KR102524264B1 - Yolk-shell structure nano composites fabricating system and method for fabricating nano composites using the same - Google Patents

Abstract

In a nanocomposite manufacturing system having a yoke-shell structure including silicon carbide and a nanocomposite manufacturing method using the same, the nanocomposite manufacturing system includes a mixing unit, a droplet chamber, a tube unit, a light source unit, and a collection unit. The mixing unit manufactures a silicone capsule by encapsulating at least one or more silicone particles. The droplet chamber disperses the silicone capsule with gas. The tube part allows the dispersed silicone capsules to flow in one direction. The light source unit provides light energy to the silicon capsule flowing in the tube unit. The collection unit collects the nanocomposite formed according to the provision of the light energy.

Description

Yoke-shell structured nanocomposite manufacturing system including silicon carbide and nanocomposite manufacturing method using the same

The present invention relates to a nanocomposite manufacturing system and a nanocomposite manufacturing method using the same, and more particularly, to a nanocomposite that is used for a light energy source and is elaborately designed to have a yoke-shell structure in which silicon particles are located. It relates to a nanocomposite manufacturing system having a yoke-shell structure that can be manufactured and a nanocomposite manufacturing method using the same.

Recently, as the demand for power storage systems with high energy storage efficiency or energy charging and discharging efficiency has rapidly increased while being miniaturized and lightweight, research and development on this has been actively conducted. In particular, silicon anode materials have the highest capacity density among these next-generation anode materials. It has been spotlighted as having high energy conversion efficiency during charging and discharging.

However, in the case of silicon anode materials, as rapid volume expansion and contraction are repeated during charging and discharging, there is a problem of inferior stability such as splitting of the material or short-circuiting of the electrical connection, which is a major obstacle to commercialization. Efforts are being made to solve this there is.

That is, in order to control or minimize the rapid volume change of silicon during the charging and discharging process as described above, research is being conducted to minimize the volume change and improve life stability by designing the electrode itself as a nanostructure and using it in combination with a carbon material. It is becoming.

In particular, as shown in FIG. 1, through the Stanford Yi Cui group in 2014, it has been found that a yolk-shell structure (Si pomegranate) performs a very ideal behavior as a stable silicon electrode. Efforts to manufacture an electrode having a yoke-shell structure that performs such an ideal behavior according to the present invention have been made, such as in Korean Patent Publication No. 10-2020-0025984.

However, in spite of this ideal behavior, the development of an effective manufacturing method has been insufficient to date due to the high cost required for the manufacture of the yoke-shell structure.

Republic of Korea Patent Publication No. 10-2020-0025984

Therefore, the technical problem of the present invention is focused on this point, and the object of the present invention is to be able to elaborately design a nanocomposite having a so-called yoke-shell structure in which silicon particles are located inside and carbon covers the outside, as well as , It relates to a nanocomposite manufacturing system having a yoke-shell structure, which can be continuously manufactured, thereby improving productivity at a relatively low cost and improving stability of the nanocomposite.

In addition, another object of the present invention relates to a method for manufacturing a nanocomposite using the nanocomposite manufacturing system.

A nanocomposite manufacturing system according to an embodiment for realizing the object of the present invention described above includes a mixing unit, a droplet chamber, a tube unit, a light source unit, and a collection unit. The mixing unit manufactures a silicone capsule by encapsulating at least one or more silicone particles. The droplet chamber disperses the silicone capsule with gas. The tube part allows the dispersed silicone capsules to flow in one direction. The light source unit provides light energy to the silicon capsule flowing in the tube unit. The collection unit collects the nanocomposite formed according to the provision of the light energy.

In one embodiment, the mixing unit may first coat at least one or more silicon particles with a low molecular weight material, and then secondarily coat a high molecular material on the silicon particles coated with the low molecular weight material.

In one embodiment, as the light energy is provided, the low-molecular material coated around the silicon particle is thermally decomposed and removed to form a void, and the high-molecular material is carbonized to form a shell. can

In one embodiment, the low molecular weight material is sodium dodecyl sulfate (SDS), cetrimonium bromide (CTAB), triton X-100 (triton X-100), ethoxylate (ethoxylate) It may be any one surfactant.

In one embodiment, the low molecular weight material may be any one of polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), and polystyrene (PS).

