, the second hard coating layer has a thickness of 0.5 to 10 μm, the carbon nanotube layer has a thickness of 0.01 to 10 μm, and the solid silver nanowire layer has a thickness of 0.01 to 10 μm. can

In another embodiment, the anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing flake graphite dispersed in the porous matrix; a first hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; an amorphous carbon layer formed on an outer circumferential surface of the first hard coating layer; a second hard coating layer formed on an outer circumferential surface of the amorphous carbon layer and containing amorphous hard carbon; The carbon nanotube layer formed on the outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano-silicon, 0 to 60% by weight of flake graphite, 5 to 50% by weight of amorphous hard carbon, 0.1 to 35% by weight of the first hard coating layer, and 0.1 to 15% by weight of the amorphous carbon layer. % by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the first hard coating layer has a thickness 0.05 to 10 μm, the amorphous carbon layer has a thickness of 0.01 to 10 μm, the second hard coating layer has a thickness of 0.5 to 10 μm, the carbon nanotube layer has a thickness of 0.01 to 10 μm, and the thickness of the second hard coating layer is 0.01 to 10 μm. The silver nanowire layer may have a thickness of 0.01 to 10 μm.

Another aspect of the present invention relates to a secondary battery including the anode active material. In one embodiment, the secondary battery includes a cathode; cathode; and an electrolyte formed between the positive electrode and the negative electrode, wherein the negative electrode includes the negative electrode active material.

In one embodiment, the secondary battery has a weight energy density of 410 mAh / g or more ( With 1.5V as a cutoff voltage, the positive electrode is prepared to have a value measured in a half-cell evaluation of a lithium (Li) electrode), and the oxide active material is LiNi _x Co _y Mn _z O ₂ (where x, y, z satisfies x + y + z = 1, 0.50 < x < 0.91, 0.04 < y < 0.25, and 0.04 < z < 0.035) and includes the oxide active material. The capacity of (based on the value measured in half-cell evaluation in which the positive electrode is a lithium (Li) electrode with 4.2V as the cutoff voltage) and the capacity of the negative electrode including the negative electrode active material are 1.04 <capacity of the negative electrode / the capacity of the anode < 1.17 relationship is satisfied, and the electrolyte includes 1.1M LiPF ₆ , 0.1M LiBoB, but ethyl carbonate (EC) / ethylmethyl carbonate (EMC) / fluoroethylene carbonate (FEC) is 65% / 30 It is included in a ratio of %/5% (based on weight %), and the full-cell secondary battery is driven in the range of 2.50 to 4.20V while repeatedly charging and discharging more than 600 times during performance evaluation, The process of charging and discharging with a capacity value of 0.1 C during the first cycle, and then charging and discharging with a capacity value of 1.0 C for 20 cycles (the second cycle to the 21st cycle) was repeatedly evaluated, The anode active material is maintained at 4.2V until the charging current reaches 0.05C during each cycle charging, and charging can be completed.

In one embodiment, the secondary battery has a weight energy density of 410 mAh / g or more ( With 1.5V as a cutoff voltage, the positive electrode is prepared to have a value measured in the evaluation of a half cell, which is a lithium (Li) electrode), and the oxide active material is LiNi _x Co _y Al ₂ It has a structure (x, y, z satisfies x + y + z = 1, 0.71x < 0.95, 0.04 < y < 0.15, and 0.03 < z < 0.15), and the capacity of the cathode containing the oxide active material (4.2 With V as the cutoff voltage, based on the value measured in half-cell evaluation in which the positive electrode is a lithium (Li) electrode) and the capacity of the negative electrode including the negative electrode active material is 1.04 < capacity of the negative electrode / capacity of the positive electrode < 1.17 relationship is satisfied, and the electrolyte includes 1.1M LiPF ₆ , 0.1M LiBoB, but ethyl carbonate (EC) / ethylmethyl carbonate (EMC) / fluoroethylene carbonate (FEC) is 65% / 30% / 5% (based on weight %), the full-cell secondary battery is driven in the range of 2.50 to 4.20V while repeatedly charging and discharging more than 600 times during the performance evaluation, and during the first cycle The process of charging and discharging with a capacity value of 0.1C, and then charging and discharging with a capacity value of 1.0C for 20 cycles (2nd cycle to 21st cycle) was repeatedly evaluated, but the negative electrode active material During each cycle charging, the charging current is maintained at 4.2V until it reaches 0.05C, and charging can be completed.

The anode active material according to the present invention has excellent electrical conductivity, low electrical resistance, excellent durability and structural stability, and minimizes the destruction of the anode active material and the decrease in energy capacity by minimizing the volume increase due to lithium ion insertion during charging and discharging. It has excellent performance, high capacity, high energy density, high power and long lifespan, excellent initial efficiency, and excellent productivity and economic feasibility.

1 shows an anode active material according to one embodiment of the present invention.
2(a) is a schematic diagram of an anode active material according to one embodiment of the present invention, and FIG. 2(b) is a schematic diagram showing volume change during lithium ion intercalation/desorption reactions of the anode active material of the present invention.
3 is a scanning electron microscope (SEM) photograph showing a cross section of the negative electrode active material of Example.
4 is a scanning electron micrograph showing a cross section of the negative electrode active material of Example.
5(a) is a scanning electron micrograph of the anode active material of Example 1, and FIG. 5(b) is a scanning electron micrograph of the anode active material of Example 1.
6 is a graph showing the particle diameter distribution of the negative electrode active material of Example 1.
FIG. 7(a) is a scanning electron micrograph of the carbon nanotube layer, FIG. 7(b) is a scanning electron micrograph of the silver nanowire layer, and FIG. 7(c) is a scanning electron micrograph of the surface of Example 1. .
8(a) is a scanning electron micrograph of the anode active material of Example 1, and FIG. 8(b) is a scanning electron micrograph of the anode active material of Comparative Example 1.
9 schematically shows the structure of a secondary battery for measuring a volume change of an anode active material during charging and discharging of Example 1 and Comparative Example 2.
10 is a graph of volume change of the negative electrode active material during charging and discharging in Example 1 and Comparative Example 2.
11 is an evaluation graph of capacity characteristics of coin half cells of Example 1 and Comparative Example 2;
12 shows life cycle evaluation results of coin half-cells of Example 1 and Comparative Example 2;
13 is a graph of impedance measurement results of coin full cells of Example 1 and Comparative Example 2 after 5 cycles of operation.
14 is a graph showing results of capacity retention rates of coin full cells of Example 1 and Comparative Example 2;
15 is a graph of the capacity retention rate results of the pouch full cells of Example 1 and Comparative Example 2.
16 is a photograph of a pouch full cell of Example 1.

In describing the present invention, if it is determined that a detailed description of a related known technology or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

In addition, the terms to be described below are terms defined in consideration of functions in the present invention, which may vary according to the intention or custom of the user or operator, so the definitions should be made based on the content throughout this specification describing the present invention.

Manufacturing method of silicon carbon composite anode active material containing silver nanowires

One aspect of the present invention relates to a method for manufacturing a silicon-carbon composite anode active material including silver nanowires.

Example 1

In one embodiment of the present invention, the negative electrode active material manufacturing method includes (S11) preparing a dried product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires; (S12) preparing a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost layer, by firing the dried product; (S13) forming a soft coating layer on an outer circumferential surface of the fired object by mixing a carbon precursor with the fired object and performing heat treatment; (S14) forming a carbon nanotube layer on the outer circumferential surface of the soft coating layer; and (S15) forming a silver nanowire layer on an outer circumferential surface of the soft coating layer.

Hereinafter, the method for preparing the anode active material will be described step by step in detail.

(S11) Dry product manufacturing step

The step is a step of preparing a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires, and then drying the first mixture to prepare a dried product.

In one embodiment, the flake graphite may include at least one of natural graphite and artificial graphite.

In one embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to a first solvent and dispersing to prepare a dispersion; And grinding the dispersion; can be prepared including.

In one embodiment, the silicon powder may have a spherical, polyhedral or elliptical shape. For example, it may be in the form of a sphere. For example, the silicon powder may have an average particle diameter (D50) of 2 to 5 μm. Under the above conditions, the dispersibility is excellent, and nano-silicon can be easily prepared.

In one embodiment, the first solvent may include one or more of water, ethanol, isopropyl alcohol, and potassium hydroxide (KOH). Mixability and dispersibility may be excellent when the first solvent is included.

In one embodiment, the first solvent may include ethanol and water (pure water) in a weight ratio of 1:0.5 to 1:1.5. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 10 parts by weight of a dispersant. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared. For example, the nano-silicon slurry may include 100 parts by weight of silicon powder, 800 to 1000 parts by weight of a first solvent, and 0.5 to 1.5 parts by weight of a dispersant.

For example, a dispersant may be added to the first solvent in the above amount and mixed, then the silicon powder may be added and mixed to prepare a dispersion, and the dispersion may be pulverized to prepare a nano-silicon slurry.

In one embodiment, the grinding may be performed by milling. In one embodiment, the milling is performed using a beads mill, a ball-mill, a high energy ball mill, a planetary mill, a stirred ball mill, or a vibration mill. (vibration mill) and the like.

For example, the ball mill may be made of a chemically inert material that does not react with the silicon powder and other organic components. For example, zirconia (ZrO ₂ ) may be included. In one embodiment, the ball mill may have an average particle diameter of 0.1 to 1 mm. Under the above conditions, nano-silicon can be easily produced.

In another embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to the first solvent and dispersing to prepare a dispersion; and pulverizing after adding a carbon-based component to the dispersion.

Here, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 20 parts by weight of a dispersant. Under the above conditions, the pulverization efficiency of the silicon powder is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

For example, the nano-silicon slurry may include isopropyl alcohol and ethanol as the first solvent in a weight ratio of 1:3 to 1:6. Dispersion and pulverization efficiency of the silicon powder may be excellent under the mixing weight ratio condition.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the carbon-based component may include at least one of carbon fibers, nano-carbon fibers, flake graphite, and multi-layer graphene. When the carbon-based component is added, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon can be easily produced.

For example, the carbon-based component may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicon powder. When introduced under the above conditions, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

More specifically, when preparing the nano-silicon slurry, a first solvent containing ethanol and isopropyl alcohol in a weight ratio of 1: 4 was prepared, and 98% by weight of stearic acid and 2% by weight of N-methyl pyrrolidone (NMP) were mixed as a dispersant so you can prepare. Then, 100 parts by weight of the silicon powder, 5 to 1500 parts by weight of the first solvent, 0.1 to 20 parts by weight of the dispersing agent, and 0.01 to 10 parts by weight of the carbon-based component (carbon fiber) are added, mixed, and pulverized with a ball mill to prepare a nano-silicon slurry can do.

For example, in the case of grinding using the ball mill, the shaft of the wet mill may be operated at a low rotational condition for 4 hours (1200 rpm, based on a chamber of 10L), and at a high rotational speed (1650 rpm) for 14 hours. As described above, nano-silicon having an average particle diameter (D50) of 98 nm can be manufactured by a wet grinding method using 0.1 mm zirconia (ZrO ₂ ) balls. In one embodiment, the nano-silicon included in the nano-silicon slurry may have an average particle diameter of 1 to 250 nm. For another example, it may be 90 to 110 nm.

In one embodiment, the graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; In addition, it may be prepared by including; pulverizing the calcined graphite mixture. When the prepared graphite ball is included, a core including a porous matrix including nano-silicon and amorphous hard carbon is easily formed, and the anode active material may have excellent capacity characteristics, durability, and structural stability. For example, during the pressurization, the density of the graphite mixture may be increased to 1.2 g/cc or more for firing.

For example, the graphite ball is prepared by preparing a graphite mixture containing 100 parts by weight of pitch and 5 to 1000 parts by weight of graphite such as artificial graphite or natural graphite having a size of 1 to 6 μm, and then mixing it with 5 to 50 atm. Graphite balls may be produced by pressurizing (compressing) under pressure conditions, firing at 400 to 650 ° C, and then pulverizing. Under the above conditions, mixing and dispersibility are excellent, and graphite balls can be easily manufactured.

For example, the graphite ball may be applied in the form of a graphite ball mixture solution. For example, the graphite mixture may further include a second solvent. In one embodiment, the second solvent may include at least one of N-methylpyrrolidone (NMP), ethanol, and water. Mixability and dispersibility may be excellent when the second solvent is included. For example, the second solvent may include all of N-methylpyrrolidone (NMP), ethanol, and water.

More specifically, the graphite ball is prepared by dissolving pitch in the N-methylpyrrolidone, mixing with ethanol, adding water (pure water) and mixing to prepare a binder solution; And adding flake graphite to the binder solution and stirring it; can be prepared including.

In one embodiment, the pitch may include one or more of petroleum pitch (pyrolysis fuel oil pitch) and coal-based pitch (coal tar pitch). When the pitch is included, when the anode active material including the graphite ball and the nano-silicon is fired at a high temperature of 800° C. or higher, amorphous carbon is coated on the inner surface of the nano-silicon surrounding the graphite ball, and the binder properties between the nano-silicon or Binder properties between the graphite ball and the nano-silicon may be excellent.

For example, the graphite ball is prepared by mixing graphite with a binder solution containing pitch and a second solvent to prepare a graphite mixture; calcining by pressing the graphite mixture; And, preparing a graphite ball by grinding and sintering the calcined graphite mixture; may be prepared including.

In one embodiment, the graphite mixture may include 500 to 2500 parts by weight of the second solvent based on 100 parts by weight of the pitch. Mixability and dispersibility may be excellent when included in the above range. For example, 800 to 1300 parts by weight may be included.

For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 3:1 to 5. When included in the above weight ratio, mixing and dispersibility are excellent, and graphite balls can be easily manufactured. For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 2:1.5 to 3.

In one embodiment, the same graphite as described above may be used. In one embodiment, the graphite ball may include at least one of natural graphite, artificial graphite, porous carbon, silicon, and tangled round carbon nanotubes.

For example, the graphite ball may be manufactured by adding 30 to 200 parts by weight of the flake graphite based on 100 parts by weight of pitch and mixing (stirring) to form a graphite ball. Graphite balls are easily formed under the above conditions, and the structural stability, high capacity and high output characteristics of the present invention may be excellent. For example, 50 to 150 parts by weight of flake graphite may be added to 100 parts by weight of the pitch.

The graphite ball may be formed in a spherical or oval shape by mixing flake graphite and pitch. In one embodiment, the graphite balls may have an average particle diameter of 0.3 to 20 μm. Under the above conditions, an anode active material can be easily formed. For example, the graphite ball may have a porous spherical shape. The graphite balls are not disintegrated in the mixed solution due to the binder properties of the pitch.

The first mixture includes the graphite balls, flake graphite, pitch, nano-silicon, and a solvent, and the solvent may include at least one of ethanol, isopropyl alcohol, and water.

In one embodiment, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.01 to 5:2 to 8:1 to 25:5 to 70. When included in the mixing weight ratio, the electrical conductivity, mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared. For example, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.1 to 3:4 to 6:5 to 10:10 to 15.

In one embodiment, the first mixture may include 1 to 5 parts by weight of pitch based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

The powder size of the negative electrode active material can be easily controlled through drying of the first mixture. For example, the drying may be performed using a spray dryer or the like. For example, the drying may be spray-dried using a spray dryer equipped with a single-fluid nozzle, a double-fluid nozzle, or a quadruple-fluid nozzle.

In one embodiment, the building may be spherical, polyhedral or elliptical. For example, it may be spherical.

In one embodiment, the dry matter may have an average particle diameter (or size) of 0.1 to 15 μm. Mixability and formability may be excellent under the above conditions.

In one embodiment, when spray drying the first mixture using a hydraulic nozzle, the dried product prepared by setting the outlet temperature to 70 ~ 130 ° C. and carrying out the air flow condition of 650 ~ 850 sccm averages The particle size may be 7 to 14 μm. In another embodiment, when the first mixture is spray-dried using a quadruple nozzle, the dried product may have an average particle diameter of 0.1 to 8 μm.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowires may be included in the first mixture in the form of a dispersion.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In another embodiment, the silver nanowire dispersion includes silver (Ag) nanowires, a first dispersant, and water, and the first dispersant is one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. may contain more than

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride. .

In one embodiment, the first mixture may include 0.01 to 5 parts by weight of silver nanowires based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

In another embodiment, the first mixture may include 0.01 to 20 parts by weight of the silver nanowire dispersion based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

(S12) Calcined product manufacturing step

The above step is a step of preparing a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost portion, by firing the dried product. In one embodiment, the firing may be carried out by raising the temperature to 600 ~ 1250 ℃. During the firing, the pitch in the dry matter is solutionized in the range of 200 ~ 300 ℃, the solvent of the pitch evaporates in the range of 350 ~ 550 ℃, and the thermosetting material in the range of 600 ~ 1250 ℃ can be carbonized. When fired under the above conditions, a core in which silver nanowires and flake graphite are dispersed in a porous matrix containing nano-silicon and amorphous hard carbon is formed, and a hard coating layer containing the amorphous hard carbon is formed on the outermost part of the core. there is.

(S13) Soft coating layer formation step

The step is a step of forming a soft coating layer on the outer circumferential surface of the fired object by mixing the carbon precursor with the fired object and performing heat treatment. In one embodiment, 0.1 to 30 parts by weight of the carbon precursor may be included based on 100 parts by weight of the fired product. When included in the above content range, the mixing property is excellent, and a soft coating layer can be easily formed.

In one embodiment, the carbon precursor is polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber (H-NBR), nitrile butadiene rubber (NBR), polyvinylidene fluoride (PVDF) ), styrene butadiene rubber (SBR) and at least one of sucrose. When the carbon precursor is included, a soft coating layer can be easily formed.

For example, the carbon precursor may further include a solvent. The solvent may include at least one of water, an ethanol-based solvent, an amide-based solvent, an ester-based solvent, and a hydrocarbon-based solvent. When the solvent is included, workability may be excellent.

The alcohol-based solvent may include at least one of methanol, ethanol, isopropanol, and butanol.

The amide-based solvent may include at least one of N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and dimethylformamide (DMF).

The hydrocarbon-based solvent may include at least one of toluene and xylene.

In one embodiment, the heat treatment may be performed at 80 to 300 °C. During heat treatment under the above conditions, a soft coating layer containing amorphous soft carbon can be easily formed.

(S14) Carbon nanotube layer formation step

The above step is a step of forming a carbon nanotube layer on the outer circumferential surface of the soft coating layer. The carbon nanotube layer may be formed by coating and drying a carbon nanotube solution on an outer circumferential surface of the soft coating layer.

In one embodiment, the carbon nanotube solution may include carbon nanotubes, carboxymethylcellulose, and a solvent. The solvent may include at least one of water and an alcohol-based solvent. For example, the carbon nanotube solution may include 0.1 to 5% by weight of carbon nanotubes, 0.01 to 3% by weight of carboxymethyl cellulose, and the balance of the solvent. After applying the carbon nanotube solution, the carbon nanotubes may be formed on the surface of the soft coating layer by drying.

For example, the carbon nanotubes may have a length of 0.1 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 5 to 50 μm.

In one embodiment, 0.01 to 50 parts by weight of the carbon nanotube solution may be included with respect to 100 parts by weight of the heat-treated intermediate. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, after the step of forming the carbon nanotube layer, the step of forming an organic coating layer on the surface of the carbon nanotube layer of the negative electrode active material may be further included.

In one embodiment, the organic coating layer may be included for the purpose of improving thermal stability and lifespan of the negative electrode active material.

In one embodiment, the organic coating layer may include at least one of a polyolefin-based compound, a polyolefin wax, and an acrylic compound. The polyolefin may include at least one of polyethylene and polypropylene.

(S15) silver nanowire layer forming step

The above step is a step of forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowire layer may be prepared by applying a silver (Ag) nanowire dispersion to the surface of the carbon nanotube layer and heat-treating at 80 to 150°C. Under the above conditions, the silver nanowire layer can be easily formed.

In another embodiment, the silver nanowire layer may be formed by chemical vapor deposition (CVD) of silver (Ag) nanowires on the outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a first dispersant, and water, and the first dispersant may include at least one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. can

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the fired product on which the carbon nanotube layer is formed. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the prepared negative electrode active material may further include a step of disintegrating and classifying the negative electrode active material using a screen, a sieve, or the like.

The prepared anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver (Ag) nanowires and flake graphite dispersed in the porous matrix; a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; a soft coating layer formed on an outer circumferential surface of the hard coating layer; a carbon nanotube layer formed on an outer circumferential surface of the soft coating layer; and a silver (Ag) nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 1 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. , 0.1 to 5% by weight of the soft coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

2nd embodiment

In another embodiment of the present invention, the negative electrode active material manufacturing method includes (S21) preparing a dry product by drying a first mixture including graphite balls, nano-silicon slurry, flake graphite, and silver nanowires; (S22) preparing a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost layer, by mixing and firing the dried product and the pitch; (S23) preparing an intermediate by mixing a carbon precursor with the burnt material and heat-treating to form a first soft coating layer and a second soft coating layer on the inner and outer circumferential surfaces of the hard coating layer, respectively; (S24) forming a carbon nanotube layer on the outer circumferential surface of the second soft coating layer; and (S25) forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

Hereinafter, the method for preparing the anode active material will be described step by step in detail.

(S21) Dry product manufacturing step

The above step is a step of preparing a dried product by preparing a first mixture including graphite balls, nano-silicon slurry, flake graphite, and silver nanowires, and then drying the first mixture.

The same graphite balls, nano-silicon slurry, flake graphite, and silver nanowires as described above may be used.

In one embodiment, the flake graphite may include at least one of natural graphite and artificial graphite.

In one embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to a first solvent and dispersing to prepare a dispersion; And grinding the dispersion; can be prepared including.

In one embodiment, the silicon powder may have a spherical, polyhedral or elliptical shape. For example, it may be in the form of a sphere. For example, the silicon powder may have an average particle diameter (D50) of 2 to 5 μm. Under the above conditions, the dispersibility is excellent, and nano-silicon can be easily prepared.

In one embodiment, the first solvent may include one or more of water, ethanol, isopropyl alcohol, and potassium hydroxide (KOH). Mixability and dispersibility may be excellent when the first solvent is included.

In one embodiment, the first solvent may include ethanol and water (pure water) in a weight ratio of 1:0.5 to 1:1.5. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 10 parts by weight of a dispersant. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared. For example, the nano-silicon slurry may include 100 parts by weight of silicon powder, 800 to 1000 parts by weight of a first solvent, and 0.5 to 1.5 parts by weight of a dispersant.

For example, a dispersant may be added to the first solvent in the above amount and mixed, then the silicon powder may be added and mixed to prepare a dispersion, and the dispersion may be pulverized to prepare a nano-silicon slurry.

