KR101290659B1 - Preparation method of silicon oxide powder using thermal plasma, and the silicon oxide powder thereby - Google Patents

Abstract

The present invention is a method for producing a silicon oxide powder using a thermal plasma, in particular a step of melting and vaporizing a pellet consisting of silicon and silicon dioxide mixed powder or silicon dioxide powder using a thermal plasma jet (step 1); Injecting a reaction gas into the thermal plasma apparatus to reduce silicon dioxide in the vaporized gas to silicon oxide (SiO _x ) (where 0.5 <x <1.5); And it provides a method for producing silicon oxide (SiO _x ) powder comprising the step (step 3) of collecting the silicon oxide reduced in step 2 to silicon oxide (SiOx) powder. In the method for producing silicon oxide (SiO _x ) powder using thermal plasma according to the present invention, a nano-sized silicon oxide powder can be synthesized in a short time using a thermal plasma jet, and easy to vaporize by using a high temperature plasma, and a process Good efficiency and easy control of process conditions. In addition, the prepared silicon oxide powder may be used as a negative electrode active material of a lithium secondary battery.

Description

Preparation method of silicon oxide powder using thermal plasma, and silicon oxide powder produced by the same {Preparation method of silicon oxide powder using thermal plasma, and the silicon oxide powder

The present invention relates to a method for producing silicon oxide (SiO _x ) powder using thermal plasma.

Recently, due to the remarkable development of portable electronic devices and communication devices, a secondary battery having a high energy density is required from the viewpoint of economical efficiency, miniaturization and light weight of the device. Currently, carbonaceous materials are mainly used as electrode active materials constituting the negative electrode of lithium secondary batteries, and lithium cobaltate is used as positive electrode active materials. However, the battery capacity of the lithium ion secondary battery configured as described is approaching the theoretical capacity, and there is a limit to increase the capacity in the future.

On the other hand, when silicon or tin is used as the negative electrode active material, the battery can be increased in capacity, but since the expansion and contraction degree associated with charging and discharging is large, the active material is undifferentiated due to expansion and contraction associated with charging and discharging or from the negative electrode current collector. There is a problem in that the characteristics are separated. In order to solve these problems, silicon oxide is drawing attention as an alternative material.

Silicon oxide is generally manufactured by vacuum agglomeration, and vacuum agglomeration is a method of producing silicon oxide by mixing silicon and silicon dioxide by heating using an electric furnace in a reaction chamber, and depositing evaporated gas on the inner wall of the agglomeration chamber. to be. However, the vacuum condensation method has a problem that the raw material must be heated for a long time, and the manufacturing efficiency is low due to the problem that the continuous process is difficult as the process is performed in a vacuum atmosphere.

For example, Korean Patent Laid-Open Publication No. 2003-0055091 discloses conductive silicon oxide powder by heat-treating particles of silicon oxide having general formula SiO _x (1 ≦ _x <1.6) at a temperature of 500 to 1200 ° C. in an organic gas or vapor atmosphere. Disclosed is a method of preparing a conductive silicon oxide powder and a conductive silicon oxide powder produced therefrom.

Korean Patent Laid-Open No. 2003-0021123 discloses a silicon oxide containing lithium by heating and reacting a mixture of a raw material powder capable of generating SiO gas and a metal lithium or lithium compound in an inert gas atmosphere or vacuum at a temperature of 8OO to 13OO ° C. A method of making a powder is disclosed.

In Korean Patent Laid-Open Publication No. 10-2007-0104848, a raw material powder mixed with silicon dioxide powder and a metal silicon powder is heated to an inert gas or a temperature of 1100 to 1450 ° C. under reduced pressure to generate silicon monoxide gas, and to precipitate the silicon monoxide gas. A method of making silicon oxide powder is disclosed.

In US Pat. No. 6,759,160 B2, a raw material powder containing at least silicon dioxide powder is gasified by heating at a temperature of 1100 to 1600 ° C. in an atmospheric pressure inert gas atmosphere or a vacuum atmosphere, and oxygen gas is continuously or intermittently injected, and a gas mixture is substrated. A method of producing silicon oxide powder is disclosed by a method of cooling to a surface to precipitate. However, in the above patents, the raw material powder is vaporized by simple high temperature heating, so that the process has to be performed for a long time.