In one embodiment, the polymeric material is polyacrylonitrile (PAN), cellulose, lignin, phenolic resin (RF), polyimide (PI), polybenzene It may be any one of midazole (polybenzimidazole, PBI).

In one embodiment, the gas is, acetylene (acetylene) or toluene (toluene) of the carbon source gas, or a mixed gas of hydrogen (H ₂ ) and an inert gas to form a reducing atmosphere.

In one embodiment, the droplet chamber may include an ultrasonic generator that provides ultrasonic waves to the silicon capsule stored in the droplet chamber and scatters them upward.

In one embodiment, the silicone capsule may be scattered along with the application of the ultrasonic waves, transported by a gas provided into the droplet chamber, and supplied to the tube unit.

In one embodiment, the tube part may include a transparent material, and the light source part may be an intense pulsed light (IPL).

In one embodiment, a cleaning unit for cleaning the silicon capsule provided with the light energy may be further included.

In the nanocomposite manufacturing method according to an embodiment for realizing the above object of the present invention, at least one silicon particle is encapsulated to prepare a silicon capsule. The silicon capsule is dispersed together with gas and flows into a tube part extending in one direction. Light energy is provided to the silicone capsule flowing in the tube part. The nanocomposite formed by providing the light energy is recovered.

In one embodiment, the silicon capsule may further include cleaning the nanocomposite produced by receiving the light energy.

According to embodiments of the present invention, as light energy is provided to the silicone capsule, the low-molecular material of the silicone capsule is thermally decomposed to form voids, and the high-molecular material is carbonized to form a shell, a so-called yolk-shell. ) structure can be easily prepared.

That is, a nanocomposite having a relatively sophisticated structure can be manufactured through a relatively simple process of providing light to a silicon capsule flowing into a tube part.

In particular, as the silicone capsule continuously flows and passes through the tube portion and light energy is continuously provided by a light source such as IPL, the nanocomposite material can be continuously manufactured and productivity can be improved.

In this case, as the silicon capsule is supplied with a gas serving as a carrier in a state of being scattered by ultrasonic waves formed inside the droplet chamber, it is possible to naturally flow to the tube part.

In particular, the gas may simultaneously serve as a carrier and at the same time serve as a carbon source when supplying the light energy or form a reducing atmosphere.

1 is a graph showing that the yoke-shell structure performs an ideal behavior as a stable silicon electrode through the prior art.
2 is a schematic diagram showing a nanocomposite manufacturing system according to an embodiment of the present invention.
FIG. 3 is a schematic diagram illustrating light applied to the tube part and silicon capsules passing through the tube part and changing in the nanocomposite manufacturing system of FIG. 2 .
4 is a flowchart illustrating a method of manufacturing a nanocomposite using the nanocomposite manufacturing system of FIG. 2 .
FIG. 5 is a flow diagram illustrating the steps of encapsulating the silicon particles of FIG. 4;

Since the present invention can be applied with various changes and can have various forms, embodiments will be described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. Like reference numerals have been used for like elements throughout the description of each figure. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms.

These terms are only used for the purpose of distinguishing one component from another. Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, the terms "comprise" or "consisting of" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in more detail.

2 is a schematic diagram showing a nanocomposite manufacturing system according to an embodiment of the present invention. FIG. 3 is a schematic diagram illustrating light applied to the tube part and silicon capsules passing through the tube part and changing in the nanocomposite manufacturing system of FIG. 2 .

2 and 3, the nanocomposite manufacturing system 10 according to this embodiment includes a droplet chamber 100, a mixing unit 150, a tube unit 300, a light source unit 400, and a collection unit 500. ), and, although not shown, may further include a cleaning unit.

The droplet chamber 100 is a container forming a predetermined storage space 101 therein, and a silicon capsule 200 is positioned in the storage space 101 therein.

The silicone capsule 200 may be modeled into a structure as shown in FIG. 3, and is manufactured in the mixing unit 150.

That is, the silicone capsule 200 manufactured in the mixing unit 150 is provided to the droplet chamber 100 through a separate connection conduit 151 and is located inside the droplet chamber 100. .

In this case, when the manufacturing of the silicone capsule 200 in the mixing unit 150 is described, first, in the mixing unit 150, at least one silicon particle 201 is firstly prepared. Coating is performed using the low molecular weight material 202 .

In this case, the low molecular weight material 202 may be coated along the outer surface of the silicon particle 201 as it is mixed in the mixing unit 150 together with the silicon particle 201 .