In one embodiment, the grinding may be performed by milling. In one embodiment, the milling is performed using a beads mill, a ball-mill, a high energy ball mill, a planetary mill, a stirred ball mill, or a vibration mill. (vibration mill) and the like.

For example, the ball mill may be made of a chemically inert material that does not react with the silicon powder and other organic components. For example, zirconia (ZrO ₂ ) may be included. In one embodiment, the ball mill may have an average particle diameter of 0.1 to 1 mm. Under the above conditions, nano-silicon can be easily produced.

In another embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to the first solvent and dispersing to prepare a dispersion; and pulverizing after adding a carbon-based component to the dispersion.

Here, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 20 parts by weight of a dispersant. Under the above conditions, the pulverization efficiency of the silicon powder is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

For example, the nano-silicon slurry may include isopropyl alcohol and ethanol as the first solvent in a weight ratio of 1:3 to 1:6. Dispersion and pulverization efficiency of the silicon powder may be excellent under the mixing weight ratio condition.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the carbon-based component may include at least one of carbon fibers, nano-carbon fibers, flake graphite, and multi-layer graphene. When the carbon-based component is added, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon can be easily produced.

For example, the carbon-based component may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicon powder. When introduced under the above conditions, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

More specifically, when preparing the nano-silicon slurry, a first solvent containing ethanol and isopropyl alcohol in a weight ratio of 1: 4 was prepared, and 98% by weight of stearic acid and 2% by weight of N-methyl pyrrolidone (NMP) were mixed as a dispersant so you can prepare. Then, 100 parts by weight of the silicon powder, 5 to 1500 parts by weight of the first solvent, 0.1 to 20 parts by weight of the dispersing agent, and 0.01 to 10 parts by weight of the carbon-based component (carbon fiber) are added, mixed, and pulverized with a ball mill to prepare a nano-silicon slurry can do.

For example, in the case of grinding using the ball mill, the shaft of the wet mill may be operated at a low rotational condition for 4 hours (1200 rpm, based on a chamber of 10L), and at a high rotational speed (1650 rpm) for 14 hours. As described above, nano-silicon having an average particle diameter (D50) of 98 nm can be manufactured by a wet grinding method using 0.1 mm zirconia (ZrO ₂ ) balls. In one embodiment, the nano-silicon included in the nano-silicon slurry may have an average particle diameter of 1 to 250 nm. For another example, it may be 90 to 110 nm.

In one embodiment, the graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; In addition, it may be prepared by including; pulverizing the calcined graphite mixture. When the prepared graphite ball is included, a core including a porous matrix including nano-silicon and amorphous hard carbon is easily formed, and the anode active material may have excellent capacity characteristics, durability, and structural stability. For example, during the pressurization, the density of the graphite mixture may be increased to 1.2 g/cc or more for firing.

For example, the graphite ball is prepared by preparing a graphite mixture containing 100 parts by weight of pitch and 5 to 1000 parts by weight of graphite such as artificial graphite or natural graphite having a size of 1 to 6 μm, and then mixing it with 5 to 50 atm. Graphite balls may be produced by pressurizing (compressing) under pressure conditions, firing at 400 to 650 ° C, and then pulverizing. Under the above conditions, mixing and dispersibility are excellent, and graphite balls can be easily manufactured.

For example, the graphite ball may be applied in the form of a graphite ball mixture solution. For example, the graphite mixture may further include a second solvent. In one embodiment, the second solvent may include at least one of N-methylpyrrolidone (NMP), ethanol, and water. Mixability and dispersibility may be excellent when the second solvent is included. For example, the second solvent may include all of N-methylpyrrolidone (NMP), ethanol, and water.

More specifically, the graphite ball is prepared by dissolving pitch in the N-methylpyrrolidone, mixing with ethanol, adding water (pure water) and mixing to prepare a binder solution; And adding flake graphite to the binder solution and stirring it; can be prepared including.

In one embodiment, the pitch may include one or more of petroleum pitch (pyrolysis fuel oil pitch) and coal-based pitch (coal tar pitch). When the pitch is included, when the anode active material including the graphite ball and the nano-silicon is fired at a high temperature of 800° C. or higher, amorphous carbon is coated on the inner surface of the nano-silicon surrounding the graphite ball, and the binder properties between the nano-silicon or Binder properties between the graphite ball and the nano-silicon may be excellent.

For example, the graphite ball is prepared by mixing graphite with a binder solution containing pitch and a second solvent to prepare a graphite mixture; calcining by pressing the graphite mixture; And, preparing a graphite ball by grinding and sintering the calcined graphite mixture; may be prepared including.

In one embodiment, the graphite mixture may include 500 to 2500 parts by weight of the second solvent based on 100 parts by weight of the pitch. Mixability and dispersibility may be excellent when included in the above range. For example, 800 to 1300 parts by weight may be included.

For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 3:1 to 5. When included in the above weight ratio, mixing and dispersibility are excellent, and graphite balls can be easily manufactured. For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 2:1.5 to 3.

In one embodiment, the same graphite as described above may be used. In one embodiment, the graphite ball may include at least one of natural graphite, artificial graphite, porous carbon, silicon, and tangled round carbon nanotubes.

For example, the graphite ball may be manufactured by adding 30 to 200 parts by weight of the flake graphite based on 100 parts by weight of pitch and mixing (stirring) to form a graphite ball. Graphite balls are easily formed under the above conditions, and the structural stability, high capacity and high output characteristics of the present invention may be excellent. For example, 50 to 150 parts by weight of flake graphite may be added to 100 parts by weight of the pitch.

The graphite ball may be formed in a spherical or oval shape by mixing flake graphite and pitch. In one embodiment, the graphite balls may have an average particle diameter of 0.3 to 20 μm. Under the above conditions, an anode active material can be easily formed. For example, the graphite ball may have a porous spherical shape. The graphite balls are not disintegrated in the mixed solution due to the binder properties of the pitch.

The first mixture includes the graphite balls, flake graphite, pitch, nano-silicon, and a solvent, and the solvent may include at least one of ethanol, isopropyl alcohol, and water.

In one embodiment, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.01 to 5:2 to 8:1 to 25:5 to 70. When included in the mixing weight ratio, the electrical conductivity, mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared. For example, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.1 to 3:4 to 6:5 to 10:10 to 15.

In one embodiment, the first mixture may further include 1 to 5 parts by weight of pitch based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

The powder size of the negative electrode active material can be easily controlled through drying of the first mixture. For example, the drying may be performed using a spray dryer or the like. For example, the drying may be spray-dried using a spray dryer equipped with a single-fluid nozzle, a double-fluid nozzle, or a quadruple-fluid nozzle.

In one embodiment, the building may be spherical, polyhedral or elliptical. For example, it may be spherical.

In one embodiment, the dry matter may have an average particle diameter (or size) of 0.1 to 15 μm. Mixability and formability may be excellent under the above conditions.

In one embodiment, when spray drying the first mixture using a hydraulic nozzle, the dried product prepared by setting the outlet temperature to 70 ~ 130 ° C. and carrying out the air flow condition of 650 ~ 850 sccm averages The particle size may be 7 to 14 μm. In another embodiment, when the first mixture is spray-dried using a quadruple nozzle, the dried product may have an average particle diameter of 0.1 to 8 μm.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowires may be included in the first mixture in the form of a dispersion.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In another embodiment, the silver nanowire dispersion includes silver (Ag) nanowires, a first dispersant, and water, and the first dispersant is one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. may contain more than

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride. .

In one embodiment, the first mixture may include 0.01 to 5 parts by weight of silver nanowires based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

In another embodiment, the first mixture may include 0.01 to 20 parts by weight of the silver nanowire dispersion based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

(S22) Calcined product manufacturing step

The above step is a step of mixing and firing the dry material and pitch to prepare a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost part.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

The calcined product may be calcined by mixing 100 parts by weight of dry matter and 0.5 to 30 parts by weight of pitch. Under the above conditions, durability and structural stability of the fired product may be excellent.

In one embodiment, the firing may be carried out by raising the temperature to 600 ~ 1250 ℃. During the firing, the pitch in the dry matter is solutionized in the range of 200 ~ 300 ℃, the solvent of the pitch evaporates in the range of 350 ~ 550 ℃, and the thermosetting material in the range of 600 ~ 1250 ℃ can be carbonized. When fired under the above conditions, a core in which silver nanowires and flake graphite are dispersed in a porous matrix containing nano-silicon and amorphous hard carbon is formed, and a hard coating layer containing the amorphous hard carbon is formed on the outermost part of the core. there is.

(S23) Soft coating layer formation step

The step is a step of preparing an intermediate body by mixing a carbon precursor with the burnt material and heat-treating to form a first soft coating layer and a second soft coating layer on the inner and outer circumferential surfaces of the hard coating layer, respectively.

In one embodiment, heat treatment may be performed by including 0.1 to 30 parts by weight of the carbon precursor with respect to 100 parts by weight of the fired product. Mixability is excellent when included within the above content range, and a first soft coating layer and a second soft coating layer are formed on the inner and outer circumferential surfaces of the hard coating layer, respectively.

In one embodiment, the carbon precursor includes at least one of polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, polyvinylidene fluoride, styrene butadiene rubber, and sucrose can do. When the carbon precursor is included, a soft coating layer can be easily formed.

For example, the carbon precursor may further include a solvent. The solvent may include at least one of water, an ethanol-based solvent, an amide-based solvent, an ester-based solvent, and a hydrocarbon-based solvent. When the solvent is included, workability may be excellent.

The alcohol-based solvent may include at least one of methanol, ethanol, isopropanol, and butanol.

The amide-based solvent may include at least one of N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and dimethylformamide (DMF).

The hydrocarbon-based solvent may include at least one of toluene and xylene.

In one embodiment, the heat treatment may be performed at 80 to 300 °C. When the heat treatment is performed under the above conditions, a first soft coating layer and a second soft coating layer each including amorphous soft carbon may be formed on the inner and outer circumferential surfaces of the hard coating layer, respectively.

In one embodiment, when the soft coating layer is formed, the soft coating layer is also formed inside the porous matrix of the core, and the graphite balls may be located inside the soft coating layer.

For example, during the heat treatment, a first soft coating layer formed on the outermost surface of the fired product, a hard coating layer formed on the outer circumferential surface of the first soft coating layer and containing the amorphous hard carbon, and formed on the outer circumferential surface of the hard coating layer It may include a second soft coating layer to be.

(S24) Carbon nanotube layer formation step

The step is a step of forming a carbon nanotube layer on the outer circumferential surface of the second soft coating layer. The carbon nanotube layer may be formed by coating and drying a carbon nanotube solution on the outer circumferential surface of the second soft coating layer.

In one embodiment, the carbon nanotube solution may include carbon nanotubes, carboxymethylcellulose, and a solvent. The solvent may include at least one of water and an alcohol-based solvent. For example, the carbon nanotube solution may include 0.1 to 5% by weight of carbon nanotubes, 0.01 to 3% by weight of carboxymethyl cellulose, and the balance of the solvent. After applying the carbon nanotube solution, the carbon nanotubes may be formed on the surface of the soft coating layer by drying.

For example, the carbon nanotubes may have a length of 0.1 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 5 to 50 μm.

In one embodiment, 0.01 to 50 parts by weight of the carbon nanotube solution may be included with respect to 100 parts by weight of the heat-treated intermediate. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, after the step of forming the carbon nanotube layer, the step of forming an organic coating layer on the surface of the carbon nanotube layer of the negative electrode active material may be further included.

In one embodiment, the organic coating layer may be included for the purpose of improving thermal stability and lifespan of the negative electrode active material.

In one embodiment, the organic coating layer may include at least one of a polyolefin-based compound, a polyolefin wax, and an acrylic compound. The polyolefin may include at least one of polyethylene and polypropylene.

(S25) Silver Nano Layer Formation Step

The above step is a step of forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer. In one embodiment, the silver nanowire layer may be prepared by applying a silver (Ag) nanowire dispersion to an outer circumferential surface of the carbon nanotube layer and heat-treating at 80 to 150°C. Under the above conditions, the silver nanowire layer can be easily formed.

In another embodiment, the silver nanowire layer may be formed by chemical vapor deposition (CVD) of silver (Ag) nanowires on the outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a first dispersant, and water, and the first dispersant includes at least one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. can do.

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the fired product on which the carbon nanotube layer is formed. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the prepared negative electrode active material may further include a step of disintegrating and classifying the negative electrode active material using a screen, a sieve, or the like.

The prepared anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver nanowires and flake graphite dispersed in the porous matrix; a first soft coating layer formed on an outer circumferential surface of the core; a hard coating layer formed on an outer circumferential surface of the first soft coating layer and containing amorphous hard carbon; a second soft coating layer formed on an outer circumferential surface of the hard coating layer; a carbon nanotube layer formed on an outer circumferential surface of the second soft coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. , 0.1 to 15 wt% of the first soft coating layer, 0.1 to 15 wt% of the second soft coating layer, 0.01 to 10 wt% of the carbon nanotube layer, and 0.01 to 10 wt% of the silver nanowire layer.

3rd embodiment

In another embodiment of the present invention, the negative electrode active material manufacturing method includes the steps of (S31) drying a first mixture containing graphite balls and nano-silicon slurry to prepare a dried product; (S32) preparing a fired product having a hard coating layer comprising amorphous hard carbon on the outermost layer by firing the dried product; (S33) preparing an intermediate body by mixing a carbon precursor and silver nanowires with the burnt product and performing a primary heat treatment to form a first soft coating layer on an outer circumferential surface of the hard coating layer; and (S34) forming a second soft coating layer on the outer circumferential surface of the first soft coating layer by mixing the intermediate, the carbon precursor, the carbon nanotubes, and the silver nanowires and performing secondary heat treatment.

(S31) Dry product manufacturing step

The above step is a step of preparing a dried product by drying the first mixture including the graphite balls and the nano-silicon slurry.

In one embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to a first solvent and dispersing to prepare a dispersion; And grinding the dispersion; can be prepared including.

In one embodiment, the silicon powder may have a spherical, polyhedral or elliptical shape. For example, it may be in the form of a sphere. For example, the silicon powder may have an average particle diameter (D50) of 2 to 5 μm. Under the above conditions, the dispersibility is excellent, and nano-silicon can be easily prepared.

In one embodiment, the first solvent may include one or more of water, ethanol, isopropyl alcohol, and potassium hydroxide (KOH). Mixability and dispersibility may be excellent when the first solvent is included.

In one embodiment, the first solvent may include ethanol and water (pure water) in a weight ratio of 1:0.5 to 1:1.5. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 10 parts by weight of a dispersant. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared. For example, the nano-silicon slurry may include 100 parts by weight of silicon powder, 800 to 1000 parts by weight of a first solvent, and 0.5 to 1.5 parts by weight of a dispersant.

For example, a dispersant may be added to the first solvent in the above amount and mixed, then the silicon powder may be added and mixed to prepare a dispersion, and the dispersion may be pulverized to prepare a nano-silicon slurry.

In one embodiment, the grinding may be performed by milling. In one embodiment, the milling is performed using a beads mill, a ball-mill, a high energy ball mill, a planetary mill, a stirred ball mill, or a vibration mill. (vibration mill) and the like.

For example, the ball mill may be made of a chemically inert material that does not react with the silicon powder and other organic components. For example, zirconia (ZrO ₂ ) may be included. In one embodiment, the ball mill may have an average particle diameter of 0.1 to 1 mm. Under the above conditions, nano-silicon can be easily produced.

In another embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to the first solvent and dispersing to prepare a dispersion; and pulverizing after adding a carbon-based component to the dispersion.

Here, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 20 parts by weight of a dispersant. Under the above conditions, the pulverization efficiency of the silicon powder is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

For example, the nano-silicon slurry may include isopropyl alcohol and ethanol as the first solvent in a weight ratio of 1:3 to 1:6. Dispersion and pulverization efficiency of the silicon powder may be excellent under the mixing weight ratio condition.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the carbon-based component may include at least one of carbon fibers, nano-carbon fibers, flake graphite, and multi-layer graphene. When the carbon-based component is added, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon can be easily produced.

For example, the carbon-based component may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicon powder. When introduced under the above conditions, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

More specifically, when preparing the nano-silicon slurry, a first solvent containing ethanol and isopropyl alcohol in a weight ratio of 1: 4 was prepared, and 98% by weight of stearic acid and 2% by weight of N-methyl pyrrolidone (NMP) were mixed as a dispersant so you can prepare. Then, 100 parts by weight of the silicon powder, 5 to 1500 parts by weight of the first solvent, 0.1 to 20 parts by weight of the dispersing agent, and 0.01 to 10 parts by weight of the carbon-based component (carbon fiber) are added, mixed, and pulverized with a ball mill to prepare a nano-silicon slurry can do.

For example, in the case of grinding using the ball mill, the shaft of the wet mill may be operated at a low rotational condition for 4 hours (1200 rpm, based on a chamber of 10L), and at a high rotational speed (1650 rpm) for 14 hours. As described above, nano-silicon having an average particle diameter (D50) of 98 nm can be manufactured by a wet grinding method using 0.1 mm zirconia (ZrO ₂ ) balls. In one embodiment, the nano-silicon included in the nano-silicon slurry may have an average particle diameter of 1 to 250 nm. For another example, it may be 90 to 110 nm.

In one embodiment, the graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; In addition, it may be prepared by including; pulverizing the calcined graphite mixture. When the prepared graphite ball is included, a core including a porous matrix including nano-silicon and amorphous hard carbon is easily formed, and the anode active material may have excellent capacity characteristics, durability, and structural stability. For example, during the pressurization, the density of the graphite mixture may be increased to 1.2 g/cc or more for firing.

For example, the graphite ball is prepared by preparing a graphite mixture containing 100 parts by weight of pitch and 5 to 1000 parts by weight of graphite such as artificial graphite or natural graphite having a size of 1 to 6 μm, and then mixing it with 5 to 50 atm. Graphite balls may be produced by pressurizing (compressing) under pressure conditions, firing at 400 to 650 ° C, and then pulverizing. Under the above conditions, mixing and dispersibility are excellent, and graphite balls can be easily manufactured.

For example, the graphite ball may be applied in the form of a graphite ball mixture solution. For example, the graphite mixture may further include a second solvent. In one embodiment, the second solvent may include at least one of N-methylpyrrolidone (NMP), ethanol, and water. Mixability and dispersibility may be excellent when the second solvent is included. For example, the second solvent may include all of N-methylpyrrolidone (NMP), ethanol, and water.

More specifically, the graphite ball is prepared by dissolving pitch in the N-methylpyrrolidone, mixing with ethanol, adding water (pure water) and mixing to prepare a binder solution; And adding flake graphite to the binder solution and stirring it; can be prepared including.

In one embodiment, the pitch may include one or more of petroleum pitch (pyrolysis fuel oil pitch) and coal-based pitch (coal tar pitch). When the pitch is included, when the anode active material including the graphite ball and the nano-silicon is fired at a high temperature of 800° C. or higher, amorphous carbon is coated on the inner surface of the nano-silicon surrounding the graphite ball, and the binder properties between the nano-silicon or Binder properties between the graphite ball and the nano-silicon may be excellent.

For example, the graphite ball is prepared by mixing graphite with a binder solution containing pitch and a second solvent to prepare a graphite mixture; calcining by pressing the graphite mixture; And, preparing a graphite ball by grinding and sintering the calcined graphite mixture; may be prepared including.

In one embodiment, the graphite mixture may include 500 to 2500 parts by weight of the second solvent based on 100 parts by weight of the pitch. Mixability and dispersibility may be excellent when included in the above range. For example, 800 to 1300 parts by weight may be included.

For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 3:1 to 5. When included in the above weight ratio, mixing and dispersibility are excellent, and graphite balls can be easily manufactured. For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 2:1.5 to 3.

In one embodiment, the same graphite as described above may be used. In one embodiment, the graphite ball may include at least one of natural graphite, artificial graphite, porous carbon, silicon, and tangled round carbon nanotubes.

For example, the graphite ball may be manufactured by adding 30 to 200 parts by weight of the flake graphite based on 100 parts by weight of pitch and mixing (stirring) to form a graphite ball. Graphite balls are easily formed under the above conditions, and the structural stability, high capacity and high output characteristics of the present invention may be excellent. For example, 50 to 150 parts by weight of flake graphite may be added to 100 parts by weight of the pitch.

The graphite ball may be formed in a spherical or oval shape by mixing flake graphite and pitch. In one embodiment, the graphite balls may have an average particle diameter of 0.3 to 20 μm. Under the above conditions, an anode active material can be easily formed. For example, the graphite ball may have a porous spherical shape. The graphite balls are not disintegrated in the mixed solution due to the binder properties of the pitch.

When the prepared graphite ball is included, a core including a porous matrix including nano-silicon and amorphous hard carbon is easily formed, and the anode active material may have excellent capacity characteristics, durability, and structural stability.

The same graphite balls and nano-silicon slurry as described above may be used.

The first mixture includes the graphite balls, nano-silicon, and a solvent, and the solvent may include at least one of ethanol, isopropyl alcohol, and water.

The first mixture may include the graphite balls and nano-silicon in a weight ratio of 1:0.5 to 70 based on solid content. When included in the mixing weight ratio, the mixing and dispersibility of the first mixture is excellent, and the negative electrode active material can be easily prepared. For example, the first mixture may include the graphite balls and nano-silicon in a weight ratio of 1:0.5 to 1:5.

The powder size of the negative electrode active material can be easily controlled through drying of the first mixture. For example, the drying may be performed using a spray dryer or the like. For example, the drying may be spray-dried using a spray dryer equipped with a single-fluid nozzle, a double-fluid nozzle, or a quadruple-fluid nozzle.

In one embodiment, the building may be spherical, polyhedral or elliptical. For example, it may be spherical.

In one embodiment, the dry matter may have an average particle diameter (or size) of 0.1 to 15 μm. Mixability and formability may be excellent under the above conditions.

In one embodiment, when spray drying the first mixture using a hydraulic nozzle, the dried product prepared by setting the outlet temperature to 70 ~ 130 ° C. and carrying out the air flow condition of 650 ~ 850 sccm averages The particle diameter may be 7 to 14 μm. In another embodiment, when the first mixture is spray-dried using a quadruple nozzle, the dried product may have an average particle diameter of 0.1 to 8 μm.

(S32) Calcined product manufacturing step

The above step is a step of preparing a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost portion, by firing the dried product.

In one embodiment, the firing may be carried out by raising the temperature to 600 ~ 1250 ℃. When fired under the above conditions, a core in which flake graphite is dispersed in a porous matrix containing nano-silicon and amorphous hard carbon is formed, and a hard coating layer containing the amorphous hard carbon may be formed on the outermost part of the core.