Thermal plasma is used in the process of vaporizing and reacting raw materials and obtaining fine particles through quenching due to the temperature of thousands of K to tens of thousands K consisting of active species such as electrons, protons and neutrons. The direction of is determined. In addition, there are advantages in that various reaction conditions such as oxidation, reduction, and nitriding atmosphere may be formed through injection of a plasma generating gas, a reaction gas, and a purge gas. Due to these advantages, the thermal plasma is widely used in the field of material production and processing, and the waste treatment environment.

Therefore, the present inventors are studying a method for producing silicon oxide powder quickly and simply, and a method for rapidly producing silicon oxide by melting and vaporizing silicon dioxide using a thermal plasma jet and reducing it to silicon oxide is disclosed. Developed and completed the present invention.

An object of the present invention is to provide a method for producing silicon oxide (SiOx) powder using a thermal plasma.

Another object of the present invention is to provide a silicon oxide (SiO _x ) powder prepared by using a thermal plasma.

In order to achieve the above object, the present invention comprises the steps of melting and vaporizing a pellet consisting of silicon and silicon dioxide mixed powder or silicon dioxide powder using a thermal plasma jet (step 1); Injecting a reaction gas into the thermal plasma apparatus to reduce silicon dioxide in the vaporized gas to silicon oxide (SiO _x ) (where 0.5 <x <1.5); And it provides a method for producing silicon oxide (SiO _x ) powder comprising the step (step 3) of collecting the silicon oxide reduced in step 2 to silicon oxide (SiO _x ) powder.

In addition, the present invention provides a silicon oxide powder, which is prepared by the above method, characterized in that the particle form and the wire form is present in a mixture.

The method for producing silicon oxide (SiO _x ) powder using thermal plasma according to the present invention can synthesize nano-sized silicon oxide powder in a short time using a thermal plasma jet, and easy to vaporize by using a high temperature plasma, Process efficiency is good, there is a feature that easy to control the process conditions, there is an effect that the continuous process is possible as the process is performed under atmospheric pressure conditions. In addition, the prepared silicon oxide powder may be used as a negative electrode active material of a lithium secondary battery.

1 is a schematic view showing a thermal plasma jet generator;
2 is a graph obtained by X-ray diffraction analysis of silicon oxide powder according to the present invention;
3 is a transmission electron micrograph of the silicon oxide powder according to the present invention;
4 is a scanning electron micrograph of a silicon oxide powder according to the present invention;
5 is a limited field diffraction analysis photograph of the silicon oxide powder according to the present invention;
6 is a graph showing energy dispersion spectroscopic analysis of silicon oxide powder according to the present invention;
7 is a graph obtained by X-ray photoelectron spectroscopic analysis of silicon oxide powder according to the present invention;
FIG. 8 is a graph analyzing a reaction in which silicon oxide is produced by reacting silicon dioxide with hydrogen or carbon monoxide through a thermodynamic equilibrium composition program.

The present invention comprises the steps of melting and vaporizing a pellet consisting of silicon and silicon dioxide mixed powder or silicon dioxide powder using a thermal plasma jet (step 1);

Injecting a reaction gas into the thermal plasma apparatus to reduce silicon dioxide in the vaporized gas to silicon oxide (SiO _x ) (where 0.5 <x <1.5); And

It provides a method for producing silicon oxide (SiO _x ) powder comprising the step (step 3) of collecting the silicon oxide reduced in step 2 to the silicon oxide (SiO _x ) powder.

Hereinafter, the present invention will be described in detail step by step.

In the method for producing silicon oxide powder according to the present invention, step 1 is a step of melting and vaporizing a pellet consisting of silicon and silicon dioxide mixed powder or silicon dioxide powder using a thermal plasma jet, for the reduction reaction due to the reaction gas The pellet is first melted and vaporized.