(S33) first soft coating layer forming step

The step is a step of preparing an intermediate body by mixing a carbon precursor and silver nanowires with the fired product and performing a primary heat treatment to form a first soft coating layer on an outer circumferential surface of the hard coating layer.

In one specific example, 0.1 to 30 parts by weight of the carbon precursor and 0.01 to 5 parts by weight of the silver nanowires may be included for 100 parts by weight of the burnt material to perform a primary heat treatment. When included within the above content range, a first soft coating layer having excellent mixing properties and excellent electrical conductivity and mechanical properties can be easily formed.

In one embodiment, the carbon precursor includes at least one of polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, polyvinylidene fluoride, styrene butadiene rubber, and sucrose can do. When the carbon precursor is included, the first soft coating layer can be easily formed.

For example, the carbon precursor may further include a solvent. The solvent may include at least one of water, an ethanol-based solvent, an amide-based solvent, an ester-based solvent, and a hydrocarbon-based solvent. When the solvent is included, workability may be excellent.

The alcohol-based solvent may include at least one of methanol, ethanol, isopropanol, and butanol.

The amide-based solvent may include at least one of N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and dimethylformamide (DMF).

The hydrocarbon-based solvent may include at least one of toluene and xylene.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowires may be mixed in a dispersion form.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In another embodiment, the silver nanowire dispersion includes silver (Ag) nanowires, a first dispersant, and water, and the first dispersant is one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. may contain more than

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride. .

In one embodiment, 0.1 to 30 parts by weight of the carbon precursor and 0.01 to 20 parts by weight of the silver nanowire dispersion may be included with respect to 100 parts by weight of the calcined product to perform a first heat treatment. When included within the above content range, a first soft coating layer having excellent mixing properties and excellent electrical conductivity and mechanical properties can be easily formed.

In one embodiment, the primary heat treatment may be performed at 80 to 300 °C. During heat treatment under the above conditions, a first soft coating layer including amorphous soft carbon and silver nanowires may be formed on an outer circumferential surface of the hard coating layer.

(S34) second soft coating layer forming step

The step is a step of forming a second soft coating layer on the outer circumferential surface of the first soft coating layer by mixing the intermediate, the carbon precursor, the carbon nanotubes, and the silver nanowires and performing secondary heat treatment.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowires may be mixed in a dispersion form.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In another embodiment, the silver nanowire dispersion includes silver (Ag) nanowires, a first dispersant, and water, and the first dispersant is one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. may contain more than

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride. .

In one embodiment, the carbon precursor includes at least one of polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, polyvinylidene fluoride, styrene butadiene rubber, and sucrose can do. When the carbon precursor is included, the first soft coating layer can be easily formed.

For example, the carbon precursor may further include a solvent. The solvent may include at least one of water, an ethanol-based solvent, an amide-based solvent, an ester-based solvent, and a hydrocarbon-based solvent. When the solvent is included, workability may be excellent.

The alcohol-based solvent may include at least one of methanol, ethanol, isopropanol, and butanol.

The amide-based solvent may include at least one of N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and dimethylformamide (DMF).

The hydrocarbon-based solvent may include at least one of toluene and xylene.

In one embodiment, the carbon nanotubes may be mixed in the form of a carbon nanotube solution. In one embodiment, the carbon nanotube solution may include carbon nanotubes, carboxymethylcellulose, and a solvent. The solvent may include at least one of water and an alcohol-based solvent. For example, the carbon nanotube solution may include 0.1 to 5% by weight of carbon nanotubes, 0.01 to 3% by weight of carboxymethyl cellulose, and the balance of the solvent. A second soft coating layer including carbon nanotubes may be easily formed on the surface of the first soft coating layer by applying the carbon nanotube solution and then drying the solution.

In one embodiment, the secondary heat treatment may be performed at 80 to 300 °C. When the heat treatment is performed under the above conditions, a second soft coating layer including amorphous soft carbon, carbon nanotubes, and silver nanowires may be formed on the outer circumferential surface of the first soft coating layer.

In one embodiment, the prepared negative electrode active material may further include a step of disintegrating and classifying the negative electrode active material using a screen, a sieve, or the like.

In one embodiment, 0.1 to 30 parts by weight of the carbon precursor, 0.01 to 50 parts by weight of carbon nanotubes (or carbon nanotube solution), and 0.01 to 5 parts by weight of silver nanowires are included with respect to 100 parts by weight of the intermediate to perform secondary heat treatment. can When included within the above content range, a second soft coating layer having excellent mixing properties and excellent electrical conductivity and mechanical properties can be easily formed.

In one embodiment, the prepared negative electrode active material may further include a step of disintegrating and classifying the negative electrode active material using a screen, a sieve, or the like.

In one embodiment, the anode active material includes a core including a porous matrix including nano-silicon (Si) and amorphous hard carbon; a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; a first soft coating layer formed on an outer circumferential surface of the hard coating layer and including soft carbon and silver nanowires; and a second soft coating layer formed on an outer circumferential surface of the first soft coating layer and including soft carbon, carbon nanotubes, and silver nanowires.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 5 to 50% by weight of amorphous hard carbon, 0.1 to 15% by weight of a hard coating layer, 0.1 to 15% by weight of a first soft coating layer, and 0.1 to 15% by weight of a second soft coating layer. 0.1 to 15% by weight, wherein the first soft coating layer includes the silver nanowires and soft carbon in a weight ratio of 1:0.5 to 1:20, and the second soft coating layer includes the silver nanowires and the carbon nanowires The tube and soft carbon may be included in a weight ratio of 1:0.01 to 5:0.5 to 20.

4th embodiment

In another embodiment of the present invention, the negative electrode active material manufacturing method includes (S41) preparing a dried product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires; (S42) preparing a first fired product having a first hard coating layer formed thereon, including amorphous hard carbon on the outermost layer, by mixing the dried product and the pitch and performing primary firing; (S43) preparing a second fired product having a second hard coating layer formed on an outer circumferential surface of the first hard coating layer by mixing the first fired product and pitch and second fired; (S44) forming a carbon nanotube layer on the outer circumferential surface of the second hard coating layer; and (S45) forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

(S41) Dry product manufacturing step

The above step is a step of preparing a dried product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires.

In one embodiment, the flake graphite may include at least one of natural graphite and artificial graphite.

In one embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to a first solvent and dispersing to prepare a dispersion; And grinding the dispersion; can be prepared including.

In one embodiment, the silicon powder may have a spherical, polyhedral or elliptical shape. For example, it may be in the form of a sphere. For example, the silicon powder may have an average particle diameter (D50) of 2 to 5 μm. Under the above conditions, the dispersibility is excellent, and nano-silicon can be easily prepared.

In one embodiment, the first solvent may include one or more of water, ethanol, isopropyl alcohol, and potassium hydroxide (KOH). Mixability and dispersibility may be excellent when the first solvent is included.

In one embodiment, the first solvent may include ethanol and water (pure water) in a weight ratio of 1:0.5 to 1:1.5. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 10 parts by weight of a dispersant. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared. For example, the nano-silicon slurry may include 100 parts by weight of silicon powder, 800 to 1000 parts by weight of a first solvent, and 0.5 to 1.5 parts by weight of a dispersant.

For example, a dispersant may be added to the first solvent in the above amount and mixed, then the silicon powder may be added and mixed to prepare a dispersion, and the dispersion may be pulverized to prepare a nano-silicon slurry.

In one embodiment, the grinding may be performed by milling. In one embodiment, the milling is performed using a beads mill, a ball-mill, a high energy ball mill, a planetary mill, a stirred ball mill, or a vibration mill. (vibration mill) and the like.

For example, the ball mill may be made of a chemically inert material that does not react with the silicon powder and other organic components. For example, zirconia (ZrO ₂ ) may be included. In one embodiment, the ball mill may have an average particle diameter of 0.1 to 1 mm. Under the above conditions, nano-silicon can be easily produced.

In another embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to the first solvent and dispersing to prepare a dispersion; and pulverizing after adding a carbon-based component to the dispersion.

Here, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 20 parts by weight of a dispersant. Under the above conditions, the pulverization efficiency of the silicon powder is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

For example, the nano-silicon slurry may include isopropyl alcohol and ethanol as the first solvent in a weight ratio of 1:3 to 1:6. Dispersion and pulverization efficiency of the silicon powder may be excellent under the mixing weight ratio condition.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the carbon-based component may include at least one of carbon fibers, nano-carbon fibers, flake graphite, and multi-layer graphene. When the carbon-based component is added, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon can be easily produced.

For example, the carbon-based component may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicon powder. When introduced under the above conditions, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

More specifically, when preparing the nano-silicon slurry, a first solvent containing ethanol and isopropyl alcohol in a weight ratio of 1: 4 was prepared, and 98% by weight of stearic acid and 2% by weight of N-methyl pyrrolidone (NMP) were mixed as a dispersant so you can prepare. Then, 100 parts by weight of the silicon powder, 5 to 1500 parts by weight of the first solvent, 0.1 to 20 parts by weight of the dispersing agent, and 0.01 to 10 parts by weight of the carbon-based component (carbon fiber) are added, mixed, and pulverized with a ball mill to prepare a nano-silicon slurry can do.

For example, in the case of grinding using the ball mill, the shaft of the wet mill may be operated at a low rotational condition for 4 hours (1200 rpm, based on a chamber of 10L), and at a high rotational speed (1650 rpm) for 14 hours. As described above, nano-silicon having an average particle diameter (D50) of 98 nm can be manufactured by a wet grinding method using 0.1 mm zirconia (ZrO ₂ ) balls. In one embodiment, the nano-silicon included in the nano-silicon slurry may have an average particle diameter of 1 to 250 nm. For another example, it may be 90 to 110 nm.

In one embodiment, the graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; In addition, it may be prepared by including; pulverizing the calcined graphite mixture. When the prepared graphite ball is included, a core including a porous matrix including nano-silicon and amorphous hard carbon is easily formed, and the anode active material may have excellent capacity characteristics, durability, and structural stability. For example, during the pressurization, the density of the graphite mixture may be increased to 1.2 g/cc or more for firing.

For example, the graphite ball is prepared by preparing a graphite mixture containing 100 parts by weight of pitch and 5 to 1000 parts by weight of graphite such as artificial graphite or natural graphite having a size of 1 to 6 μm, and then mixing it with 5 to 50 atm. Graphite balls may be produced by pressurizing (compressing) under pressure conditions, firing at 400 to 650 ° C, and then pulverizing. Under the above conditions, mixing and dispersibility are excellent, and graphite balls can be easily manufactured.

For example, the graphite ball may be applied in the form of a graphite ball mixture solution. For example, the graphite mixture may further include a second solvent. In one embodiment, the second solvent may include at least one of N-methylpyrrolidone (NMP), ethanol, and water. Mixability and dispersibility may be excellent when the second solvent is included. For example, the second solvent may include all of N-methylpyrrolidone (NMP), ethanol, and water.

More specifically, the graphite ball is prepared by dissolving pitch in the N-methylpyrrolidone, mixing with ethanol, adding water (pure water) and mixing to prepare a binder solution; And adding flake graphite to the binder solution and stirring it; can be prepared including.

In one embodiment, the pitch may include one or more of petroleum pitch (pyrolysis fuel oil pitch) and coal-based pitch (coal tar pitch). When the pitch is included, when the anode active material including the graphite ball and the nano-silicon is fired at a high temperature of 800° C. or higher, amorphous carbon is coated on the inner surface of the nano-silicon surrounding the graphite ball, and the binder properties between the nano-silicon or Binder properties between the graphite ball and the nano-silicon may be excellent.

For example, the graphite ball is prepared by mixing graphite with a binder solution containing pitch and a second solvent to prepare a graphite mixture; calcining by pressing the graphite mixture; And, preparing a graphite ball by grinding and sintering the calcined graphite mixture; may be prepared including.

In one embodiment, the graphite mixture may include 500 to 2500 parts by weight of the second solvent based on 100 parts by weight of the pitch. Mixability and dispersibility may be excellent when included in the above range. For example, 800 to 1300 parts by weight may be included.

For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 3:1 to 5. When included in the above weight ratio, mixing and dispersibility are excellent, and graphite balls can be easily manufactured. For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 2:1.5 to 3.

In one embodiment, the same graphite as described above may be used. In one embodiment, the graphite ball may include at least one of natural graphite, artificial graphite, porous carbon, silicon, and tangled round carbon nanotubes.

For example, the graphite ball may be manufactured by adding 30 to 200 parts by weight of the flake graphite based on 100 parts by weight of pitch and mixing (stirring) to form a graphite ball. Graphite balls are easily formed under the above conditions, and the structural stability, high capacity and high output characteristics of the present invention may be excellent. For example, 50 to 150 parts by weight of flake graphite may be added to 100 parts by weight of the pitch.

The graphite ball may be formed in a spherical or oval shape by mixing flake graphite and pitch. In one embodiment, the graphite balls may have an average particle diameter of 0.3 to 20 μm. Under the above conditions, an anode active material can be easily formed. For example, the graphite ball may have a porous spherical shape. The graphite balls are not disintegrated in the mixed solution due to the binder properties of the pitch.

The first mixture includes the graphite balls, flake graphite, pitch, nano-silicon, and a solvent, and the solvent may include at least one of ethanol, isopropyl alcohol, and water.

In one embodiment, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.01 to 5:2 to 8:1 to 25:5 to 70. When included in the mixing weight ratio, the electrical conductivity, mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared. For example, the first mixture may include the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.1 to 3:4 to 6:5 to 10:10 to 15.

In one embodiment, the first mixture may include 1 to 5 parts by weight of pitch based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

The powder size of the negative electrode active material can be easily controlled through drying of the first mixture. For example, the drying may be performed using a spray dryer or the like. For example, the drying may be spray-dried using a spray dryer equipped with a single-fluid nozzle, a double-fluid nozzle, or a quadruple-fluid nozzle.

In one embodiment, the building may be spherical, polyhedral or elliptical. For example, it may be spherical.

In one embodiment, the dry matter may have an average particle diameter (or size) of 0.1 to 15 μm. Mixability and formability may be excellent under the above conditions.

In one embodiment, when spray drying the first mixture using a hydraulic nozzle, the dried product prepared by setting the outlet temperature to 70 ~ 130 ° C. and carrying out the air flow condition of 650 ~ 850 sccm averages The particle size may be 7 to 14 μm. In another embodiment, when the first mixture is spray-dried using a quadruple nozzle, the dried product may have an average particle diameter of 0.1 to 8 μm.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowires may be included in the first mixture in the form of a dispersion.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In another embodiment, the silver nanowire dispersion includes silver (Ag) nanowires, a first dispersant, and water, and the first dispersant is one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. may contain more than

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride. .

In one embodiment, the first mixture may include 0.01 to 5 parts by weight of silver nanowires based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

In one embodiment, the first mixture may include 0.01 to 20 parts by weight of the silver nanowire dispersion based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

(S42) 1st plastic product manufacturing step

The step is a step of preparing a first fired product in which a first hard coating layer containing amorphous hard carbon is formed on the outermost layer by mixing the dry material and the pitch and firing the first. In one embodiment, 1 to 30 parts by weight of pitch may be mixed with respect to 100 parts by weight of the dried material. Under the above conditions, the first hard coating layer can be easily formed.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

In one embodiment, the primary firing may be carried out by raising the temperature to 600 ~ 1250 ℃. During the firing, the pitch in the dried material is liquefied in the range of 200 ~ 300 ℃, the solvent of the pitch evaporates in the range of 350 ~ 550 ℃, and the thermosetting material in the range of 600 ~ 1250 ℃ can be carbonized. When fired under the above conditions, a core in which flake graphite is dispersed in a porous matrix containing nano-silicon and first amorphous hard carbon is formed, and a first hard coating layer containing the amorphous hard carbon may be formed on the outermost part of the core. there is.

(S43) 2nd plastic product manufacturing step

The step is a step of preparing a second fired product in which a second hard coating layer is formed on the outer circumferential surface of the first hard coating layer by mixing the first fired product and pitch and second fired.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

In one embodiment, 1 to 30 parts by weight of pitch may be mixed with respect to 100 parts by weight of the primary firing material. Under these conditions, the second hard coating layer can be easily formed.

In one embodiment, the secondary firing may be carried out by raising the temperature to 600 ~ 1250 ℃. During the firing, the pitch is solutionized in the range of 200 ~ 300 ℃, the solvent of the pitch evaporates in the area of 350 ~ 550 ℃, and the thermosetting material in the area of 600 ~ 1250 ℃ can be carbonized. When fired under the above conditions, a first hard coating layer containing amorphous hard carbon is formed on the outermost part of the core in which flake graphite is dispersed in a porous matrix containing nano-silicon and first amorphous hard carbon, and the first hard carbon is formed. A secondary fired product having a second hard coating layer containing the amorphous hard carbon formed on the outer circumferential surface of the coating layer may be manufactured.

(S44) Carbon Nanotube Layer Forming Step

The step is a step of forming a carbon nanotube layer on the outer circumferential surface of the second hard coating layer. The carbon nanotube layer may be formed by applying and drying a carbon nanotube solution on the outer circumferential surface of the second hard coating layer.

In one embodiment, the carbon nanotube solution may include carbon nanotubes, carboxymethylcellulose, and a solvent. The solvent may include at least one of water and an alcohol-based solvent. For example, the carbon nanotube solution may include 0.1 to 5% by weight of carbon nanotubes, 0.01 to 3% by weight of carboxymethyl cellulose, and the balance of the solvent. After applying the carbon nanotube solution, the carbon nanotubes may be formed on the surface of the soft coating layer by drying.

For example, the carbon nanotubes may have a length of 0.1 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 5 to 50 μm.

In one embodiment, 0.01 to 50 parts by weight of the carbon nanotube solution may be included with respect to 100 parts by weight of the second fired material. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, after the step of forming the carbon nanotube layer, the step of forming an organic coating layer on the surface of the carbon nanotube layer of the negative electrode active material may be further included.

In one embodiment, the organic coating layer may be included for the purpose of improving thermal stability and lifespan of the negative electrode active material.

In one embodiment, the organic coating layer may include at least one of a polyolefin-based compound, a polyolefin wax, and an acrylic compound. The polyolefin may include at least one of polyethylene and polypropylene.

(S45) Silver Nano Layer Formation Step

The above step is a step of forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer. In one embodiment, the silver nanowire layer may be prepared by applying a silver (Ag) nanowire dispersion to an outer circumferential surface of the carbon nanotube layer and heat-treating at 80 to 150°C. Under the above conditions, the silver nanowire layer can be easily formed.

In another embodiment, the silver nanowire layer may be formed by chemical vapor deposition (CVD) of silver (Ag) nanowires on the outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a first dispersant, and water, and the first dispersant includes at least one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. can do.

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight of the secondary firing material in which the carbon nanotubes are formed. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the prepared negative electrode active material may further include a step of disintegrating and classifying the negative electrode active material using a screen, a sieve, or the like.

In one embodiment, the anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing flake graphite and silver nanowires dispersed in the porous matrix; a first hard coating layer and a second hard coating layer sequentially formed on an outer circumferential surface of the core and each containing amorphous hard carbon; a carbon nanotube layer formed on an outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 35% by weight of a first hard coating layer. % by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

5th embodiment

In another embodiment of the present invention, the negative electrode active material manufacturing method includes (S51) preparing a dried product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, and flake graphite; (S52) preparing a first fired product having a first hard coating layer comprising amorphous hard carbon on the outermost layer by first firing the dried product; (S53) preparing an intermediate body in which a soft coating layer is formed on an outer circumferential surface of the first hard coating layer by mixing a carbon precursor with the first fired product and performing heat treatment; (S54) preparing a secondary firing product by mixing pitch with the intermediate and performing secondary firing; (S55) forming a carbon nanotube layer on the outer circumferential surface of the second fired product; and (S56) forming a silver nanowire layer on the outer circumferential surface of the carbon nanotube layer. A second hard coating layer containing hard carbon is sequentially formed.

(S51) Dry product manufacturing step

The above step is a step of preparing a dry product by drying a first mixture including graphite balls, nano-silicon slurry, pitch, and flake graphite.

In one embodiment, the flake graphite may include at least one of natural graphite and artificial graphite.

In one embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to a first solvent and dispersing to prepare a dispersion; And grinding the dispersion; can be prepared including.

In one embodiment, the silicon powder may have a spherical, polyhedral or elliptical shape. For example, it may be in the form of a sphere. For example, the silicon powder may have an average particle diameter (D50) of 2 to 5 μm. Under the above conditions, the dispersibility is excellent, and nano-silicon can be easily prepared.

In one embodiment, the first solvent may include one or more of water, ethanol, isopropyl alcohol, and potassium hydroxide (KOH). Mixability and dispersibility may be excellent when the first solvent is included.

In one embodiment, the first solvent may include ethanol and water (pure water) in a weight ratio of 1:0.5 to 1:1.5. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 10 parts by weight of a dispersant. Under the above conditions, mixing and dispersibility are excellent, and nano-silicon can be easily prepared. For example, the nano-silicon slurry may include 100 parts by weight of silicon powder, 800 to 1000 parts by weight of a first solvent, and 0.5 to 1.5 parts by weight of a dispersant.

For example, a dispersant may be added to the first solvent in the above amount and mixed, then the silicon powder may be added and mixed to prepare a dispersion, and the dispersion may be pulverized to prepare a nano-silicon slurry.

In one embodiment, the grinding may be performed by milling. In one embodiment, the milling is performed using a beads mill, a ball-mill, a high energy ball mill, a planetary mill, a stirred ball mill, or a vibration mill. (vibration mill) and the like.

For example, the ball mill may be made of a chemically inert material that does not react with the silicon powder and other organic components. For example, zirconia (ZrO ₂ ) may be included. In one embodiment, the ball mill may have an average particle diameter of 0.1 to 1 mm. Under the above conditions, nano-silicon can be easily produced.

In another embodiment, the nano-silicon slurry is prepared by adding silicon powder and a dispersant to the first solvent and dispersing to prepare a dispersion; and pulverizing after adding a carbon-based component to the dispersion.

Here, the nano-silicon slurry may include 100 parts by weight of silicon powder, 5 to 1500 parts by weight of a first solvent, and 0.1 to 20 parts by weight of a dispersant. Under the above conditions, the pulverization efficiency of the silicon powder is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

For example, the nano-silicon slurry may include isopropyl alcohol and ethanol as the first solvent in a weight ratio of 1:3 to 1:6. Dispersion and pulverization efficiency of the silicon powder may be excellent under the mixing weight ratio condition.

The dispersant may include at least one of polyvinylpyrrolidone, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, stearic acid, palmitic acid, oleic acid and lauric acid. can When the dispersing agent is included, the silicon powder has excellent dispersibility, so that nano-silicon can be easily prepared. For example, stearic acid may be included. For example, the dispersant may be used by mixing stearic acid and N-methylpyrrolidone (NMP).

In one embodiment, the carbon-based component may include at least one of carbon fibers, nano-carbon fibers, flake graphite, and multi-layer graphene. When the carbon-based component is added, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon can be easily produced.

For example, the carbon-based component may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicon powder. When introduced under the above conditions, the pulverization speed of the silicon powder is increased, and the pulverization efficiency is excellent, so that nano-silicon is easily produced, and re-agglomeration of the pulverized silicon is suppressed, thereby increasing the pulverization efficiency.

More specifically, when preparing the nano-silicon slurry, a first solvent containing ethanol and isopropyl alcohol in a weight ratio of 1: 4 was prepared, and 98% by weight of stearic acid and 2% by weight of N-methyl pyrrolidone (NMP) were mixed as a dispersant so you can prepare. Then, 100 parts by weight of the silicon powder, 5 to 1500 parts by weight of the first solvent, 0.1 to 20 parts by weight of the dispersing agent, and 0.01 to 10 parts by weight of the carbon-based component (carbon fiber) are added, mixed, and pulverized with a ball mill to prepare a nano-silicon slurry can do.

For example, in the case of grinding using the ball mill, the shaft of the wet mill may be operated at a low rotational condition for 4 hours (1200 rpm, based on a chamber of 10L), and at a high rotational speed (1650 rpm) for 14 hours. As described above, nano-silicon having an average particle diameter (D50) of 98 nm can be manufactured by a wet grinding method using 0.1 mm zirconia (ZrO ₂ ) balls. In one embodiment, the nano-silicon included in the nano-silicon slurry may have an average particle diameter of 1 to 250 nm. For another example, it may be 90 to 110 nm.

In one embodiment, the graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; In addition, it may be prepared by including; pulverizing the calcined graphite mixture. When the prepared graphite ball is included, a core including a porous matrix including nano-silicon and amorphous hard carbon is easily formed, and the anode active material may have excellent capacity characteristics, durability, and structural stability. For example, during the pressurization, the density of the graphite mixture may be increased to 1.2 g/cc or more for firing.

For example, the graphite ball is prepared by preparing a graphite mixture containing 100 parts by weight of pitch and 5 to 1000 parts by weight of graphite such as artificial graphite or natural graphite having a size of 1 to 6 μm, and then mixing it with 5 to 50 atm. Graphite balls may be produced by pressurizing (compressing) under pressure conditions, firing at 400 to 650 ° C, and then pulverizing. Under the above conditions, mixing and dispersibility are excellent, and graphite balls can be easily manufactured.

For example, the graphite ball may be applied in the form of a graphite ball mixture solution. For example, the graphite mixture may further include a second solvent. In one embodiment, the second solvent may include at least one of N-methylpyrrolidone (NMP), ethanol, and water. Mixability and dispersibility may be excellent when the second solvent is included. For example, the second solvent may include all of N-methylpyrrolidone (NMP), ethanol, and water.

More specifically, the graphite ball is prepared by dissolving pitch in the N-methylpyrrolidone, mixing with ethanol, adding water (pure water) and mixing to prepare a binder solution; And adding flake graphite to the binder solution and stirring it; can be prepared including.

In one embodiment, the pitch may include one or more of petroleum pitch (pyrolysis fuel oil pitch) and coal-based pitch (coal tar pitch). When the pitch is included, when the anode active material including the graphite ball and the nano-silicon is fired at a high temperature of 800° C. or higher, amorphous carbon is coated on the inner surface of the nano-silicon surrounding the graphite ball, and the binder properties between the nano-silicon or Binder properties between the graphite ball and the nano-silicon may be excellent.

For example, the graphite ball is prepared by mixing graphite with a binder solution containing pitch and a second solvent to prepare a graphite mixture; calcining by pressing the graphite mixture; And, preparing a graphite ball by grinding and sintering the calcined graphite mixture; may be prepared including.

In one embodiment, the graphite mixture may include 500 to 2500 parts by weight of the second solvent based on 100 parts by weight of the pitch. Mixability and dispersibility may be excellent when included in the above range. For example, 800 to 1300 parts by weight may be included.

For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 3:1 to 5. When included in the above weight ratio, mixing and dispersibility are excellent, and graphite balls can be easily manufactured. For example, the second solvent may include N-methylpyrrolidone, ethanol, and water in a weight ratio of 1:1 to 2:1.5 to 3.

In one embodiment, the same graphite as described above may be used. In one embodiment, the graphite ball may include at least one of natural graphite, artificial graphite, porous carbon, silicon, and tangled round carbon nanotubes.

For example, the graphite ball may be manufactured by adding 30 to 200 parts by weight of the flake graphite based on 100 parts by weight of pitch and mixing (stirring) to form a graphite ball. Graphite balls are easily formed under the above conditions, and the structural stability, high capacity and high output characteristics of the present invention may be excellent. For example, 50 to 150 parts by weight of flake graphite may be added to 100 parts by weight of the pitch.

The graphite ball may be formed in a spherical or oval shape by mixing flake graphite and pitch. In one embodiment, the graphite balls may have an average particle diameter of 0.3 to 20 μm. Under the above conditions, an anode active material can be easily formed. For example, the graphite ball may have a porous spherical shape. The graphite balls are not disintegrated in the mixed solution due to the binder properties of the pitch.

The first mixture includes the graphite balls, flake graphite, pitch, nano-silicon, and a solvent, and the solvent may include at least one of ethanol, isopropyl alcohol, and water.

In one embodiment, the first mixture may include the graphite balls, flake graphite, pitch, and nano-silicon in a weight ratio of 1:2 to 8:1 to 25:5 to 70. When included in the mixing weight ratio, the electrical conductivity, mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared. For example, the first mixture may include the graphite balls, flake graphite, pitch, and nano-silicon in a weight ratio of 1:4 to 6:5 to 10:10 to 15.

In one embodiment, the first mixture may include 1 to 5 parts by weight of pitch based on 100 parts by weight of the nano-silicon. Under the above conditions, the mixing and dispersibility of the first mixture are excellent, and an anode active material can be easily prepared.

The powder size of the negative electrode active material can be easily controlled through drying of the first mixture. For example, the drying may be performed using a spray dryer or the like. For example, the drying may be spray-dried using a spray dryer equipped with a single-fluid nozzle, a double-fluid nozzle, or a quadruple-fluid nozzle.

In one embodiment, the building may be spherical, polyhedral or elliptical. For example, it may be spherical.

In one embodiment, the dry matter may have an average particle diameter (or size) of 0.1 to 15 μm. Mixability and formability may be excellent under the above conditions.

In one embodiment, when spray drying the first mixture using a hydraulic nozzle, the dried product prepared by setting the outlet temperature to 70 ~ 130 ° C. and carrying out the air flow condition of 650 ~ 850 sccm averages The particle size may be 7 to 14 μm. In another embodiment, when the first mixture is spray-dried using a quadruple nozzle, the dried product may have an average particle diameter of 0.1 to 8 μm.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

(S52) 1st firing product manufacturing step

The above step is a step of preparing a first fired product having a first hard coating layer including amorphous hard carbon on the outermost layer by first firing the dried product.

In one embodiment, the primary firing may be carried out by raising the temperature to 600 ~ 1250 ℃. During the firing, the pitch in the dried material is liquefied in the range of 200 ~ 300 ℃, the solvent of the pitch evaporates in the range of 350 ~ 550 ℃, and the thermosetting material in the range of 600 ~ 1250 ℃ can be carbonized. When fired under the above conditions, a core in which flake graphite is dispersed in a porous matrix containing nano-silicon and amorphous hard carbon is formed, and a first hard coating layer containing the amorphous hard carbon may be formed on the outermost part of the core.

(S53) intermediate manufacturing step

The step is a step of preparing an intermediate body in which a soft coating layer is formed on an outer circumferential surface of the first hard coating layer by mixing a carbon precursor with the first fired product and performing heat treatment.

In one embodiment, heat treatment may be performed by including 0.1 to 30 parts by weight of the carbon precursor with respect to 100 parts by weight of the first fired material. When included in the content range, the mixing property is excellent, and an intermediate in which a soft coating layer is formed on the outer circumferential surface of the first hard coating layer may be formed.

In one embodiment, the carbon precursor includes at least one of polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, polyvinylidene fluoride, styrene butadiene rubber, and sucrose can do. When the carbon precursor is included, a soft coating layer can be easily formed.

For example, the carbon precursor may further include a solvent. The solvent may include at least one of water, an ethanol-based solvent, an amide-based solvent, an ester-based solvent, and a hydrocarbon-based solvent. When the solvent is included, workability may be excellent.

The alcohol-based solvent may include at least one of methanol, ethanol, isopropanol, and butanol.

The amide-based solvent may include at least one of N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and dimethylformamide (DMF).

The hydrocarbon-based solvent may include at least one of toluene and xylene.

In one embodiment, the heat treatment may be performed at 80 to 300 °C. During heat treatment under the above conditions, a soft coating layer can be easily formed on the outer circumferential surface of the first hard coating layer.

(S54) 2nd plastic product manufacturing step

The step is a step of preparing a secondary fired product by mixing pitch with the intermediate and performing secondary firing.

In one embodiment, the pitch may include one or more of petroleum-based pitch (pyrolysis fuel oil pitch), polyimide (polyimide), polyacrylonitrile (PAN), and coal-based pitch (coal tar pitch). When the pitch is included, binder characteristics and capacity characteristics may be excellent.

In one embodiment, heat treatment may be performed by including 0.1 to 30 parts by weight of the pitch based on 100 parts by weight of the intermediate. Mixability may be excellent when included within the above content range.

In one embodiment, the secondary firing may be carried out by raising the temperature to 600 ~ 1250 ℃. During the firing, the pitch is solutionized in the range of 200 ~ 300 ℃, the solvent of the pitch evaporates in the area of 350 ~ 550 ℃, and the thermosetting material in the area of 600 ~ 1250 ℃ can be carbonized. In the second firing under the above conditions, in the second firing product, a first hard coating layer containing amorphous hard carbon, an amorphous carbon layer, and a second hard coating layer containing amorphous hard carbon are sequentially formed on the outermost part.

(S55) Carbon nanotube layer formation step

The step is a step of forming a carbon nanotube layer on the outer circumferential surface of the second hard coating layer. The carbon nanotube layer may be formed by applying and drying a carbon nanotube solution on the outer circumferential surface of the second hard coating layer.

In one embodiment, the carbon nanotube solution may include carbon nanotubes, carboxymethylcellulose, and a solvent. The solvent may include at least one of water and an alcohol-based solvent. For example, the carbon nanotube solution may include 0.1 to 5% by weight of carbon nanotubes, 0.01 to 3% by weight of carboxymethyl cellulose, and the balance of the solvent. After applying the carbon nanotube solution, the carbon nanotubes may be formed on the surface of the soft coating layer by drying.

For example, the carbon nanotubes may have a length of 0.1 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 5 to 50 μm.

In one embodiment, 0.01 to 50 parts by weight of the carbon nanotube solution may be included with respect to 100 parts by weight of the heat-treated intermediate. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, after the step of forming the carbon nanotube layer, the step of forming an organic coating layer on the surface of the carbon nanotube layer of the negative electrode active material may be further included.

In one embodiment, the organic coating layer may be included for the purpose of improving thermal stability and lifespan of the negative electrode active material.

In one embodiment, the organic coating layer may include at least one of a polyolefin-based compound, a polyolefin wax, and an acrylic compound. The polyolefin may include at least one of polyethylene and polypropylene.

(S56) Silver Nanowire Layer Forming Step

The above step is a step of forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowire layer may be prepared by applying a silver (Ag) nanowire dispersion to an outer circumferential surface of the carbon nanotube layer and heat-treating at 80 to 150°C. Under the above conditions, the silver nanowire layer can be easily formed.

In another embodiment, the silver nanowire layer may be formed by chemical vapor deposition (CVD) of silver (Ag) nanowires on the outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowires prepared by a conventional method may be used without limitation. For example, the silver nanowire is made of a reducing solvent such as a diol, glycol, and polyol compound containing two or more hydroxyl groups (-OH) in a molecule, and a reducing solvent such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid. After mixing the water-soluble polymer, it is heated to prepare a mixed solution, and an ammonium-based compound, a nitrate compound, and a metal salt containing silver (Ag) are sequentially added to the mixed solution and reacted to produce silver nanowires.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a binder, and a dispersion solvent, and the dispersion solvent may include at least one of water and an organic solvent. The binder may include at least one of polyolefin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyacrylic acid.

In one embodiment, the silver nanowire dispersion includes silver nanowires, a first dispersant, and water, and the first dispersant includes at least one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether. can do.

In another embodiment, the silver nanowire dispersion includes silver nanowires, a second dispersing agent, and an organic solvent, and the dispersing agent may include at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and polyvinylidene fluoride.

In one embodiment, 0.01 to 50 parts by weight of the silver nanowire layer may be included with respect to 100 parts by weight of the heat-treated fired product. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the prepared negative electrode active material may further include a step of disintegrating and classifying the negative electrode active material using a screen, a sieve, or the like.

In one embodiment, the anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing flake graphite dispersed in the porous matrix; a first hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; an amorphous carbon layer formed on an outer circumferential surface of the first hard coating layer; a second hard coating layer formed on an outer circumferential surface of the amorphous carbon layer and containing amorphous hard carbon; a carbon nanotube layer formed on an outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano-silicon, 0 to 60% by weight of flake graphite, 5 to 50% by weight of amorphous hard carbon, 0.1 to 35% by weight of the first hard coating layer, and 0.1 to 15% by weight of the amorphous carbon layer. % by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

Silicon carbon composite anode active material containing silver nanowires

Another aspect of the present invention relates to a silicon carbon composite anode active material containing silver nanowires prepared by a method for manufacturing a silicon carbon composite anode active material containing silver nanowires.

Example 1

1 shows a silicon carbon composite anode active material having a double layer structure according to one embodiment of the present invention. Referring to FIG. 1, the anode active material 100 includes a porous matrix including nano-silicon (Si) 12 and amorphous hard carbon 14, silver nanowires (not shown), and flake graphite dispersed in the porous matrix. a core 10 comprising (16); A hard coating layer 20 formed on the outer circumferential surface of the core 10; A soft coating layer 30 formed on the outer circumferential surface of the hard coating layer 20; and a carbon nanotube layer 40 formed on an outer circumferential surface of the soft coating layer 30 . and a silver (Ag) nanowire layer 50 formed on an outer circumferential surface of the carbon nanotube layer 40 .

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 1 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. , 0.1 to 5% by weight of the soft coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

In one embodiment, the negative active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the soft coating layer has a thickness of 0.05 to 15 μm. 5 μm, the hard coating layer may have a thickness of 0.05 μm to 5 μm, the carbon nanotube layer may have a thickness of 0.01 μm to 10 μm, and the silver nanowire layer may have a thickness of 0.01 μm to 10 μm.

In one embodiment, the anode active material 100 may have a spherical or oval shape. For example, it may be spherical.

In one embodiment, the negative electrode active material may have an average diameter of 0.5 to 50 μm. Under the condition of the average diameter, high capacity, high output characteristics and structural stability are excellent, and volume expansion during charging and discharging is minimized, thereby providing excellent long lifespan characteristics. For example, it may be 5 to 15 μm.

In one embodiment, the negative electrode active material is porous, and the porosity of the surface may be 20 to 60% by volume. Under the above conditions, electrolyte impregnability and structural stability may be excellent, and high capacity, high output characteristics and structural stability may be excellent.

In one embodiment, the negative electrode active material may have a particle density of 1.2 to 2.0 g/cm ³ . In another embodiment, the negative electrode active material may have a particle density of 0.8 to 1.2 g/cm ³ . Under the above conditions, light weight and structural stability may be excellent.

In one embodiment, the negative electrode active material may have an average pore size of 0.5 to 2 μm. In another embodiment, the negative electrode active material may have an average pore size of 0.01 to 0.1 μm. Under the above conditions, structural stability, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have an average particle diameter (d50) of 5 to 7 μm. In another embodiment, the negative electrode active material may have an average particle diameter (d50) of 8 to 11 μm.

In one embodiment, the negative electrode active material may have a weight capacity ratio of 450 to 1800 mAh/g. Under the above conditions, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have a tap density of 0.65 to 1.3 g/cm ³ . In one embodiment, the negative electrode active material may have a specific surface area (BET) of 3.5 to 15 m ² /g. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

core

The core 10 includes a porous matrix including nano-silicon (Si) 12 and amorphous hard carbon 14, and silver nanowires (not shown) and flake graphite 16 dispersed in the porous matrix. Referring to FIG. 1 , amorphous hard carbon may be formed surrounding the entire surface of the core 10 . Under the above conditions, structural stability is excellent to prevent cracking and destruction, and capacity degradation can be minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the core may have an average diameter (or maximum length) of 1 to 30 μm. Under the above conditions, high capacity and high output characteristics may be excellent, and structural stability may be excellent. For example, it may be 1 to 15 μm.

The core may be spherical or elliptical. For example, it may be spherical.

In one embodiment, the amorphous hard carbon may include at least one of hard carbon formed by firing graphite balls and hard carbon formed by firing pitch.

In one embodiment, the amorphous hard carbon may be included in an amount of 5 to 50% by weight based on the total weight of the negative electrode active material. When included within the above range, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, the amorphous hard carbon may be included in an amount of 5 to 35% by weight. For another example, the amorphous hard carbon may be included in an amount of 10 to 35% by weight.

The nano-silicon may be included to secure high capacity and high output characteristics. In one embodiment, the nano-silicon may have an average diameter of 1.5 μm or less. For example, the nano-silicon may have a smaller diameter than the core. When included within the above range, mixing and dispersibility may be excellent, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be 60 nm to 100 nm. Another example may be 40 to 120 nm.

In one embodiment, the nano-silicon may be spherical, polyhedral, elliptical or irregular. For example, it may be spherical.

In one embodiment, the nano-silicon may be included in an amount of 25 to 80% by weight based on the total weight of the negative electrode active material. In the above content range, mixing properties and durability may be excellent, and high capacity and high output characteristics may be excellent.

For example, the nano-silicon may be included in an amount of 25 to 55% by weight based on the total weight of the anode active material. In another embodiment, the nano-silicon may be included in an amount of 45 to 80% by weight. Under the above conditions, high capacity and high output characteristics may be excellent.

When the silver nanowires are included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

For example, 0.01 to 5% by weight of the silver nanowires may be included with respect to the total weight of the negative electrode active material. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics. For another example, 0.05 to 5% by weight may be included.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the flake graphite may be included in an amount of 1 to 60% by weight based on the total weight of the negative electrode active material. When included within the above range, mixing and dispersibility may be excellent, and electrical conductivity, high capacity and high power characteristics of the anode active material may be excellent.

In one embodiment, the flake graphite may have an average size of 0.2 to 8 μm. The "size" may mean the "maximum length" of flake graphite. Mixability and dispersibility may be excellent under the average size condition, and electrical conductivity, high capacity, and high power characteristics of the anode active material may be excellent. For example, the average size may be 0.2 to 2 μm.

Referring to FIG. 1 , the anode active material 100 may further include a conductive powder 18 dispersed in a porous matrix. In one embodiment, the conductive powder may include at least one of carbon black, acetylene black, ketjen black, and furnace black. For example, carbon black may be included.

In one embodiment, the conductive powder may have an average particle diameter of 5 nm to 10 μm. Mixability and dispersibility may be excellent under the above conditions.

In one embodiment, the conductive powder may be included in an amount greater than 0 and less than 25% by weight based on the total weight of the negative electrode active material. When included in the above range, mixing and dispersibility may be excellent, and conductivity, high capacity and high output characteristics may be excellent. For example, 5 to 25% by weight may be included.

In one embodiment, when the conductive powder is further included, it may be further included in the nano-silicon slurry in the drying product manufacturing step. For another example, conductive powder may be further included during pitch mixing for firing. For another example, the outer circumferential surface of the fired product may be coated by adding conductive powder.

hard coating layer

A hard coating layer 20 containing amorphous hard carbon is formed on the outer circumferential surface of the core. The hard coating layer may have a thickness of 0.05 to 5 μm. Within this range, durability and structural stability of the present invention may be excellent.

In one embodiment, the amorphous hard carbon may include at least one of hard carbon formed by firing graphite balls and hard carbon formed by firing pitch.

The hard coating layer may be included in an amount of 0.1 to 10% by weight based on the total weight of the negative electrode active material. When included within the above range, durability and structural stability of the present invention may be excellent. For example, the hard coating layer may be included in an amount of 5 to 10% by weight based on the total weight of the negative electrode active material. For another example, the hard coating layer may be included in an amount of 10 to 35% by weight based on the total weight of the negative electrode active material.

soft coating layer

The soft coating layer 30 is formed on the outer circumferential surface 20 of the hard coating layer. The soft coating layer includes amorphous soft carbon and may be formed by heat-treating a carbon precursor. In one embodiment, the core (or hard coating layer) has a higher hardness than the soft coating layer. Under the above conditions, high-capacity and high-output characteristics are excellent, structural stability is excellent, and volume expansion is minimized during charging and discharging, so that long lifespan characteristics may be excellent.

2(a) is a schematic diagram of an anode active material according to one embodiment of the present invention, and FIG. 2(b) is a schematic diagram showing volume change during lithium ion intercalation/desorption reactions of the anode active material of the present invention. On the other hand, the biggest cause of the capacity reduction of the silicon-based negative electrode active material is a fracture phenomenon due to a large volume change that occurs during intercalation/desorption of lithium ions.

Referring to FIG. 2, when lithium is inserted into the anode active material 100, the external soft coating layer 30 increases in volume, but the internal hard coating layer 20 containing less lithium ions is relatively volume increases less. The stress gradient of the anode active material may generate stress that changes throughout the anode active material. Therefore, the anode active material of the present invention applies a structure of a soft coating layer having a soft property and a hard coating layer having a hard property, thereby generating a stress gradient and minimizing volume expansion during the lithium ion insertion process, It has excellent structural stability to prevent cracking and destruction, a stable SEI layer 200 is formed on the outer circumferential surface, and it has excellent long lifespan characteristics by minimizing capacity degradation.

In one embodiment, the soft coating layer 30 may have a thickness of 0.05 to 5 μm. In the above thickness range, cracking and destruction of the negative electrode active material may be prevented during lithium ion insertion/desorption reactions, and capacity degradation may be minimized, thereby providing excellent long lifespan characteristics. For example, the soft coating layer may have a thickness of 0.1 to 1.5 μm.