The thermal plasma is an ionizing gas composed of electrons, ions, atoms, and molecules generated by a plasma torch using a direct current arc or a high frequency inductively coupled discharge. In one embodiment of the present invention, the thermal plasma jet, as shown in Figure 1, the torch unit (1) for supplying a heat source for melting and vaporizing pellets made of silicon and silicon dioxide mixed powder or silicon dioxide powder; A power supply device 2 for supplying power to the torch unit 1; A crucible 3 for fixing the pellets; A copper support (4) for fixing the crucible (3) but capable of water cooling with a double pipe; A blower 5 for exhaust gas treatment; A mass flow controller 6 for accurately injecting a small amount of reaction gas; A generating gas line (7) for supplying a plasma generating gas to the torch unit (1); A reaction gas line 8 for supplying a reaction gas; And a purge gas line 9 for supplying gas to form the reaction atmosphere in a pressurized atmosphere. The torch unit 1 uses a tungsten cathode rod and an anode nozzle, and injects a plasma generating gas between the anode nozzle and the cathode rod to generate a plasma jet. In addition, in order to protect the torch part 1 from high temperature heat, both electrodes are cooled by water cooling, and the reactor in which the reaction takes place is made of a stainless steel double tube with a window, and the inside can be seen. By using the ultra-high temperature thermal plasma, the pellet melting and vaporization of the step 1 can be performed in a short time compared to the conventional simple heating or combustion method. In order to prevent the inflow of oxygen into the reactor, argon gas is injected into the purge gas to generate a plasma jet under a pressurized atmosphere, and the crucible (3) having pellets fixed to reduce the impact that may be applied to the crucible (3) is It is desirable to approach the plasma jet slowly. In addition, the crucible 3 is preferably made of a metal having a high melting point or a sublimable material having a high temperature sublimation point so as not to be melted in a high temperature thermal plasma jet.

Argon, nitrogen, and a mixed gas of argon and nitrogen may be used as the thermal plasma generating gas for generating thermal plasma in step 1, and it is preferable to use a mixed gas of argon and nitrogen. The argon is a Group 8 element, which is easy to emit electrons with relatively little energy, and does not react with other reaction gases, and thus does not generate by-products. In addition, the nitrogen may provide heat required for evaporation of the silicon and silicon dioxide mixed powder pellet as the reaction heat generated during the recombination process by the gasification reaction (2N → N ₂ ) as the diatomic molecule. Accordingly, the mixed gas of argon and nitrogen can obtain a higher temperature plasma without generating byproducts.

When the pellet of step 1 consists of a mixed powder of silicon and silicon dioxide, the silicon and silicon dioxide are mixed in a molar ratio of 0.5: 1 to 4: 1. The process of silicon and silicon dioxide reacting in the solid phase to become silicon monoxide causes a rapid reaction as the boiling point is lowered. In the case of a single reaction of silicon and silicon dioxide, the reaction does not easily occur due to the higher boiling point. Therefore, when the mixing of the silicon and silicon dioxide is carried out at a ratio outside the molar ratio, only one component of silicon or silicon dioxide is left during the reaction so that the reaction hardly occurs, and thus regardless of the molar ratio of silicon and silicon dioxide There is a problem that reaction products are similarly produced.

In the silicon oxide powder manufacturing method according to the present invention, step 2 is a step of reducing the silicon dioxide in the vaporized gas to silicon oxide by injecting a reaction gas into the thermal plasma device. At this time, hydrogen or carbon monoxide may be used as the reaction gas of step 2, and silicon dioxide is reduced to silicon oxide by reaction of silicon dioxide and the reaction gas. In this case, in the reduced silicon oxide (SiO _x ) x is in the range of 0.5 <x <1.5, it is possible to control the x value by adjusting the flow rate of hydrogen or carbon monoxide.