In one embodiment, the soft coating layer may be included in an amount of 0.1 to 5% by weight based on the total weight of the negative electrode active material. When included within the above range, cracking and destruction of the anode active material during lithium ion insertion/desorption reactions may be prevented, and capacity degradation may be minimized, resulting in excellent long lifespan characteristics. For example, the soft coating layer may be included in an amount of 0.1 to 3.0% by weight based on the total weight of the negative electrode active material. For example, 0.5 to 2% by weight may be included.

In one embodiment, the soft coating layer and the hard coating layer may be included in a weight ratio of 1:2 to 1:8. When included in the above weight ratio, the durability and structural stability of the negative electrode active material are excellent, and the ?tip喚? The effect of preventing destruction may be excellent.

Carbon nanotube layer

The carbon nanotube layer 40 is formed on the outer circumferential surface of the soft coating layer 30 . When the carbon nanotube layer is included, electrical conductivity is improved, and high-capacity and high-output effects may be excellent.

For example, the anode active material 100 may include a carbon nanotube layer including carbon nanotubes at the outermost part of the soft coating layer 30 . The carbon nanotube layer may mean a layer formed by the carbon nanotube spaces. For example, in the carbon nanotube layer, the carbon nanotubes are inserted into pores formed on the outermost surface or part of the core and the soft coating layer, or the carbon nanotubes are irregularly dispersed and adhered to the outer circumferential surface of the powder. can be For another example, the carbon nanotube layer 40 may be in a form in which carbon nanotubes are fixed by a binder or attached by van der Waals forces.

The carbon nanotubes may include at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and roped carbon nanotubes. there is.

In one embodiment, the carbon nanotube layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.05 to 5% by weight may be included.

For example, the carbon nanotube layer may have a thickness of 0.01 to 10 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotube layer may have a thickness of 1 to 10 μm.

For example, the carbon nanotubes may have a length of 0.01 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 0.5 to 50 μm.

silver nanowire layer

The silver nanowire layer 50 is formed on the outer circumferential surface of the carbon nanotube layer 40 . When the silver nanowire layer is included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire layer 50 may be fixed in an irregularly dispersed form by fixing the silver nanowires to the surface of the carbon nanotube layer by a binder.

For example, the silver nanowire layer 50 may be formed by crossing silver nanowires on the surface of the carbon nanotube layer 40 in a network form.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may have a thickness of 0.01 to 10 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.01 to 3% by weight may be included.

2nd embodiment

An anode active material according to another embodiment of the present invention includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver nanowires and flake graphite dispersed in the porous matrix; a first soft coating layer formed on an outer circumferential surface of the core; a hard coating layer formed on an outer circumferential surface of the first soft coating layer and containing amorphous hard carbon; a second soft coating layer formed on an outer circumferential surface of the hard coating layer; a carbon nanotube layer formed on an outer circumferential surface of the second soft coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. , 0.1 to 15 wt% of the first soft coating layer, 0.1 to 15 wt% of the second soft coating layer, 0.01 to 10 wt% of the carbon nanotube layer, and 0.01 to 10 wt% of the silver nanowire layer.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the first soft coating layer has a thickness 0.05 to 5 μm, the second soft coating layer has a thickness of 0.5 to 10 μm, the hard coating layer has a thickness of 0.05 to 5 μm, the carbon nanotube layer has a thickness of 0.01 to 10 μm, and the The silver nanowire layer may have a thickness of 0.01 to 10 μm.

In one embodiment, the negative electrode active material may have an average diameter of 0.5 to 50 μm. Under the condition of the average diameter, high capacity, high output characteristics and structural stability are excellent, and volume expansion during charging and discharging is minimized, thereby providing excellent long lifespan characteristics. For example, it may be 5 to 15 μm.

In one embodiment, the negative electrode active material is porous, and the porosity of the surface may be 20 to 50% by volume. Under the above conditions, electrolyte impregnability and structural stability may be excellent, and high capacity, high output characteristics and structural stability may be excellent.

In one embodiment, the negative electrode active material may have a particle density of 1.2 to 2.0 g/cm ³ . In another embodiment, the negative electrode active material may have a particle density of 0.8 to 1.2 g/cm ³ . Under the above conditions, light weight and structural stability may be excellent.

In one embodiment, the negative electrode active material may have an average pore size of 0.5 to 2 μm. In another embodiment, the negative electrode active material may have an average pore size of 0.01 to 0.1 μm. Under the above conditions, structural stability, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have an average particle diameter (d50) of 5 to 7 μm. In another embodiment, the negative electrode active material may have an average particle diameter (d50) of 8 to 11 μm.

In one embodiment, the negative electrode active material may have a weight capacity ratio of 650 to 1600 mAh/g. Under the above conditions, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have a tap density of 0.65 to 1.3 g/cm ³ . In one embodiment, the negative electrode active material may have a specific surface area (BET) of 1.5 to 6 m ² /g. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

core

The core includes a porous matrix including nano-silicon (Si) and amorphous hard carbon, and silver nanowires and flake graphite dispersed in the porous matrix. The amorphous hard carbon may be formed surrounding the entire surface of the core. Under the above conditions, structural stability is excellent to prevent cracking and destruction, and capacity degradation can be minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the core may have an average diameter (or maximum length) of 1 to 30 μm. Under the above conditions, high capacity and high output characteristics may be excellent, and structural stability may be excellent. For example, it may be 1 to 15 μm.

For example, the porous matrix may have a porous structure by combining nano-silicon with the amorphous hard carbon. In one embodiment, the porous matrix may have a porosity of 5 to 80%. Under the above conditions, the electrolyte solution impregnability may be excellent, and high capacity, high output characteristics and structural stability may be excellent.

The core may be spherical or elliptical. For example, it may be spherical.

In one embodiment, the amorphous hard carbon may include at least one of hard carbon formed by firing graphite balls and hard carbon formed by firing pitch.

In one embodiment, the amorphous hard carbon of the core may be included in an amount of 5 to 50% by weight based on the total weight of the negative electrode active material. When included within the above range, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, the amorphous hard carbon may be included in an amount of 5 to 35% by weight. For another example, the amorphous hard carbon may be included in an amount of 10 to 35% by weight.

The nano-silicon may be included to secure high capacity and high output characteristics. In one embodiment, the nano-silicon may have an average diameter of 1.5 μm or less. For example, the nano-silicon may have a smaller diameter than the core. When included within the above range, mixing and dispersibility may be excellent, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be 60 nm to 100 nm. Another example may be 40 to 120 nm.

In one embodiment, the nano-silicon may be spherical, polyhedral, elliptical or irregular. For example, it may be spherical.

In one embodiment, the nano-silicon may be included in an amount of 25 to 80% by weight based on the total weight of the negative electrode active material. In the above content range, mixing properties and durability may be excellent, and high capacity and high output characteristics may be excellent. For example, 25 to 55% by weight may be included. In another embodiment, the nano-silicon may be included in an amount of 45 to 80% by weight.

When the silver nanowires are included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

For example, 0.01 to 5% by weight of the silver nanowires may be included with respect to the total weight of the negative electrode active material. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics. For another example, 0.05 to 5% by weight may be included.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the flake graphite may be included in an amount of 0 to 60% by weight based on the total weight of the negative electrode active material. When included within the above range, mixing and dispersibility may be excellent, and electrical conductivity, high capacity and high power characteristics of the anode active material may be excellent.

In one embodiment, the flake graphite may have an average size of 0.2 to 8 μm. The "size" may mean the "maximum length" of flake graphite. Mixability and dispersibility may be excellent under the average size condition, and electrical conductivity, high capacity, and high power characteristics of the anode active material may be excellent. For example, the average size may be 0.2 to 2 μm.

The anode active material may further include a conductive powder dispersed in a porous matrix. In one embodiment, the conductive powder may include at least one of carbon black, acetylene black, ketjen black, and furnace black. For example, carbon black may be included.

In one embodiment, the conductive powder may have an average particle diameter of 5 nm to 10 μm. Mixability and dispersibility may be excellent under the above conditions.

In one embodiment, the conductive powder may be included in an amount greater than 0 and less than 25% by weight based on the total weight of the negative electrode active material. When included in the above range, mixing and dispersibility may be excellent, and conductivity, high capacity and high output characteristics may be excellent. For example, 5 to 25% by weight may be included.

1st soft coating layer

The first soft coating layer is formed on the outer circumferential surface of the core. The first soft coating layer may include amorphous soft carbon and may be formed by heat-treating a carbon precursor. Under the above conditions, high-capacity and high-output characteristics are excellent, structural stability is excellent, and volume expansion is minimized during charging and discharging, so that long lifespan characteristics may be excellent.

In one embodiment, the first soft coating layer may have a thickness of 0.05 to 5 μm. In the above thickness range, cracking and destruction of the negative electrode active material may be prevented during lithium ion insertion/desorption reactions, and capacity degradation may be minimized, thereby providing excellent long lifespan characteristics. For example, the first soft coating layer may have a thickness of 0.1 to 1.5 μm.

In one embodiment, the first soft coating layer may be included in an amount of 0.1 to 15% by weight based on the total weight of the negative electrode active material. When included within the above range, cracking and destruction of the anode active material during lithium ion insertion/desorption reactions may be prevented, and capacity degradation may be minimized, resulting in excellent long lifespan characteristics. For example, 0.5 to 5% by weight may be included.

hard coating layer

The hard coating layer includes amorphous hard carbon and is formed on an outer circumferential surface of the first soft coating layer. In one embodiment, the hard coating layer may have a thickness of 0.01 to 10 μm. Durability and structural stability may be excellent in the above thickness range. For example, the hard coating layer may have a thickness of 0.05 to 5 μm.

In one embodiment, the hard coating layer may be included in an amount of 0.1 to 10% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be included in 5 to 10% by weight. For another example, 10 to 20% by weight may be included.

2nd soft coating layer

The second soft coating layer is formed on the outer circumferential surface of the hard coating layer. The second soft coating layer includes amorphous soft carbon and may be formed by heat-treating a carbon precursor. In one embodiment, the second soft coating layer may have a thickness of 0.1 to 5 μm. In the above thickness range, cracking and destruction of the negative electrode active material may be prevented during lithium ion insertion/desorption reactions, and capacity degradation may be minimized, thereby providing excellent long lifespan characteristics.

In one embodiment, the second soft coating layer may be included in an amount of 0.5 to 5.0% by weight based on the total weight of the negative electrode active material. When included within the above range, cracking and destruction of the anode active material during lithium ion insertion/desorption reactions may be prevented, and capacity degradation may be minimized, resulting in excellent long lifespan characteristics. For example, 0.5 to 2% by weight may be included.

In one embodiment, the second soft coating layer may have a thickness of 0.5 to 10 μm. In the above thickness range, cracking and destruction of the negative electrode active material may be prevented during lithium ion insertion/desorption reactions, and capacity degradation may be minimized, thereby providing excellent long lifespan characteristics. For example, the second soft coating layer may have a thickness of 0.5 to 5 μm.

In one embodiment, the sum of the first soft coating layer and the second soft coating layer may be included in an amount of 0.5 to 5.0% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

In one embodiment, the first soft coating layer, the second soft coating layer, and the hard coating layer may be included in a weight ratio of 1:0.5 to 3:3 to 8. When included in the above weight ratio, the durability and structural stability of the negative electrode active material are excellent, and the ?tip喚? The effect of preventing destruction may be excellent.

Carbon nanotube layer

A carbon nanotube layer is formed on the outer circumferential surface of the second soft coating layer. When the carbon nanotube layer is included, electrical conductivity is improved, and high-capacity and high-output effects may be excellent.

For example, the anode active material may include a carbon nanotube layer including carbon nanotubes at the outermost part of the second soft coating layer. The carbon nanotube layer may mean a layer formed by the carbon nanotube spaces. For example, in the carbon nanotube layer, the carbon nanotubes are inserted into pores formed on the outermost surface or part of the core and the second soft coating layer, or the carbon nanotubes are irregularly dispersed on the outer circumferential surface of the powder. may be in the form of For another example, the carbon nanotube layer may be in a form in which the carbon nanotubes are fixed by a binder or attached by van der Waals force.

The carbon nanotubes may include at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and roped carbon nanotubes. there is.

In one embodiment, the carbon nanotube layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.05 to 5% by weight may be included.

For example, the carbon nanotube layer may have a thickness of 0.01 to 10 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotube layer may have a thickness of 1 to 10 μm.

For example, the carbon nanotubes may have a length of 0.01 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 0.5 to 50 μm.

silver nanowire layer

A silver nanowire layer is formed on an outer circumferential surface of the carbon nanotube layer. When the silver nanowire layer is included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire layer may be fixed in an irregularly dispersed form by fixing the silver nanowires to the outer circumferential surface of the carbon nanotube layer by a binder.

For example, the silver nanowire layer may be formed by crossing silver nanowires in a network form on the outer circumferential surface of the carbon nanotube layer.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may have a thickness of 0.01 to 10 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.01 to 3% by weight may be included.

3rd embodiment

An anode active material according to another embodiment of the present invention includes a core including a porous matrix including nano-silicon (Si) and amorphous hard carbon; a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; a first soft coating layer formed on an outer circumferential surface of the hard coating layer and including soft carbon and silver nanowires; and a second soft coating layer formed on an outer circumferential surface of the first soft coating layer and including soft carbon, carbon nanotubes, and silver nanowires.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 5 to 50% by weight of amorphous hard carbon, 0.1 to 15% by weight of a hard coating layer, 0.1 to 15% by weight of a first soft coating layer, and 0.1 to 15% by weight of a second soft coating layer. 0.1 to 15% by weight, wherein the first soft coating layer includes the silver nanowires and soft carbon in a weight ratio of 1:0.5 to 1:20, and the second soft coating layer includes the silver nanowires and the carbon nanowires The tube and soft carbon may be included in a weight ratio of 1:0.01 to 5:0.5 to 20.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the hard coating layer has a thickness of 0.05 to 5 μm, and the first soft coating layer has a thickness of 0.05 ~ 5㎛, and the second soft coating layer may have a thickness of 0.5 ~ 10㎛.

In one embodiment, the negative electrode active material may have an average pore size of 0.5 to 2 μm. In another embodiment, the negative electrode active material may have an average pore size of 0.01 to 0.1 μm. Under the above conditions, structural stability, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have an average particle diameter (d50) of 5 to 7 μm. In another embodiment, the negative electrode active material may have an average particle diameter (d50) of 8 to 11 μm.

In one embodiment, the negative electrode active material may have a weight capacity ratio of 800 to 2000 mAh/g. Under the above conditions, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have a tap density of 0.65 to 1.3 g/cm ³ . In one embodiment, the negative electrode active material may have a specific surface area of 0.8 to 2.5 m ² /g. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

core

The core includes nano-silicon (Si) and amorphous hard carbon. The amorphous hard carbon may be formed surrounding the entire surface of the core. Under the above conditions, structural stability is excellent to prevent cracking and destruction, and capacity degradation can be minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the core may have an average diameter (or maximum length) of 1 to 30 μm. Under the above conditions, high capacity and high output characteristics may be excellent, and structural stability may be excellent. For example, it may be 1 to 15 μm.

For example, the porous matrix may have a porous structure by combining nano-silicon with the amorphous hard carbon. In one embodiment, the porous matrix may have a porosity of 5 to 80%. Under the above conditions, the electrolyte solution impregnability may be excellent, and high capacity, high output characteristics and structural stability may be excellent.

The core may be spherical or elliptical. For example, it may be spherical.

In one embodiment, the amorphous hard carbon may include at least one of hard carbon formed by firing graphite balls and hard carbon formed by firing pitch.

In one embodiment, the amorphous hard carbon of the core may be included in an amount of 5 to 50% by weight based on the total weight of the negative electrode active material. When included within the above range, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, the amorphous hard carbon may be included in an amount of 5 to 35% by weight. For another example, the amorphous hard carbon may be included in an amount of 10 to 35% by weight.

The nano-silicon may be included to secure high capacity and high output characteristics. In one embodiment, the nano-silicon may have an average diameter of 1.5 μm or less. For example, the nano-silicon may have a smaller diameter than the core. When included within the above range, mixing and dispersibility may be excellent, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be 60 nm to 100 nm. Another example may be 40 to 120 nm.

In one embodiment, the nano-silicon may be spherical, polyhedral, elliptical or irregular. For example, it may be spherical.

In one embodiment, the nano-silicon may be included in an amount of 25 to 80% by weight based on the total weight of the negative electrode active material. In the above content range, mixing properties and durability may be excellent, and high capacity and high output characteristics may be excellent. For example, 25 to 55% by weight may be included. In another embodiment, the nano-silicon may be included in an amount of 45 to 80% by weight.

The anode active material may further include a conductive powder dispersed in a porous matrix. In one embodiment, the conductive powder may include at least one of carbon black, acetylene black, ketjen black, and furnace black. For example, carbon black may be included.

In one embodiment, the conductive powder may have an average particle diameter of 5 nm to 10 μm. Mixability and dispersibility may be excellent under the above conditions.

In one embodiment, the conductive powder may be included in an amount greater than 0 and less than 25% by weight based on the total weight of the negative electrode active material. When included in the above range, mixing and dispersibility may be excellent, and conductivity, high capacity and high output characteristics may be excellent. For example, 5 to 25% by weight may be included.

hard coating layer

The hard coating layer includes amorphous hard carbon and is formed on an outer circumferential surface of the first soft coating layer. In one embodiment, the hard coating layer may have a thickness of 0.01 to 10 μm. Durability and structural stability may be excellent in the above thickness range. For example, the hard coating layer may have a thickness of 0.05 to 5 μm.

In one embodiment, the hard coating layer may be included in an amount of 0.1 to 15% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be included in 5 to 10% by weight. For another example, 10 to 20% by weight may be included.

1st soft coating layer

The first soft coating layer is formed on an outer circumferential surface of the hard coating layer. The first soft coating layer may include amorphous soft carbon and may be formed by heat-treating a carbon precursor and silver nanowires. Under the above conditions, high-capacity and high-output characteristics are excellent, structural stability is excellent, and volume expansion is minimized during charging and discharging, so that long lifespan characteristics may be excellent.

When the silver nanowires are included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

For example, nanowires included in the first soft coating layer may be included in an amount of 0.01 to 5% by weight based on the total weight of the negative electrode active material. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics. Other examples may include 0.1 to 3.5% by weight.

In one embodiment, the first soft coating layer may have a thickness of 0.01 to 5 μm. In the above thickness range, cracking and destruction of the negative electrode active material may be prevented during lithium ion insertion/desorption reactions, and capacity degradation may be minimized, thereby providing excellent long lifespan characteristics. For example, the first soft coating layer may have a thickness of 0.05 to 5 μm.

In one embodiment, the first soft coating layer may be included in an amount of 0.1 to 15% by weight based on the total weight of the negative electrode active material. When included within the above range, cracking and destruction of the anode active material during lithium ion insertion/desorption reactions may be prevented, and capacity degradation may be minimized, resulting in excellent long lifespan characteristics. For example, the first soft coating layer may be included in an amount of 0.5 to 5.0% by weight based on the total weight of the negative electrode active material.

The first soft coating layer may include the silver nanowires and soft carbon in a weight ratio of 1:0.5 to 1:20. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics.

2nd soft coating layer

The second soft coating layer is formed on the outer circumferential surface of the first soft coating layer. The second soft coating layer includes amorphous soft carbon, carbon nanotubes, and silver nanowires, and may be formed by heat-treating the carbon nanotubes (or the carbon nanotube solution), the silver nanowires, and the carbon precursor. Under the above conditions, electrical conductivity, high capacity, and high output characteristics are excellent, structural stability is excellent, and volume expansion during charging and discharging is minimized, so that long lifespan characteristics may be excellent.

The carbon nanotubes of the second soft coating layer may be inserted into pores formed on the surface or part of the core and the second soft coating layer, or the carbon nanotubes may be irregularly dispersed and adhered to the outer circumferential surface of the powder. . For another example, the carbon nanotube layer may be in a form in which the carbon nanotubes are fixed by a binder or attached by van der Waals force.

The carbon nanotubes may include at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and roped carbon nanotubes. there is.

For example, the carbon nanotubes may have a length of 0.01 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 5 to 50 μm.

When the silver nanowires are included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under these conditions, durability and electrical conductivity may be excellent.

For example, 0.01 to 6% by weight of the silver nanowires included in the second soft coating layer may be included with respect to the total weight of the negative electrode active material. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics. For another example, 0.05 to 5.5% by weight may be included.

In one embodiment, the second soft coating layer may have a thickness of 0.1 to 10 μm. In the above thickness range, cracking and destruction of the negative electrode active material may be prevented during lithium ion insertion/desorption reactions, and capacity degradation may be minimized, thereby providing excellent long lifespan characteristics. For example, the second soft coating layer may have a thickness of 0.5 to 10 μm.

In one embodiment, the second soft coating layer may be included in an amount of 0.1 to 15% by weight based on the total weight of the negative electrode active material. When included within the above range, electrical conductivity is excellent, cracking and destruction of the anode active material are prevented during lithium ion intercalation/desorption reactions, and capacity degradation is minimized, resulting in excellent long lifespan characteristics. For example, 0.1 to 3% by weight may be included.

The second soft coating layer may include the silver nanowires, carbon nanotubes, and soft carbon in a weight ratio of 1:0.01 to 5:0.5 to 20. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics.

In one embodiment, the first soft coating layer, the second soft coating layer, and the hard coating layer may be included in a weight ratio of 1:0.3 to 2:1 to 10. When included in the above weight ratio, the electrical conductivity, durability, and structural stability of the anode active material are excellent, and the ?tip喚? The effect of preventing destruction may be excellent.

4th embodiment

An anode active material according to another embodiment of the present invention includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing flake graphite and silver nanowires dispersed in the porous matrix; a first hard coating layer and a second hard coating layer sequentially formed on an outer circumferential surface of the core and each containing amorphous hard carbon; a carbon nanotube layer formed on an outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 35% by weight of a first hard coating layer. % by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the first hard coating layer has a thickness 0.05 to 10 μm, the second hard coating layer may have a thickness of 0.5 to 10 μm, the carbon nanotube layer may have a thickness of 0.01 to 10 μm, and the silver nanowire layer may have a thickness of 0.01 to 10 μm. there is.

In one embodiment, the negative electrode active material may have an average particle diameter (d50) of 5 to 7 μm. In another embodiment, the negative electrode active material may have an average particle diameter (d50) of 8 to 11 μm.

In one embodiment, the first hard coating layer may be included in an amount of 5 to 25% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

In one embodiment, the second hard coating layer may be included in an amount of 3 to 15% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have a weight capacity ratio of 1000 to 1550 mAh/g. Under the above conditions, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have a tap density of 0.55 to 1.3 g/cm ³ . In one embodiment, the negative electrode active material may have a specific surface area of 1.5 to 10 m ² /g. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

core

The core includes a porous matrix including nano-silicon (Si) and amorphous hard carbon, and silver nanowires and flake graphite dispersed in the porous matrix. The amorphous hard carbon may be formed surrounding the entire surface of the core. Under the above conditions, structural stability is excellent to prevent cracking and destruction, and capacity degradation can be minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the core may have an average diameter (or maximum length) of 1 to 30 μm. Under the above conditions, high capacity and high output characteristics may be excellent, and structural stability may be excellent. For example, it may be 1 to 15 μm.

For example, the porous matrix may have a porous structure by combining nano-silicon with the amorphous hard carbon. In one embodiment, the porous matrix may have a porosity of 5 to 80%. Under the above conditions, the electrolyte solution impregnability may be excellent, and high capacity, high output characteristics and structural stability may be excellent.

The core may be spherical or elliptical. For example, it may be spherical.

In one embodiment, the amorphous hard carbon may include at least one of hard carbon formed by firing graphite balls and hard carbon formed by firing pitch.

In one embodiment, the amorphous hard carbon of the core may be included in an amount of 5 to 50% by weight based on the total weight of the negative electrode active material. When included within the above range, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, the amorphous hard carbon may be included in an amount of 5 to 35% by weight. For another example, the amorphous hard carbon may be included in an amount of 10 to 35% by weight.

The nano-silicon may be included to secure high capacity and high output characteristics. In one embodiment, the nano-silicon may have an average diameter of 1.5 μm or less. For example, the nano-silicon may have a smaller diameter than the core. When included within the above range, mixing and dispersibility may be excellent, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be 60 nm to 100 nm. Another example may be 40 to 120 nm.

In one embodiment, the nano-silicon may be spherical, polyhedral, elliptical or irregular. For example, it may be spherical.

In one embodiment, the nano-silicon may be included in an amount of 25 to 80% by weight based on the total weight of the negative electrode active material. In the above content range, mixing properties and durability may be excellent, and high capacity and high output characteristics may be excellent. For example, 25 to 55% by weight may be included. In another embodiment, the nano-silicon may be included in an amount of 45 to 80% by weight.

When the silver nanowires are included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

For example, 0.01 to 5% by weight of the silver nanowires may be included with respect to the total weight of the negative electrode active material. Under the above conditions, the anode active material may have excellent electrical conductivity, high capacity and high output characteristics. For another example, 0.2 to 2.5% by weight may be included.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the flake graphite may be included in an amount of 0 to 60% by weight based on the total weight of the negative electrode active material. When included within the above range, mixing and dispersibility may be excellent, and electrical conductivity, high capacity and high power characteristics of the anode active material may be excellent.

In one embodiment, the flake graphite may have an average size of 0.2 to 8 μm. The "size" may mean the "maximum length" of flake graphite. Mixability and dispersibility may be excellent under the average size condition, and electrical conductivity, high capacity, and high power characteristics of the anode active material may be excellent. For example, the average size may be 0.2 to 2 μm.

The anode active material may further include a conductive powder dispersed in a porous matrix. In one embodiment, the conductive powder may include at least one of carbon black, acetylene black, ketjen black, and furnace black. For example, carbon black may be included.

In one embodiment, the conductive powder may have an average particle diameter of 5 nm to 10 μm. Mixability and dispersibility may be excellent under the above conditions.

In one embodiment, the conductive powder may be included in an amount greater than 0 and less than 25% by weight based on the total weight of the negative electrode active material. When included in the above range, mixing and dispersibility may be excellent, and conductivity, high capacity and high output characteristics may be excellent. For example, 5 to 25% by weight may be included.

1st hard coating layer

The first hard coating layer includes amorphous hard carbon and is formed on the outer circumferential surface of the core. In one embodiment, the first hard coating layer may have a thickness of 0.01 to 10 μm. Durability and structural stability may be excellent in the above thickness range. For example, the thickness may be 0.05 to 10 μm.

In one embodiment, the first hard coating layer may be included in an amount of 0.1 to 35% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be 10 to 35% by weight. For example, 5 to 25% by weight may be included.

2nd hard coating layer

The second hard coating layer includes amorphous hard carbon and is formed on an outer circumferential surface of the first hard coating layer. In one embodiment, the second hard coating layer may have a thickness of 0.01 to 10 μm. Durability and structural stability may be excellent in the above thickness range. For example, the thickness may be 0.5 to 10 μm.

In one embodiment, the second hard coating layer may be included in an amount of 0.1 to 35% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For example, 3 to 15% by weight may be included.

In one embodiment, the first hard coating layer may have higher hardness than the second hard coating layer. Under the above conditions, volume expansion during the insertion of lithium ions is minimized, structural stability is excellent, cracking and destruction are prevented, and capacity degradation is minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the second hard coating layer and the first hard coating layer may be included in a weight ratio of 1 to 1.5:1 to 4. When included in the above weight ratio, the electrical conductivity, durability, and structural stability of the negative electrode active material are excellent, and the ?tip喚? The effect of preventing destruction may be excellent.

Carbon nanotube layer

A carbon nanotube layer is formed on the outer circumferential surface of the second hard coating layer. When the carbon nanotube layer is included, electrical conductivity is improved, and high-capacity and high-output effects may be excellent.

For example, the anode active material may include a carbon nanotube layer including carbon nanotubes at the outermost part of the second hard coating layer. The carbon nanotube layer may mean a layer formed by the carbon nanotube spaces. For example, in the carbon nanotube layer, the carbon nanotubes are inserted into pores formed on the outermost surface or part of the core and the second hard coating layer, or the carbon nanotubes are irregularly dispersed on the outer circumferential surface of the powder. may be in the form of For another example, the carbon nanotube layer may be in a form in which the carbon nanotubes are fixed by a binder or the like or attached by van der Waals forces.

The carbon nanotubes may include at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and roped carbon nanotubes. there is.

In one embodiment, the carbon nanotube layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.05 to 5% by weight may be included.

For example, the carbon nanotube layer may have a thickness of 0.01 to 10 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotube layer may have a thickness of 1 to 10 μm.

For example, the carbon nanotubes may have a length of 0.01 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 0.5 to 50 μm.

silver nanowire layer

A silver nanowire layer is formed on an outer circumferential surface of the carbon nanotube layer. When the silver nanowire layer is included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire layer may be fixed in an irregularly dispersed form by fixing the silver nanowires to the outer circumferential surface of the carbon nanotube layer by a binder.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may have a thickness of 0.01 to 10 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.01 to 3% by weight may be included.

5th embodiment

An anode active material according to another embodiment of the present invention includes a core containing a porous matrix containing nano-silicon (Si) and amorphous hard carbon and flake graphite dispersed in the porous matrix; a first hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; an amorphous carbon layer formed on an outer circumferential surface of the first hard coating layer; a second hard coating layer formed on an outer circumferential surface of the amorphous carbon layer and containing amorphous hard carbon; The carbon nanotube layer formed on the outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

In one embodiment, the anode active material includes 25 to 80% by weight of nano-silicon, 0 to 60% by weight of flake graphite, 5 to 50% by weight of amorphous hard carbon, 0.1 to 35% by weight of the first hard coating layer, and 0.1 to 15% by weight of the amorphous carbon layer. % by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.

In one embodiment, the negative electrode active material has an average diameter of 5 to 15 μm, the core has a diameter of 1 to 15 μm, the flake graphite has an average size of 0.2 to 8 μm, and the first hard coating layer has a thickness 0.05 to 10 μm, the amorphous carbon layer has a thickness of 0.01 to 10 μm, the second hard coating layer has a thickness of 0.5 to 10 μm, the carbon nanotube layer has a thickness of 0.01 to 10 μm, and the thickness of the second hard coating layer is 0.01 to 10 μm. The silver nanowire layer may have a thickness of 0.01 to 10 μm.

In one embodiment, the negative electrode active material may have a particle density of 1.2 to 2.0 g/cm ³ . In another embodiment, the negative electrode active material may have a particle density of 0.8 to 1.2 g/cm ³ . Under the above conditions, light weight and structural stability may be excellent.

In one embodiment, the negative electrode active material is porous, and the porosity of the surface (or the surface of the silver nanowire layer) may be 25 to 50% by volume. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have an average pore size of 0.5 to 2 μm. In another embodiment, the negative electrode active material may have an average pore size of 0.01 to 0.1 μm. Under the above conditions, structural stability, high capacity and high output characteristics may be excellent.

In one embodiment, the nano-silicon may be included in an amount of 25 to 55% by weight based on the total weight of the negative electrode active material. In another embodiment, the nano-silicon may be included in an amount of 45 to 80% by weight. Under the above conditions, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have an average particle diameter (d50) of 5 to 7 μm. In another embodiment, the negative electrode active material may have an average particle diameter (d50) of 8 to 11 μm.

In one embodiment, the negative electrode active material may have a weight capacity ratio of 800 to 1550 mAh/g. Under the above conditions, high capacity and high output characteristics may be excellent.

In one embodiment, the negative electrode active material may have a tap density of 0.55 to 1.3 g/cm ³ . In one embodiment, the negative electrode active material may have a specific surface area of 0.6 to 3.0 m ² /g. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

core

The core includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and flake graphite dispersed in the porous matrix. The amorphous hard carbon may be formed surrounding the entire surface of the core. Under the above conditions, structural stability is excellent to prevent cracking and destruction, and capacity degradation can be minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the core may have an average diameter (or maximum length) of 1 to 30 μm. Under the above conditions, high capacity and high output characteristics may be excellent, and structural stability may be excellent. For example, it may be 1 to 15 μm.

For example, the porous matrix may have a porous structure by combining nano-silicon with the amorphous hard carbon. In one embodiment, the porous matrix may have a porosity of 5 to 80%. Under the above conditions, the electrolyte solution impregnability may be excellent, and high capacity, high output characteristics and structural stability may be excellent.

The core may be spherical or elliptical. For example, it may be spherical.

In one embodiment, the amorphous hard carbon may include at least one of hard carbon formed by firing graphite balls and hard carbon formed by firing pitch.

In one embodiment, the amorphous hard carbon of the core may be included in an amount of 5 to 50% by weight based on the total weight of the negative electrode active material. When included within the above range, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, the amorphous hard carbon may be included in an amount of 5 to 35% by weight. For another example, the amorphous hard carbon may be included in an amount of 10 to 35% by weight.

The nano-silicon may be included to secure high capacity and high output characteristics. In one embodiment, the nano-silicon may have an average diameter of 1.5 μm or less. For example, the nano-silicon may have a smaller diameter than the core. When included within the above range, mixing and dispersibility may be excellent, durability and structural stability of the porous matrix may be excellent, and high capacity and high output characteristics may be excellent. For example, it may be 60 nm to 100 nm. Another example may be 40 to 120 nm.

In one embodiment, the nano-silicon may be spherical, polyhedral, elliptical or irregular. For example, it may be spherical.

In one embodiment, the nano-silicon may be included in an amount of 25 to 80% by weight based on the total weight of the negative electrode active material. In the above content range, mixing properties and durability may be excellent, and high capacity and high output characteristics may be excellent. For example, 25 to 55% by weight may be included. In another embodiment, the nano-silicon may be included in an amount of 45 to 80% by weight.

The flake graphite may be included to secure conductivity, high output and high capacity characteristics of the negative electrode active material. The flake graphite may include at least one of natural graphite and artificial graphite. The flake graphite may be prepared by exfoliating or pulverizing spherical graphite, but is not limited thereto.

In one embodiment, the flake graphite may include a crystal form in which a plurality of regular hexagonal planes of carbon atoms are stacked and have a thickness in a direction perpendicular to the hexagonal planes. The flake graphite may have a higher surface area than spherical graphite of the same capacity, excellent economic feasibility, and excellent conductivity and high capacity characteristics.

In one embodiment, the flake graphite may be included in an amount of 0 to 60% by weight based on the total weight of the negative electrode active material. When included within the above range, mixing and dispersibility may be excellent, and electrical conductivity, high capacity and high power characteristics of the anode active material may be excellent.

In one embodiment, the flake graphite may have an average size of 0.2 to 8 μm. The "size" may mean the "maximum length" of flake graphite. Mixability and dispersibility may be excellent under the average size condition, and electrical conductivity, high capacity, and high power characteristics of the anode active material may be excellent. For example, the average size may be 0.2 to 2 μm.

The anode active material may further include a conductive powder dispersed in a porous matrix. In one embodiment, the conductive powder may include at least one of carbon black, acetylene black, ketjen black, and furnace black. For example, carbon black may be included.

In one embodiment, the conductive powder may have an average particle diameter of 5 nm to 10 μm. Mixability and dispersibility may be excellent under the above conditions.

In one embodiment, the conductive powder may be included in an amount greater than 0 and less than 25% by weight based on the total weight of the negative electrode active material. When included in the above range, mixing and dispersibility may be excellent, and conductivity, high capacity and high output characteristics may be excellent. For example, 5 to 25% by weight may be included.

1st hard coating layer

The first hard coating layer includes amorphous hard carbon and is formed on the outer circumferential surface of the core. In one embodiment, the first hard coating layer may have a thickness of 0.05 to 10 μm. Durability and structural stability may be excellent in the above thickness range.

In one embodiment, the first hard coating layer may be included in an amount of 0.1 to 35% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For another example, 5 to 25% by weight may be included.

Amorphous Carbon Layer

The amorphous carbon layer may be formed in a process of firing the carbon precursor after heat treatment. The amorphous carbon layer may include amorphous carbon. For example, amorphous hard carbon may be included.

In one embodiment, the amorphous carbon layer may have a thickness of 0.01 to 10 μm. Durability and structural stability may be excellent in the above thickness range.

In one embodiment, the amorphous carbon layer may be included in an amount of 0.1 to 15% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For example, 0.5 to 5% by weight may be included.

2nd hard coating layer

The second hard coating layer includes amorphous hard carbon and is formed on an outer circumferential surface of the amorphous carbon layer. In one embodiment, the second hard coating layer may have a thickness of 0.01 to 10 μm. Durability and structural stability may be excellent in the above thickness range. For example, the thickness may be 0.5 to 10 μm.

In one embodiment, the second hard coating layer may be included in an amount of 0.1 to 35% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent. For example, 3 to 15% by weight may be included.

In one embodiment, the sum of the amorphous carbon layer and the second hard coating layer may be included in an amount of 3 to 15% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

In one embodiment, the first hard coating layer and the second hard coating layer may have higher hardness than the amorphous carbon layer. Under the above conditions, volume expansion during the insertion of lithium ions is minimized, structural stability is excellent, cracking and destruction are prevented, and capacity degradation is minimized, resulting in excellent long lifespan characteristics.

In one embodiment, the amorphous carbon layer, the second hard coating layer, and the first hard coating layer may be included in a weight ratio of 1:0.5 to 3:1.5 to 4. When included in the above weight ratio, the electrical conductivity, durability, and structural stability of the anode active material are excellent, and the ?tip喚? The effect of preventing destruction may be excellent.

In one embodiment, the sum of the amorphous carbon layer and the second hard coating layer may be included in an amount of 3 to 15% by weight based on the total weight of the negative electrode active material. Under the above conditions, structural stability may be excellent, and high capacity and high output characteristics may be excellent.

Carbon nanotube layer

A carbon nanotube layer is formed on the outer circumferential surface of the second hard coating layer. When the carbon nanotube layer is included, electrical conductivity is improved, and high-capacity and high-output effects may be excellent.

For example, the anode active material may include a carbon nanotube layer including carbon nanotubes at the outermost part of the second hard coating layer. The carbon nanotube layer may mean a layer formed by the carbon nanotube spaces. For example, in the carbon nanotube layer, the carbon nanotubes are inserted into pores formed on the outermost surface or part of the core and the second hard coating layer, or the carbon nanotubes are adhered to the outer circumferential surface of the powder in an irregularly dispersed form. may be in the form of For another example, the carbon nanotube layer may be in a form in which the carbon nanotubes are fixed by a binder or attached by van der Waals forces.

The carbon nanotubes may include at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and roped carbon nanotubes. there is.

In one embodiment, the carbon nanotube layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.05 to 5% by weight may be included.

For example, the carbon nanotube layer may have a thickness of 0.01 to 10 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotube layer may have a thickness of 1 to 10 μm.

For example, the carbon nanotubes may have a length of 0.01 to 50 μm. Under the above conditions, structural stability and electrical conductivity of the anode active material may be excellent. For example, the carbon nanotubes may have a length of 0.5 to 50 μm.

silver nanowire layer

The silver nanowire layer is formed on an outer circumferential surface of the carbon nanotube layer. When the silver nanowire layer is included, electrical conductivity of the anode active material is improved, and high-capacity and high-output effects can be further improved.

In one embodiment, the silver nanowire layer may be fixed in an irregularly dispersed form by fixing the silver nanowires to the outer circumferential surface of the carbon nanotube layer by a binder.

In one embodiment, the silver nanowire may have a diameter of 5 to 300 nm and a length of 0.1 to 50 μm. Under the above conditions, durability and electrical conductivity may be excellent.

In one embodiment, the silver nanowire layer may be included in an amount of 0.01 to 10% by weight based on the total weight of the negative electrode active material. When included under the above conditions, structural stability, electrical conductivity, high capacity and high output characteristics of the negative electrode active material may be excellent. For example, 0.05 to 5% by weight may be included. Other examples may include 0.05 to 3.5% by weight.

Secondary Battery Containing Silicon Carbon Composite Negative Active Material Containing Silver Nanowires

Another aspect of the present invention relates to a secondary battery including the silicon carbon composite anode active material having a double layer structure. In one embodiment, the secondary battery includes a cathode; cathode; and an electrolyte formed between the positive electrode and the negative electrode, wherein the negative electrode includes the negative electrode active material.

The secondary battery may include a lithium secondary battery. In one embodiment, the lithium secondary battery includes a positive electrode including a positive electrode active material; a negative electrode disposed spaced apart from the positive electrode and including the negative electrode active material; an electrolyte disposed between the cathode and anode; and a separator disposed between the negative electrode and the positive electrode to prevent electrical short circuit between the negative electrode and the positive electrode.

In one embodiment, the positive electrode and the negative electrode may be manufactured by applying a mixture including an active material, a conductive material, and a binder to one surface of an electrode plate (current collector), followed by drying and pressing.

In one embodiment, the positive electrode plate and the negative electrode plate may each include one or more of copper, stainless steel, aluminum, nickel, and titanium.

In one embodiment, the cathode active material may include a composite oxide of metal and lithium. The metal may include at least one of cobalt (Co), manganese (Mn), aluminum (Al), and nickel (Ni). For example, one or more of lithium-nickel oxide, lithium-nickel-cobalt oxide, lithium-nickel-cobalt-manganese oxide, and lithium-nickel-cobalt-aluminum oxide may be included.

In one embodiment, the conductive material is natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, carbon fiber, metal-based fiber, carbon fluoride, aluminum, nickel powder, zinc oxide, potassium titanate, titanium oxide, and polyphenyl. One or more of the ren-based compounds may be included.

In one embodiment, the binder is polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene - Propylene-diene monomer (EPDM), styrene-based rubber, and fluorine-based rubber may be included.

In one embodiment, a conventional separator may be used. For example, the separator may include at least one of polyester, polyethylene, polypropylene, and polytetrafluoroethylene (PTFE). The separator may be in the form of a non-woven fabric or a woven fabric. The separator is porous with an average pore diameter of 0.01 to 10 µm, and the separator may have a thickness of 5 to 500 µm.

In one embodiment, the electrolyte may include a non-aqueous organic solvent and a lithium salt. For example, the non-aqueous organic solvent may include at least one of carbonate-based, ester-based, ether-based, and ketone-based solvents. The carbonate-based solvent is dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylmethyl carbonate (EMC), ethylpropyl carbonate (EPC), ethylene carbonate (EC ), propylene carbonate (PC) and butylene carbonate (BC).

The ester solvent may include one or more of butyrolactone, decanolide, valerolactone, caprolactone, n-methyl acetate, n-ethyl acetate and n-propyl acetate. . The ether-based solvent may include dibutyl ether and the like. The ketone-based solvent may include polymethylvinyl ketone.

The lithium salt may act as a source of lithium ions in a battery. For example, the lithium salt is LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiN(CF ₃ SO ₂ ) ₂ , LiN(C ₂ F ₅ SO ₂ ) ₂ , LiAlO ₄ and LiAlCl ₄ may include one or more of, but is not limited thereto.

In one embodiment, the electrolyte is vinylene carbonate, vinyl ethylene carbonate, monofluoroethylene carbonate, difluoroethylene carbonate and succinic anhydride , 1,3-propane sultone (1,3-propane sultone) may further include one or more.

In one embodiment, the lithium secondary battery may include a prismatic battery, a cylindrical battery, and a pouch-type battery.

In one embodiment, the secondary battery may have a weight energy density of 550 mAh/g or more of the negative electrode during 600 or more charge/discharge cycles.

In one embodiment, when the secondary battery is discharged to a capacity value of 2C to 3C when evaluating the performance of the negative electrode of the half battery cell, the negative electrode may have a gravimetric energy density of 410 mAh/g or more.

In one embodiment, the secondary battery may have a negative electrode capacity of 550 to 850 mAh/g. In another example, the capacity of the negative electrode may exceed 850 mAh/g.

In one embodiment, the secondary battery may have a density of 1.1 g/cc or more and a capacity of 410 mAh/g or more during 600 charge/discharge cycles.

In one embodiment, the secondary battery may have a density of 1.1 to 1.52 g/cc of the negative electrode during initial charge/discharge cycles of 600 times.

In one embodiment, the secondary battery may have an expansion rate of 15 to 35% of the negative electrode when charging 0.01V using a half battery cell at 410 mAh/g to 450 mAh/g of the negative electrode.

In one embodiment, the secondary battery may have an expansion rate of 25 to 55% of the negative electrode when charging 0.01V using a half battery cell at 450 mAh/g to 550 mAh/g of the negative electrode.

In one embodiment, the secondary battery is driven at 2.5 to 4.2V, and the secondary battery is charged and discharged with a capacity value of 0.1C for 1 cycle, and then charged and discharged with a capacity value of 1.0C for 20 cycles. When the driving is repeated, in each cycle of charging, the charging current is maintained at 4.2V until it reaches 0.05C, and charging can be completed.