In the method for producing silicon oxide powder according to the present invention, step 3 is a step of collecting the silicon oxide reduced in step 2 into silicon oxide (SiO _x ) powder. The silicon oxide powder collection of step 3 is performed by cooling silicon oxide in a high temperature gaseous state, and the silicon oxide powder is cooled and collected into silicon oxide powder using a water cooling method of quenching with 15 to 25 ° C. cooling water. By cooling the silicon oxide in a gaseous state with the cooling water at the above temperature, the temperature of the silicon oxide can be drastically reduced, thereby preventing the growth of the silicon oxide particles to capture nano-sized silicon oxide powder.

In addition, the present invention provides a silicon oxide powder is prepared by the above production method, the particle form and the wire form is mixed.

In this case, the particle size of the silicon oxide powder in the form of a particle is 25 to 45nm, the particle size of the wire form is 150 to 350nm.

Silicon oxide powder according to the present invention can be used as a negative electrode active material of a lithium secondary battery, when using the silicon oxide powder as a negative electrode active material to achieve high capacity of the battery and at the same time the expansion and contraction problems associated with conventional charging and discharging, A secondary battery having excellent characteristics can be manufactured by solving the problem of micronization of the active material and separation of the active material from the negative electrode current collector.

Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited by the following examples.

Example 1 Preparation of Silicon Oxide Powder Using Thermal Plasma

Silicon oxide powder was synthesize | combined using the direct current thermal plasma jet apparatus shown in FIG. The power of the DC thermal plasma apparatus was operated at 11.7 kW, and 15 L / min of argon gas and 3 L / min of nitrogen gas were mixed into the plasma gas injector of the torch and discharged to generate a plasma jet. Detailed operating conditions are shown in Table 1 below.

Operating condition Plasma power 300 A, 39 V (11.7 kW) Plasma generating gas Argon 15L / min, Nitrogen 3L / min Reaction gas Hydrogen 0.5 L / min Purge gas Argon 20L / min Pellet composition Silicon: Silicon dioxide = 2: 1

The pellet prepared by mixing silicon and silicon dioxide powder in the composition of Table 1 was placed in a tungsten crucible and placed on a copper support. The copper support can be adjusted in height up and down using this to approach the crucible containing the pellet to the generated plasma jet. The crucible was preheated for about 5 minutes at about 80 mm away from the torch to vaporize the pellet after it was completely melted to prevent thermal shock of the crucible. After that, the crucible was raised to about 40 mm away from the torch. Rapid vaporization begins. At the same time, hydrogen was supplied into the reactor at a flow rate of 0.5 L / min to react with silicon dioxide in the gaseous state to reduce the silicon oxide, and the reduced silicon oxide was collected through the reactor wall by cooling the double tube reactor.

Experimental Example 1 X-ray Diffraction Analysis

In order to determine the crystallinity of the silicon oxide powder, the silicon oxide powder of Example 1 was analyzed by X-ray diffraction, and the results are shown in FIG. 2.

As shown in FIG. 2, it was confirmed that the silicon oxide powder of Example 1 was crystalline silicon and amorphous SiO _x , and the cs calculated value of the crystal size was 7 nm by measuring the width of the diffraction line. Can be.

Experimental Example 2 Microstructure Analysis

(1) transmission electron microscope analysis

In order to analyze the microstructure of the silicon oxide powder, the silicon oxide powder of Example 1 was observed with a transmission electron microscope, and the results are shown in FIG. 3.

As shown in FIG. 3, when the silicon oxide powder particles of Example 1 were observed with a transmission electron microscope, it can be seen that crystalline and amorphous mixtures exist in one particle. In addition, when observing the entire silicon oxide powder, it can be seen that the particle form and the nanowire form are present in a mixture. Through this, it can be seen that the silicon oxide powder according to the present invention was prepared in the form of a mixture of crystalline silicon and amorphous SiO _x , it was confirmed that the prepared nano powder is mixed in the form of particles and nanowires.

(2) Scanning electron microscope analysis

In order to analyze the microstructure of the silicon oxide powder, the silicon oxide powder of Example 1 was observed with a scanning electron microscope, and the results are shown in FIG. 4.