In one embodiment, the secondary battery has a weight energy density of 410 mAh / g or more ( With 1.5V as a cutoff voltage, the positive electrode is prepared to have a value measured in a half-cell evaluation of a lithium (Li) electrode), and the oxide active material is LiNi _x Co _y Mn _z O ₂ (where x, y, z satisfies x + y + z = 1, 0.50 < x < 0.91, 0.04 < y < 0.25, and 0.04 < z < 0.035) and includes the oxide active material. The capacity of (based on the value measured in half-cell evaluation in which the positive electrode is a lithium (Li) electrode with 4.2V as the cutoff voltage) and the capacity of the negative electrode including the negative electrode active material are 1.04 <capacity of the negative electrode / the capacity of the anode < 1.17 relationship is satisfied, and the electrolyte includes 1.1M LiPF ₆ , 0.1M LiBoB, but ethyl carbonate (EC) / ethylmethyl carbonate (EMC) / fluoroethylene carbonate (FEC) is 65% / 30 It is included in a ratio of %/5% (based on weight %), and the full-cell secondary battery is driven in the range of 2.50 to 4.20V while repeatedly charging and discharging more than 600 times during performance evaluation, The process of charging and discharging with a capacity value of 0.1 C during the first cycle, and then charging and discharging with a capacity value of 1.0 C for 20 cycles (the second cycle to the 21st cycle) was repeatedly evaluated, The anode active material is maintained at 4.2V until the charging current reaches 0.05C during each cycle charging, and charging can be completed.

In one embodiment, the secondary battery has a weight energy density of 410 mAh / g or more ( With 1.5V as a cutoff voltage, the positive electrode is prepared to have a value measured in the evaluation of a half cell, which is a lithium (Li) electrode), and the oxide active material is LiNi _x Co _y Al ₂ It has a structure (x, y, z satisfies x + y + z = 1, 0.71x < 0.95, 0.04 < y < 0.15, and 0.03 < z < 0.15), and the capacity of the cathode containing the oxide active material (4.2 With V as the cutoff voltage, based on the value measured in half-cell evaluation in which the positive electrode is a lithium (Li) electrode) and the capacity of the negative electrode including the negative electrode active material is 1.04 < capacity of the negative electrode / capacity of the positive electrode < 1.17 relationship is satisfied, and the electrolyte includes 1.1M LiPF ₆ , 0.1M LiBoB, but ethyl carbonate (EC) / ethylmethyl carbonate (EMC) / fluoroethylene carbonate (FEC) is 65% / 30% / 5% (based on weight %), the full-cell secondary battery is driven in the range of 2.50 to 4.20V while repeatedly charging and discharging more than 600 times during the performance evaluation, and during the first cycle The process of charging and discharging with a capacity value of 0.1C, and then charging and discharging with a capacity value of 1.0C for 20 cycles (2nd cycle to 21st cycle) was repeatedly evaluated, but the negative electrode active material During each cycle charging, the charging current is maintained at 4.2V until it reaches 0.05C, and charging can be completed.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention by this in any sense. Contents not described herein can be technically inferred by those skilled in the art, so descriptions thereof will be omitted.

Examples and Comparative Examples

Example 1

(1) Preparation of graphite balls: A graphite mixture in powder form was prepared by dry mixing artificial graphite (3 μm flake graphite) and pitch in a weight ratio of 1:1 to 3:1. The graphite mixture was pressurized and compressed under conditions of 5 to 50 atm, fired at 400 to 650° C., and then pulverized to prepare spherical graphite balls having an average particle diameter of 5 μm.

(2) Preparation of nano-silicon slurry: stearic acid (14.4 g) was added to and dissolved in the first solvent (16200 g) in which ethanol and pure water were mixed in a weight ratio of 1:1. When all stearic acid was dissolved, spherical silicon powder (1800 g) having an average particle diameter (d50) of 2 to 5 μm was added to the first solvent, dissolved, and then milled and pulverized to prepare a nano-silicon slurry having an average particle diameter (d50) of 98 nm. .

(3) Preparation of silver nanowires: silver nanowires manufactured by a known method were prepared. In addition, a first dispersant was prepared by mixing polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether (product name: triton x-100, Duksan Science). Then, a silver nanowire dispersion was prepared by mixing the silver nanowires, the first dispersant, and water.

(4) Preparation of a first mixture and dried material: A first mixture was prepared by mixing and stirring the graphite balls, nano-silicon slurry, silver nanowire dispersion, pitch, and flake graphite (0.2-2 μm). The first mixture included graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.01 to 3:2 to 8:1 to 15:5 to 70 based on solid content. Then, the first mixture was dried at 120° C. using a spray dryer to prepare a spherical dried product having an average particle diameter of 9 to 11 μm.

(5) Calcining and heat treatment: The dried product was heated to 800 to 1150° C. and calcined to prepare a calcined product. A hard coating layer containing amorphous hard carbon was formed on the outer circumferential surface of the fired product (core). Then, 100 parts by weight of the fired material and 1 to 30 parts by weight of a carbon precursor (including polyimide and dimethylformamide) were mixed and heat-treated at 80 to 300° C. to form a soft coating layer.

(5) Formation of a carbon nanotube layer: A carbon nanotube solution containing 1% by weight of carbon nanotubes, 0.5% by weight of carboxymethylcellulose, and the remaining amount of a solvent was prepared. Next, a carbon nanotube layer was formed by mixing and drying the carbon nanotube solution on the outer circumferential surface of the soft coating layer of the heat-treated fired product.

(6) Formation of a silver nanowire layer: A silver nanowire dispersion was prepared by mixing the silver nanowires, the first dispersing agent, and water under the same conditions as the silver nanowires 3 . Then, a silver (Ag) nanowire dispersion was applied to the surface of the soft coating layer and heat-treated at 80 to 150° C. to form a silver nanowire layer. The prepared powder was classified using a 325 mesh sieve to prepare a spherical negative electrode active material having an average particle diameter (d50) of 10.5 μm.

The anode active material includes 25 to 55% by weight of nano silicon, 1 to 60% by weight of flake graphite, 0.05 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, 5 to 10% by weight of hard coating layer, and 5 to 10% by weight of soft coating layer. 0.1 to 3% by weight, 0.1 to 2% by weight of the carbon nanotube layer, and 0.01 to 3% by weight of the silver nanowire layer.

3 is a scanning electron micrograph showing a cross section of the negative active material of Example 1, and FIG. 4 is a scanning electron micrograph showing a cross section of the negative active material of Example 1. Referring to FIGS. 3 and 4, the anode active material of Example 1 includes a porous matrix including nano-silicon (Si) 12 and an amorphous hard carbon layer 14 and flake graphite 16 dispersed in the porous matrix. It can be seen that a hard coating layer and a soft coating layer are sequentially formed on the outermost surface of the core, and a carbon nanotube layer and a silver nanowire layer are formed on an outer circumferential surface of the soft coating layer.

Referring to FIGS. 3 and 4, in Example 1, pores P are formed on the surface and inside of the core including the nano-silicon 12 and the amorphous hard carbon layer 12, and flake graphite ( 16) is a dispersed structure. In addition, it can be seen that the micropores A are formed in the center of the core at the position where the graphite ball was located.

5(a) is a scanning electron micrograph of the anode active material of Example 1, and FIG. 5(b) is a scanning electron micrograph of the anode active material of Example 1. Referring to FIG. 5, it can be seen that in Example 1, a silver nanowire layer is formed on the outer circumferential surface of the soft coating layer.

6 is a graph showing the particle diameter distribution of the negative electrode active material of Example. Referring to FIG. 6, it can be seen that the negative electrode active material of Example 1 has a spherical shape with an average particle diameter (d50) of 10.5 μm.

FIG. 7(a) is a scanning electron micrograph of the carbon nanotube layer, FIG. 7(b) is a scanning electron micrograph of the silver nanowire layer, and FIG. 7(c) is a scanning electron micrograph of the surface of Example 1. . Referring to FIG. 7, in Example 1, it can be seen that a carbon nanotube layer including carbon nanotubes having an average size of 1 to 20 μm is formed on the surface, and a silver nanowire layer is formed on the surface of the carbon nanotubes. can

Example 2

(1) Preparation of a first mixture and dried material: The same graphite balls, nano-silicon slurry, flake graphite, and silver nanowire dispersion as in Example 1 were prepared. Then, in the same manner as in Example 1, the graphite balls, silver nanowire dispersion, flake graphite, and nanosilicon slurry were mixed and stirred to obtain a first mixture (graphite balls based on solid content, silver nanowires, flake graphite, and nanosilicon slurry) 1:0.01 to 5:2 to 8:5 to 70 weight ratio) was prepared, and then dried to prepare a dried product.

(2) Calcined product, heat treatment, and intermediate preparation: The dried product and pitch were mixed, heated to 800 ~ 1150 ° C., and calcined to prepare a calcined product. A hard coating layer containing amorphous hard carbon was formed on the outer circumferential surface of the fired product (core). Then, 100 parts by weight of the calcined product and 1 to 30 parts by weight of a carbon precursor (including polyimide and dimethylformamide) are mixed and heat-treated at 80 to 300 ° C., thereby forming a first soft coating layer on the inner and outer circumferential surfaces of the hard coating layer. And a second soft coating layer was formed to prepare an intermediate body.

(3) Carbon nanotube layer formation: A carbon nanotube layer was formed by mixing and drying a carbon nanotube solution under the same conditions as in Example 1 on the outer circumferential surface of the second soft coating layer of the intermediate body.

(4) Formation of silver nanowire layer: A silver nanowire dispersion was prepared under the same conditions as in Example 1. Then, a silver (Ag) nanowire dispersion was applied to the outer circumferential surface of the carbon nanotube layer and heat-treated at 80 to 150° C. to form a silver nanowire layer. The prepared powder was classified using a 325 mesh sieve to prepare a spherical negative electrode active material having an average particle diameter (d50) of 10.5 μm.

The prepared anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver nanowires and flake graphite dispersed in the porous matrix; a first soft coating layer formed on an outer circumferential surface of the core; a hard coating layer formed on an outer circumferential surface of the first soft coating layer and containing amorphous hard carbon; a second soft coating layer formed on an outer circumferential surface of the hard coating layer; a carbon nanotube layer formed on an outer circumferential surface of the second soft coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

The anode active material includes 25 to 55% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.1 to 2% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, 5 to 10% by weight of hard coating layer, and 1st soft 0.1 to 15% by weight of the coating layer, 0.1 to 15% by weight of the second soft coating layer, 0.1 to 3% by weight of the carbon nanotube layer, and 0.05 to 1.5% by weight of the silver nanowire layer.

Example 3

(1) Preparation of the first mixture and dried material: Graphite balls and nano-silicon slurry were prepared in the same manner as in Example 1. Then, in the same manner as in Example 1, a first mixture containing graphite balls and nano-silicon slurry in a weight ratio of 1:0.5 to 1:5 was dried to prepare a dried product.

(2) Calcined product and primary heat treatment: The dried product was heated to 800 to 1150° C. and calcined to prepare a calcined product having a hard coating layer including amorphous hard carbon on the outermost layer. Then, a silver nanowire dispersion was prepared in the same manner as in Example 1, 100 parts by weight of the fired product, 0.1 to 30 parts by weight of the silver nanowire dispersion, 1 to 30 parts by weight of carbon precursor (including polyimide and dimethylformamide) An intermediate was prepared by mixing parts by weight and performing a primary heat treatment at 80 to 300° C. to form a first soft coating layer on the outer circumferential surface of the hard coating layer.

(3) Second heat treatment: A carbon nanotube solution and a silver nanowire dispersion were prepared in the same manner as in Example 1 above. Then, 100 parts by weight of the intermediate, 1 to 30 parts by weight of the carbon nanotube solution, 0.1 to 15 parts by weight of the silver nanowire dispersion, and 1 to 30 parts by weight of the carbon precursor (including polyimide and dimethylformamide) were mixed, and 80 to 300 parts by weight were mixed. A second soft coating layer was formed on the outer circumferential surface of the first soft coating layer by secondary heat treatment at ° C., and then classified using a 325 mesh sieve to prepare an anode active material having an average particle diameter (d50) of 8 to 11 μm.

The anode active material includes a core including a porous matrix including nano-silicon (Si) and amorphous hard carbon, a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon, and a silver nano layer formed on the outer circumferential surface of the hard coating layer. A first soft coating layer including wire and soft carbon, and a second soft coating layer structure formed on an outer circumferential surface of the first soft coating layer and including carbon nanotubes, silver nanowires, and soft carbon.

The anode active material includes 25 to 80% by weight of nano silicon, 5 to 50% by weight of amorphous hard carbon, 0.1 to 15% by weight of a hard coating layer, 0.1 to 15% by weight of a first soft coating layer, and 0.1 to 15% by weight of a second soft coating layer. %, wherein the first soft coating layer includes the silver nanowires and soft carbon in a weight ratio of 1:2 to 1:10, and the second soft coating layer includes the silver nanowires, carbon nanotubes, and soft carbon was included in a weight ratio of 1:0.01 to 5:0.5 to 20.

Example 4

(1) Preparation of a first mixture and dried product: A first mixture including graphite balls, nano-silicon slurry, silver nanowires, flake graphite, and pitch was dried in the same manner as in Example 1 to prepare a dried product.

(2) Production of primary and secondary calcined products: Mixing 100 parts by weight of the dry material and 1 to 30 parts by weight of pitch, raising the temperature to 800 to 1150 ° C, and firing the first, containing amorphous hard carbon in the outermost shell, 1 A first fired product having a hard coating layer was prepared. Then, 100 parts by weight of the first fired material and 1 to 30 parts by weight of pitch are mixed, the temperature is raised to 800 to 1150 ° C, and the second fired product is fired to form a second hard coating layer on the outer circumferential surface of the first hard coating layer. was manufactured.

(3) Carbon nanotube layer formation: A carbon nanotube layer was formed by mixing and drying a carbon nanotube solution under the same conditions as in Example 1 on the outer circumferential surface of the second hard coating layer of the second fired product.

(4) Silver nanowire layer formation: A silver nanowire dispersion same as in Example 1 was mixed and dried on the outer circumferential surface of the carbon nanotube layer to form a silver nanowire layer, and then classified using a 325 mesh sieve to obtain an average An anode active material having a particle size (d50) of 8 to 11 μm was prepared.

The anode active material is sequentially formed on a core including a porous matrix including nano-silicon (Si) and amorphous hard carbon and flake graphite dispersed in the porous matrix, and on an outer circumferential surface of the core, each containing amorphous hard carbon. It was formed including a first hard coating layer and a second hard coating layer, a carbon nanotube layer formed on the outer circumferential surface of the second hard coating layer, and a nanowire layer structure formed on the outer circumferential surface of the carbon nanotube.

The negative electrode active material is 25 to 55% by weight of nano-silicon, 60% by weight of flake graphite, 5 to 50% by weight of amorphous hard carbon, 5 to 25% by weight of the first hard coating layer, and 3 to 15% by weight of the second hard coating layer. , 0.1 to 3% by weight of the carbon nanotube layer and 0.2 to 2.5% by weight of the silver nanowire layer.

Example 5

(1) Preparation of the first mixture and dry matter: A first mixture containing graphite balls, nano-silicon slurry, flake graphite and pitch in the same manner as in Example 1 (graphite balls based on solid content, flake graphite, pitch and nano-silicon 1: 2 to 8: 1 to 15: 5 to 70 weight ratio) was dried to prepare a dried product.

(2) Preparation of the first fired product and intermediate: The dried product was heated to 800 ~ 1150 ° C. and first fired to prepare a first fired product having a first hard coating layer formed on the outermost layer containing amorphous hard carbon. Then, 1 to 30 parts by weight of a carbon precursor (including polyimide and dimethylformamide) was mixed with 100 parts by weight of the first fired product and heat-treated to prepare an intermediate in which a soft coating layer was formed on the outer circumferential surface of the first hard coating layer.

(3) Preparation of secondary firing: 1 to 30 parts by weight of pitch were mixed with 100 parts by weight of the intermediate, and secondary firing was performed at 800 to 1150 ° C to prepare a secondary fired product. In the secondary fired product, a first hard coating layer containing amorphous hard carbon, an amorphous carbon layer, and a second hard coating layer containing amorphous hard carbon were sequentially formed on the outermost side.

(4) Carbon nanotube layer formation: A carbon nanotube layer was formed by mixing and drying a carbon nanotube solution under the same conditions as in Example 1 on the outer circumferential surface of the second hard coating layer of the second fired product.

(5) Forming a silver nanowire layer: mixing and drying the silver nanowire dispersion on the outer circumferential surface of the carbon nanotube layer to form a silver nanowire layer, and then classifying using a 325 mesh sieve to obtain an average particle diameter (d50) of 8 An anode active material having a thickness of ~11 μm was prepared.

The anode active material includes a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing flake graphite dispersed in the porous matrix; a first hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon; an amorphous carbon layer formed on an outer circumferential surface of the first hard coating layer; a second hard coating layer formed on an outer circumferential surface of the amorphous carbon layer and containing amorphous hard carbon; a carbon nanotube layer formed on an outer circumferential surface of the second hard coating layer; and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

The anode active material includes 25 to 55% by weight of nano silicon, 0 to 60% by weight of flake graphite, 5 to 50% by weight of amorphous hard carbon, 5 to 25% by weight of the first hard coating layer, 0.1 to 5% by weight of an amorphous carbon layer, 2 0.1 to 10% by weight of the hard coating layer, 0.1 to 3% by weight of the carbon nanotube layer, and 0.05 to 3.5% by weight of the silver nanowire layer were included.

Comparative Example 1

An anode active material was prepared in the same manner as in Example 1, except that the core did not include silver nanowires and the silver nanowire layer was not formed on the outer circumferential surface of the soft coating layer.

Comparative Example 2

An anode active material was prepared in the same manner as in Example 1, except that a carbon nanotube layer and a silver nanowire layer were sequentially formed on the surface of the fired product on which the hard coating layer containing amorphous hard carbon was formed on the outer circumferential surface.

The anode active material includes a porous matrix including nano-silicon (Si) and amorphous carbon, a core including flake graphite dispersed in the porous matrix, a hard coating layer formed on an outer circumferential surface of the core, and carbon formed on an outer circumferential surface of the hard coating layer. It was formed to have a structure including a nanotube layer and a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.

The anode active material includes 25 to 55% by weight of nano silicon, 1 to 60% by weight of flake graphite, 0.05 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, 5 to 10% by weight of hard coating layer, and carbon nanotubes. 0.1 to 2% by weight of the layer and 0.01 to 10% by weight of the silver nanowire layer.

8(a) is a scanning electron micrograph of the anode active material of Example 1, and FIG. 8(b) is a scanning electron micrograph of the anode active material of Comparative Example 1. Referring to FIG. 8, it can be seen that the negative electrode active material of Example 1 has a silver nanowire layer formed on the surface of the carbon nanotube layer.

Property evaluation

(1) Analysis of density, pore characteristics, and measurement of specific surface area: Particle density, porosity, pore size, tap density, and specific surface area (BET method) were measured for the anode active materials of Examples and Comparative Examples, and the results are shown in Table 1 below. showed up The porosity and pore size are measured using a pore distribution measuring instrument (manufacturer: Micromeritics / product name: Autopore IV), and the tap density is the apparent surface of the negative active material obtained by filling the container with the negative active material of the Examples and Comparative Examples and then vibrating it. Density was measured using a tap density meter.

(2) Measurement of surface resistance, volume resistance, and electrical conductivity: The surface resistance and volume resistance of the anode active materials of the above examples and comparative examples were measured using a resistance meter (manufacturer: Mitsubishi, product name: LORESTA) -GP), and the electrical conductivity of the Examples and Comparative Examples was measured with an electrical conductivity meter (manufacturer: Mitsubishi, product name: LORESTA-GP), and the results are shown in Table 1 below.

(3) Measurement of negative electrode expansion rate: A slurry mixture (79% by weight of natural graphite, 14.8% by weight of negative electrode active materials of Examples and Comparative Examples, 1.4% by weight of carboxymethyl cellulose (CMC), 1.4% by weight of styrene-butadiene rubber (SBR)) on one side of the negative electrode conductor Weight % and artificial graphite (SFG6) 3.5% by weight) were applied and dried to prepare a negative electrode (capacity 410 ~ 450 mAh / g), and lithium metal was prepared as a positive electrode. The electrolyte (electrolyte) includes 60% by weight of ethylene carbonate (EC), 35% by weight of ethylmethyl carbonate (EMC), and 5% by weight of fluoroethylene carbonate (FEC), and an electrolyte solution in which a lithium salt (LiPF ₆ ) of 1M concentration is dissolved. (electrolyte) was prepared. Then, an electrode assembly was prepared by interposing a porous separator between the positive electrode and the negative electrode, placed inside a case, and an electrolyte was injected into the case to prepare a coin-type half cell (Coin Half Cell 2032), respectively.

For the half-cells of Examples and Comparative Examples, an electrode plate having a current density of 2.5 mA/cm ² was fabricated, the thickness of the negative electrode was measured when charging up to 0.01C/0.01V under CCCV conditions, and then the expansion rate compared to the initial thickness of the negative electrode. was measured and the results are shown in Table 1 below.

Referring to the results of Table 1, Examples 1 to 5 of the present invention have excellent electrical conductivity and low surface/volume resistivity compared to Comparative Example 1, and excellent electrical conductivity compared to Comparative Example 2, and surface/volume resistance are excellent. It was found that the volume resistance and the expansion coefficient of the cathode were low.

Experimental Example (1): Evaluation of volume change of negative electrode active material according to charging and discharging

With respect to Example 1 and Comparative Example 2, the volume change of the negative electrode active material according to charging and discharging was measured. FIG. 9 schematically shows an apparatus for measuring a volume change of an anode active material during charging and discharging of Example 1 and Comparative Example 2.

A negative electrode was prepared by applying and drying the negative electrode active material prepared in Examples and Comparative Examples together with a binder on both sides of the negative electrode conductor, and using NCM622 material having a weight ratio of nickel, cobalt, and manganese of 6:2:2 to form a positive electrode An anode was prepared by applying it to a conductive plate. The electrolyte (electrolyte) includes 60% by weight of ethylene carbonate (EC), 35% by weight of ethylmethyl carbonate (EMC), and 5% by weight of fluoroethylene carbonate (FEC), and an electrolyte solution in which a lithium salt (LiPF ₆ ) of 1M concentration is dissolved. (electrolyte) was prepared.

Then, as shown in FIG. 9, an electrode assembly was prepared by disposing a negative electrode and an anode on both sides of the negative electrode at a distance from each other in the case, and placing a porous separator between the negative electrode and the positive electrode, respectively, and disposed inside the case. Then, an electrolyte was injected into the case to manufacture a secondary battery.

The secondary batteries of Example 1 and Comparative Example 2 were charged and discharged 100 times at 1C at 45°C, respectively. During the charging and discharging, the thickness change of the negative electrode was measured using a linear gauge probe, and the results are shown in FIG. 10 below.

10 is a graph of volume change of the negative electrode active material during charging and discharging of Example 1 and Comparative Example 2. Referring to FIG. 10, the negative electrode active material of Example 1 had a lower volume change during charging and discharging than Comparative Example 2, and through this, cracking and destruction of the negative electrode active material during lithium ion insertion/desorption reactions were prevented and capacity was reduced. By minimizing , it was found that the long lifespan characteristics were excellent.

Experimental Example (2): Lithium secondary battery (coin type half cell) manufacturing

A slurry mixture (79.2% by weight of natural graphite, 14.2% by weight of the anode active materials of Example 1 and Comparative Example 2, 1.4% by weight of carboxymethylcellulose (CMC), 1.4% by weight of styrene-butadiene rubber (SBR) and artificial Graphite (SFG6) 3.5% by weight) was applied and dried to prepare a negative electrode (capacity 479 mAh / g), and lithium metal was prepared as a positive electrode. The electrolyte (electrolyte) includes 60% by weight of ethylene carbonate (EC), 35% by weight of ethylmethyl carbonate (EMC), and 5% by weight of fluoroethylene carbonate (FEC), and an electrolyte solution in which a lithium salt (LiPF ₆ ) of 1M concentration is dissolved. (electrolyte) was prepared.

Then, an electrode assembly was prepared by interposing a porous separator between the positive electrode and the negative electrode, placed inside a case, and an electrolyte solution was injected into the case to prepare a coin-type half cell (Coin Half Cell 2032).

* Evaluation of capacity characteristics: The capacity characteristics of the half cell of the above example were evaluated. Specifically, the half cell of the embodiment was charged and discharged under 0.1 C/0.1 C conditions, and the charge and discharge capacity was measured in the first charge and discharge cycle, and the results are shown in FIG. 11 below. The evaluation of the capacity characteristics was carried out under the condition that the charge upper limit voltage at room temperature (25° C.) was 4.2V and the discharge end voltage was 2.7V.

11 is an evaluation graph of capacity characteristics of coin half cells of Example 1 and Comparative Example 2; Referring to FIG. 11, the half cell of Example 1 had a 1 cycle (0.1C/0.1C) efficiency of 90.2%, and the capacity and efficiency of the anode active material of Example 1 calculated therefrom were 1282mAh/g and 87.2%, respectively. It was found to have an efficiency of %.

12 shows life cycle evaluation results of coin half-cells of Example 1 and Comparative Example 2; Referring to FIG. 12, it was found that Example 1 had better cycle life characteristics than Comparative Example 2.

Experimental Example (3): Lithium secondary battery (coin type full cell) manufacturing

NCM622 material having a weight ratio of nickel, cobalt, and manganese of 6:2:2 was applied to a cathode conductor plate to prepare a cathode, and a slurry mixture (79% by weight of natural graphite, Example 1 and Comparative Example 1) was coated on one side of the cathode conductor. 14.7% by weight of the negative electrode active material of Example 2, 1.4% by weight of carboxymethylcellulose (CMC), 1.4% by weight of styrene-butadiene rubber (SBR), and 3.5% by weight of artificial graphite (SFG6)) were applied and dried to obtain a negative electrode (capacity: 483mAh/g). ) was prepared, and an electrolyte solution was prepared in the same manner as in Experimental Example (1).

Then, an electrode assembly was prepared by interposing a porous separator between the positive electrode and the negative electrode, placed inside the case, and an electrolyte was injected into the case to prepare a coin-type full cell 2032 secondary battery. . At this time, the discharge capacity ratio (N/P ratio) of the negative active material/positive active material of the secondary battery was 1.07, and the current density of the negative electrode was 2.9 mAh/cm ² (@ 0.1C).

* Impedance measurement: After 5 cycles of operation for the secondary batteries of Example 1 and Comparative Example 2, the impedance was measured by EIS (electrochemical impedance spectroscopy), and the results are shown in FIG. 13 below. Referring to FIG. 13, it was found that Example 1 had lower resistance than Comparative Example 2.

* Capacity retention rate evaluation: The capacity retention rate when the secondary batteries of Example 1 and Comparative Example 2 were operated for 100 cycles under 1C charge/1C discharge conditions was evaluated, and the results are shown in FIG. 14 below. 14 is a graph showing results of capacity retention rates of coin full cells of Example 1 and Comparative Example 2; Referring to FIG. 14, it can be seen that the full cell of Example 1 has an efficiency of 84.6% for one cycle (0.1C/0.1C), which is superior to that of Comparative Example 2 in capacity retention rate.

Experimental Example (4): Lithium secondary battery (pouch type full cell) manufacturing

A positive electrode, a negative electrode (capacity: 478 mAh/g), and an electrolyte prepared in the same manner as in Experimental Example (2) were prepared. Then, an electrode assembly was prepared by interposing a porous separator between the positive and negative electrodes, placed inside a pouch, and an electrolyte was injected into the pouch to prepare a pouch full cell 2032 secondary battery. . At this time, the discharge capacity ratio (N/P ratio) of the negative active material/positive active material of the secondary battery was 1.07, the current density of the negative electrode was 2.9 mAh/cm ² (@ 0.1C), and the pouch cell capacity was 1150 mAh.

* Secondary battery efficiency, capacity, and long life (capacity retention rate) evaluation: Secondary battery efficiency, capacity, and long life (capacity retention rate) were evaluated for the secondary batteries (pouch-type full cell) of the above examples and comparative examples.

For the above Examples and Comparative Examples, evaluation was performed with 1.0C charge, cutoff 0.05C, and 4.2V/1.0C discharge 2.7V as one cycle, and charge/discharge during 1 cycle (0.1C/0.1C) operation. Efficiency and charge/discharge efficiency during standard cycle (1 cycle, 0.2C/0.2C) operation were evaluated, and the capacity of the negative electrode active material was calculated therefrom, and the results are shown in Table 2 below. In the case of long life (capacity retention rate) evaluation, the capacity retention rates of the secondary batteries of Example 1 and Comparative Example 2 were evaluated during 800 cycle operation, and the results are shown in FIG. 14 below.

15 is a graph of the capacity retention rate results of the pouch full cells of Example 1 and Comparative Example 2. Referring to FIG. 15, it was found that Example 1 had superior long lifespan characteristics to Comparative Example 2. It was found that the full cell of Example had a conversion efficiency of 84.5% in one cycle (0.1C/0.1C) and an efficiency of 98.9% in a standard cycle (0.2C/0.2C).

Experimental Example (5): Lithium secondary battery (pouch type full cell) manufacturing

A lithium secondary battery in the form of a pouch cell as shown in FIG. 16 was manufactured. Specifically, the anode was prepared by mixing natural graphite and the anode active material prepared in Examples and Comparative Examples with a binder and then applying them to the anode conductor plate. The cathode was manufactured by coating the anode conductor plate using NCM622 material with a weight ratio of nickel, cobalt, and manganese of 6:2:2.

At this time, 90% by weight of a mixed solution of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) mixed in a weight ratio of 3: 5: 2 and a fluoroethylene carbonate (FEC) solution as an organic solvent used in the electrolyte solution 10% by weight was mixed and used. LiPF ₆ was used as a lithium salt, and the electrolyte concentration was set to 1M. Conductor plates, binders, pouches, etc. were manufactured using products commonly used in lithium secondary batteries. The completed pouch cell had a capacity of about 1500 mAh.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

10: core 12: nano silicon
14: amorphous hard carbon layer 16: flake graphite
18: conductive powder 20 hard coating layer
30: soft coating layer 40: carbon nanotube layer
50: silver nanowire layer 100: negative active material
200: SEI layer

Claims (31)

drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires to prepare a dried product;
Calcining the dried product to produce a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost portion;
forming a soft coating layer on an outer circumferential surface of the fired object by mixing a carbon precursor with the fired object and performing heat treatment;
forming a carbon nanotube layer on an outer circumferential surface of the soft coating layer; and
and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.
drying a first mixture including graphite balls, nano-silicon slurry, flake graphite, and silver nanowires to prepare a dried product;
preparing a fired product having a hard coating layer formed thereon, including amorphous hard carbon at the outermost layer, by mixing and firing the dried product and the pitch;
preparing an intermediate by mixing a carbon precursor with the fired product and heat-treating to form a first soft coating layer and a second soft coating layer on the inner and outer circumferential surfaces of the hard coating layer, respectively;
forming a carbon nanotube layer on an outer circumferential surface of the second soft coating layer; and
and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.
Preparing a dry product by drying the first mixture including graphite balls and nano-silicon slurry;
Calcining the dried product to produce a fired product having a hard coating layer formed thereon, including amorphous hard carbon on the outermost layer;
preparing an intermediate body by mixing a carbon precursor and silver nanowires with the fired product and performing a first heat treatment to form a first soft coating layer on an outer circumferential surface of the hard coating layer; and
and forming a second soft coating layer on the outer circumferential surface of the first soft coating layer by mixing the intermediate, the carbon precursor, the carbon nanotubes, and the silver nanowires and performing secondary heat treatment. .
drying a first mixture including graphite balls, nano-silicon slurry, pitch, flake graphite, and silver nanowires to prepare a dried product;
Preparing a first fired product having a first hard coating layer comprising amorphous hard carbon on an outermost layer by mixing the dried product and the pitch and performing primary firing;
preparing a second fired product having a second hard coating layer formed on an outer circumferential surface of the first hard coating layer by mixing the first fired product and pitch and second fired;
forming a carbon nanotube layer on an outer circumferential surface of the second hard coating layer; and
and forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer.
Drying a first mixture including graphite balls, nano-silicon slurry, pitch, and flake graphite to prepare a dried product;
Preparing a first fired product on which a first hard coating layer containing amorphous hard carbon is formed on an outermost layer by performing primary firing on the dried product;
preparing an intermediate body in which a soft coating layer is formed on an outer circumferential surface of the first hard coating layer by mixing a carbon precursor with the first fired product and performing heat treatment;
Preparing a secondary firing product by mixing pitch with the intermediate body and performing secondary firing; and
forming a carbon nanotube layer on an outer circumferential surface of the second fired product;
Forming a silver nanowire layer on an outer circumferential surface of the carbon nanotube layer;
In the secondary fired product, a first hard coating layer containing amorphous hard carbon, an amorphous carbon layer, and a second hard coating layer containing amorphous hard carbon are sequentially formed on the outermost surface.
According to any one of claims 1 to 5,
The nano-silicon slurry is prepared by dispersing and dispersing silicon powder and a dispersant in a first solvent; And grinding the dispersion; is prepared including,
The graphite ball is prepared by preparing a graphite mixture including pitch and graphite; pressurizing the graphite mixture and firing it at 400 to 650 ° C; And, the step of pulverizing the calcined graphite mixture; characterized in that the negative electrode active material manufacturing method comprising a.
The method of claim 6, wherein the first solvent includes one or more of water, ethanol, isopropyl alcohol and potassium hydroxide (KOH),
The graphite mixture further comprises a second solvent of at least one of N-methylpyrrolidone (NMP), ethanol and water.
The method according to any one of claims 1 to 3 and 5, wherein the carbon precursor is polyimide, polyacrylonitrile, polyvinylpyrrolidone, glucose, cellulose, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, polyvinyl A method for producing an anode active material comprising at least one of leaden fluoride, styrene butadiene rubber and sucrose.
The method of claim 1, wherein the first mixture includes the graphite balls, silver nanowires, flake graphite, pitch, and nanosilicon in a weight ratio of 1:0.01 to 5:2 to 8:1 to 25:5 to 70 A negative electrode active material manufacturing method.
The method of claim 1 , wherein the silver nanowire layer is prepared by applying a silver (Ag) nanowire dispersion to an outer circumferential surface of the carbon nanotube layer and heat-treating at 80 to 150° C.
The silver nanowire dispersion includes silver nanowires, a binder, and a dispersing solvent;
The dispersing solvent is a negative electrode active material manufacturing method, characterized in that it comprises at least one of water and organic solvents.
11. The method of claim 10, wherein the silver nanowire dispersion includes silver nanowires, a first dispersant, and water,
The method for producing a negative electrode active material, wherein the first dispersant comprises at least one of polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyethylene octylphenyl ether.
11. The method of claim 10, wherein the silver nanowire dispersion includes silver nanowires, a second dispersant, and an organic solvent,
The dispersant is a negative electrode active material manufacturing method characterized in that it comprises at least one of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber and polyvinylidene fluoride.
11. The method of claim 10, wherein the silver nanowire layer is formed by chemical vapor deposition (CVD) of silver (Ag) nanowires on an outer circumferential surface of the carbon nanotube layer.
A porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver (Ag) nanowires and flake graphite dispersed in the porous matrix;
a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon;
a soft coating layer formed on an outer circumferential surface of the hard coating layer;
a carbon nanotube layer formed on an outer circumferential surface of the soft coating layer; and
A negative active material comprising a silver (Ag) nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.
15. The method of claim 14, wherein the anode active material is 25 to 80% by weight of nano silicon, 1 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowires, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. An anode active material comprising 0.1 to 5 wt% of a soft coating layer, 0.01 to 10 wt% of a carbon nanotube layer, and 0.01 to 10 wt% of a silver nanowire layer.
The method of claim 14, wherein the negative electrode active material has an average diameter of 5 ~ 15㎛,
The core has a diameter of 1 to 15 μm,
The flake graphite has an average size of 0.2 to 8 μm,
The soft coating layer has a thickness of 0.05 to 5 μm,
The hard coating layer has a thickness of 0.05 to 5 μm,
The carbon nanotube layer has a thickness of 0.01 to 10 μm, and
The negative electrode active material, characterized in that the silver nanowire layer has a thickness of 0.01 ~ 10㎛.
a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and a core containing silver nanowires and flake graphite dispersed in the porous matrix;
a first soft coating layer formed on an outer circumferential surface of the core;
a hard coating layer formed on an outer circumferential surface of the first soft coating layer and containing amorphous hard carbon;
a second soft coating layer formed on an outer circumferential surface of the hard coating layer;
a carbon nanotube layer formed on an outer circumferential surface of the second soft coating layer; and
A negative electrode active material comprising a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.
18. The method of claim 17, wherein the anode active material is 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, and 0.1 to 10% by weight of hard coating layer. wt%, 0.1 to 15 wt% of the first soft coating layer, 0.1 to 15 wt% of the second soft coating layer, 0.01 to 10 wt% of the carbon nanotube layer, and 0.01 to 10 wt% of the silver nanowire layer. negative electrode active material.
The method of claim 17, wherein the negative electrode active material has an average diameter of 5 ~ 15㎛,
The core has a diameter of 1 to 15 μm,
The flake graphite has an average size of 0.2 to 8 μm,
The first soft coating layer has a thickness of 0.05 to 5 μm,
The hard coating layer has a thickness of 0.05 to 5 μm,
The second soft coating layer has a thickness of 0.5 to 10 μm,
The carbon nanotube layer has a thickness of 0.01 to 10 μm, and
The negative electrode active material, characterized in that the silver nanowire layer has a thickness of 0.01 ~ 10㎛.
a core including a porous matrix including nano-silicon (Si) and amorphous hard carbon;
a hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon;
a first soft coating layer formed on an outer circumferential surface of the hard coating layer and including soft carbon and silver nanowires; and
and a second soft coating layer formed on an outer circumferential surface of the first soft coating layer and including soft carbon, carbon nanotubes, and silver nanowires.
21. The method of claim 20, wherein the anode active material is nano-silicon 25 ~ 80% by weight, amorphous hard carbon 5 ~ 50% by weight, hard coating layer 0.1 ~ 15% by weight, first soft coating layer 0.1 ~ 15% by weight, and second soft Including 0.1 to 15% by weight of the coating layer,
The first soft coating layer includes the silver nanowires and soft carbon in a weight ratio of 1:0.5 to 1:20,
The negative electrode active material, characterized in that the second soft coating layer comprises the silver nanowires, carbon nanotubes and soft carbon in a weight ratio of 1:0.01 to 5:0.5 to 20.
The method of claim 20, wherein the negative electrode active material has an average diameter of 5 ~ 15㎛,
The core has a diameter of 1 to 15 μm,
The hard coating layer has a thickness of 0.05 to 5 μm,
The first soft coating layer has a thickness of 0.05 to 5 μm, and
The negative electrode active material, characterized in that the second soft coating layer has a thickness of 0.5 ~ 10㎛
A core including a porous matrix containing nano-silicon (Si) and amorphous hard carbon, and flake graphite and silver nanowires dispersed in the porous matrix;
a first hard coating layer and a second hard coating layer sequentially formed on an outer circumferential surface of the core and each containing amorphous hard carbon;
a carbon nanotube layer formed on an outer circumferential surface of the second hard coating layer; and
A negative electrode active material comprising a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.
24. The method of claim 23, wherein the anode active material is 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 0.01 to 5% by weight of silver nanowire, 5 to 50% by weight of amorphous hard carbon, 0.1% by weight of the first hard coating layer. An anode active material comprising 0.1 to 35 wt% of a second hard coating layer, 0.01 to 10 wt% of a carbon nanotube layer, and 0.01 to 10 wt% of a silver nanowire layer.
The method of claim 23, wherein the negative electrode active material has an average diameter of 5 ~ 15㎛,
The core has a diameter of 1 to 15 μm,
The flake graphite has an average size of 0.2 to 8 μm,
The first hard coating layer has a thickness of 0.05 to 10 μm,
The second hard coating layer has a thickness of 0.5 to 10 μm,
The carbon nanotube layer has a thickness of 0.01 to 10 μm, and
The negative electrode active material, characterized in that the silver nanowire layer has a thickness of 0.01 ~ 10㎛.
A core containing a porous matrix containing nano-silicon (Si) and amorphous hard carbon and flake graphite dispersed in the porous matrix;
a first hard coating layer formed on an outer circumferential surface of the core and containing amorphous hard carbon;
an amorphous carbon layer formed on an outer circumferential surface of the first hard coating layer;
a second hard coating layer formed on an outer circumferential surface of the amorphous carbon layer and containing amorphous hard carbon;
The carbon nanotube layer formed on the outer circumferential surface of the second hard coating layer; and
A negative electrode active material comprising a silver nanowire layer formed on an outer circumferential surface of the carbon nanotube layer.
27. The method of claim 26, wherein the anode active material comprises 25 to 80% by weight of nano silicon, 0 to 60% by weight of flake graphite, 5 to 50% by weight of amorphous hard carbon, 0.1 to 35% by weight of the first hard coating layer, and 0.1% by weight of amorphous carbon layer. A negative electrode active material comprising ~15% by weight, 0.1 to 35% by weight of the second hard coating layer, 0.01 to 10% by weight of the carbon nanotube layer, and 0.01 to 10% by weight of the silver nanowire layer.
The method of claim 26, wherein the negative electrode active material has an average diameter of 5 ~ 15㎛,
The core has a diameter of 1 to 15 μm,
The flake graphite has an average size of 0.2 to 8 μm,
The first hard coating layer has a thickness of 0.05 to 10 μm,
The amorphous carbon layer has a thickness of 0.01 to 10 μm,
The second hard coating layer has a thickness of 0.5 to 10 μm,
The carbon nanotube layer has a thickness of 0.01 to 10 μm, and
The negative electrode active material, characterized in that the silver nanowire layer has a thickness of 0.01 ~ 10㎛.
anode;
cathode; and
Including; electrolyte formed between the anode and the cathode,
The negative electrode includes the negative electrode active material according to any one of claims 14, 17, 20, 23 and 26. A secondary battery.
The method of claim 29, wherein the secondary battery manufactures a full cell secondary battery including the negative electrode, a positive electrode including an oxide active material, and an electrolyte and evaluates performance,
The negative electrode has a capacity of 410 mAh / g or more of gravimetric energy density (based on the value measured in the evaluation of a half cell in which the positive electrode is a lithium (Li) electrode with 1.5V as a cutoff voltage). become,
The oxide active material has a structure of LiNi _x Co _y Mn _z O ₂ (where x, y, z is x+y+z=1, and satisfies 0.50<x<0.91, 0.04<y<0.25, and 0.04<z<0.035) ),
The capacity of the positive electrode including the oxide active material (based on the value measured in half-cell evaluation in which the positive electrode is a lithium (Li) electrode with 4.2V as a cutoff voltage) and the negative electrode including the negative electrode active material The capacity satisfies the relationship 1.04 < capacity of negative electrode / capacity of positive electrode < 1.17,
The electrolyte includes 1.1M LiPF ₆ and 0.1M LiBoB, but the ratio of ethyl carbonate (EC) / ethyl methyl carbonate (EMC) / fluoroethylene carbonate (FEC) is 65% / 30% / 5% (based on weight%) It includes,
The full-cell secondary battery is driven in the range of 2.50 to 4.20V while repeatedly charging and discharging more than 600 times during performance evaluation, and charging and discharging with a capacity value of 0.1C during the first cycle, , After that, for 20 cycles (2nd cycle to 21st cycle), the process of charging and discharging with a capacity value of 1.0C was repeatedly evaluated,
The negative electrode active material is maintained at 4.2V until a charging current reaches 0.05C during each cycle charging, and the charging is completed.
The method of claim 29, wherein the secondary battery manufactures a full cell secondary battery including the negative electrode, a positive electrode including an oxide active material, and an electrolyte and evaluates performance,
The negative electrode has a capacity of 410 mAh / g or more of gravimetric energy density (based on the value measured in the evaluation of a half cell in which the positive electrode is a lithium (Li) electrode with 1.5V as a cutoff voltage). become,
The oxide active material has a structure of LiNi _x Co _y Al ₂ (x, y, z satisfies x+y+z=1, 0.71x<0.95, 0.04<y<0.15, and 0.03<z<0.15),
The capacity of the positive electrode including the oxide active material (based on the value measured in half-cell evaluation in which the positive electrode is a lithium (Li) electrode with 4.2V as a cutoff voltage) and the negative electrode including the negative electrode active material The capacity satisfies the relationship 1.04 < capacity of negative electrode / capacity of positive electrode < 1.17,
The electrolyte includes 1.1M LiPF ₆ and 0.1M LiBoB, but the ratio of ethyl carbonate (EC) / ethyl methyl carbonate (EMC) / fluoroethylene carbonate (FEC) is 65% / 30% / 5% (based on weight%) It includes,
The full-cell secondary battery is driven in the range of 2.50 to 4.20V while repeatedly charging and discharging more than 600 times during performance evaluation, and charging and discharging with a capacity value of 0.1C during the first cycle, , After that, for 20 cycles (2nd cycle to 21st cycle), the process of charging and discharging with a capacity value of 1.0C was repeatedly evaluated,
The negative electrode active material is maintained at 4.2V until a charging current reaches 0.05C during each cycle charging, and charging is completed.