As shown in Figure 4, it can be seen that the silicon oxide powder of Example 1 is present in the form of a mixture of particles and nanowires, the particle size of the particle shape is several tens nm, the particle size of the wire shape is several hundred nm. Able to know. Through this, it was confirmed that the silicon oxide powder according to the present invention is prepared by mixing tens of nm particle size and several hundred nm size nanowire form.

<Experiment 3> Selected area (electron) diffraction

In order to analyze the crystallinity of the silicon oxide powder, the silicon oxide powder of Example 1 was limited field diffraction analysis, the results are shown in FIG.

As shown in Fig. 5, when the entire silicon oxide powder of Example 1 was observed, the crystal plane of silicon was observed. In addition, when observing only the nanowire portion of the silicon oxide powder separately, it can be seen that the crystal plane is not observed and the nanowire portion is amorphous. Through this, it was confirmed that the particulate form of the silicon oxide powder according to the present invention is crystalline silicon, and the wire form part is amorphous SiO _x .

Experimental Example 4 Energy Dispersive Spectroscopy

In order to analyze the composition of the silicon oxide powder, the silicon oxide powder of Example 1 was subjected to energy dispersion spectroscopic analysis, and the results are shown in FIG. 6.

As shown in FIG. 6, it turns out that the silicon oxide powder of Example 1 is comprised from the silicon (Si) and oxygen (O) atom. Through this, it was confirmed that the silicon oxide powder according to the present invention was made of high purity nano powder without containing other impurities.

Experimental Example 5 X-Ray Photoelectron Spectroscopy (XPS)

In order to confirm the component ratio of the silicon oxide powder, the silicon oxide powder of Example 1 was subjected to X-ray photoelectron spectroscopic analysis, and the results are shown in FIG. 7.

X-ray photoelectron spectroscopy is calculated by the binding energy of electrons in an atom, and the binding energy has a unique value depending on the atom. Therefore, by observing the spectra of the photoelectron through the X-ray photoelectron spectroscopic analysis it is possible to quantitatively analyze the chemical bonding state and the element. As a result of the analysis based on this, as shown in FIG. 7, it can be seen that the silicon oxide powder of Example 1 is SiO _1.33 , and the silicon oxide powder according to the present invention is a silicon oxide powder in which silicon and silicon dioxide react or It was confirmed that it was prepared by reduction from silicon to silicon oxide.

Experimental Example 6 Analysis of Thermodynamic Equilibrium Composition

The reaction in which silicon dioxide reacts with hydrogen or carbon monoxide to produce silicon oxide was analyzed using a thermodynamic equilibrium program, and the results are shown in FIG. 8.

As shown in FIG. 8, it can be seen that silicon dioxide (SiO _x ) is produced by the reaction of silicon dioxide with hydrogen or carbon monoxide. At this time, it can be seen that the silicon dioxide is produced at the same time the fraction of silicon dioxide is lowered at a temperature of about 2000 ℃. Through this, it was confirmed that the silicon oxide is produced in accordance with the production method of the present invention.

1: torch
2: power supply
3: crucible
4: copper support
5: blower
6: flow controller
7: generated gas line
8: reaction gas line
9: purge gas line

Claims (8)

After generating a thermal plasma jet using 15 L / min of argon and 3 L / min of nitrogen as a generating gas, tungsten was fixed to a support made of copper by pellets made of silicon and silicon dioxide mixed powder mixed in a 2: 1 molar ratio. Charging the crucible with a material and transferring the crucible to the generated thermal plasma jet under an atmosphere in which argon at a flow rate of 20 L / min is injected as a purge gas to melt and vaporize the mixed powder (step 1);
Injecting hydrogen as a reaction gas into the thermal plasma apparatus at a flow rate of 0.5 L / min to reduce silicon dioxide in the vaporized gas to silicon oxide (SiO _x ) (where 0.5 <x <1.5) (step 2); And
Method for producing a silicon oxide powder (SiO _x), a step (Step 3) for rapid cooling by a silicon oxide reduced at the second step 15 to the cooling water of 25 ℃ collection of silicon oxide (SiO _x) powder. delete delete delete delete delete delete delete

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