In addition, although FIG. 3 illustrates that the low molecular weight material 202 is coated along the outer circumferential surface of one of the silicon particles 201, the low molecular weight material is coated along the outer circumferential surface in a state in which a plurality of silicon particles are adjacently bonded to each other. It could be.

The low-molecular-weight material 202 is a material with a relatively low molecular weight, for example, sodium dodecyl sulfate (SDS), cetrimonium bromide (CTAB), triton X-100 (triton X-100). 100), ethoxylate, or any one of the surfactants. Alternatively, polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polystyrene (PS) It may be any one of low molecular weight polymers.

In this way, after the low molecular weight material 202 is coated on the silicon particle 201, the high molecular material 203 is additionally coated on the outer surface of the low molecular weight material 202 secondarily.

In this way, for two times of coating of different materials, the mixing unit 150, although not shown, may be divided into a plurality of mixing units so that the two coating processes can proceed separately from each other.

The coating of the high molecular material 203 is also similar to the coating of the low molecular material 202, by providing the high molecular material 203 to the silicon particles coated with the low molecular material, and Mixing can be done.

As such, when the polymer material 203 is additionally coated, as shown in FIG. 3 , the polymer material 203 is coated to cover the outside of the low molecular material 202, and the silicon particles 201 The low molecular weight material 202 is interposed between the high molecular material 203 and the high molecular material 203 .

The polymeric material 203 is a material having a relatively high molecular weight, for example, polyacrylonitrile (PAN), cellulose, lignin, phenolic resin (RF), It may be a high-molecular polymer that is any one of polyimide (PI) and polybenzimidazole (PBI).

As described above, the low-molecular material 202 and the high-molecular material 202 are sequentially coated on the outside of the at least one silicon particle 201, and encapsulation of the silicon particle 201 is performed. The encapsulated silicon particles are hereinafter referred to as silicone capsules 200 for convenience of explanation.

The droplet chamber 100 is provided with an ultrasonic generator 130 at the bottom, and the ultrasonic generator 130 generates ultrasonic waves 131 upward in the storage space 101 of the droplet chamber 100. .

As the ultrasonic waves 131 are generated, the silicon capsules 200 located in the storage space 101 of the droplet chamber 100 scatter upward.

In this case, the silicone capsules 200 are located in the storage space 101 in the form of droplets, and are scattered upward as shown in FIG. 2 according to the provision of the ultrasonic waves 131. and become fluid.

Meanwhile, an inlet conduit 110 is connected to one side of the droplet chamber 100, and gas G is provided through the inlet conduit 110.

The gas (G) is provided to the inside of the droplet chamber 100 through the inlet conduit 110, and is a carrier for the silicon capsules 200 scattered upward according to the provision of the ultrasonic waves 131. By serving as a carrier, the silicon capsules 200 together with the gas G flow to the tube part 300 through the outlet conduit 120 connected to the upper part of the droplet chamber 100. will do

The gas (G) may be, for example, a carbon source gas such as acetylene or toluene, and thus, the silicon capsule 200 is carbonized through the provision of light energy, which will be described later. process can be accelerated.

Alternatively, the gas (G) may be, for example, a mixed gas in which hydrogen (H ₂ ) and an inert gas such as nitrogen (N ₂ ) or argon (Ar) are mixed. A reducing atmosphere can be formed when energy is supplied.

That is, the gas (G) serves as a carrier of the scattering flow of the silicon capsules 200 inside the droplet chamber 100, and supplies light energy in the process of passing through the tube part 300. It serves as a carbon source or forms a reducing atmosphere.

The tube part 300 has one end connected to the outlet conduit 120 connected to the upper part of the droplet chamber 100 and, as shown, extends along one direction and has a tube shape. .

In this case, a collection conduit 510 is connected to the other end of the tube part 300, and the collection conduit 510 is connected to the sunip unit 500.

The tube unit 300 may be in the form of a single tube extending in one direction, but, alternatively, a plurality of tubes diverging from the outlet conduit 120 may be formed of a plurality of tubes extending parallel to each other.

In this way, if the branched tubes are, they can be joined again through the collecting conduit 510.

In addition, the tube part 300 includes a transparent material, and may be formed of, for example, a quartz material. That is, as the tube part 300 is formed transparently, light energy provided from the light source part 400 can be more effectively provided to the silicon capsule 200 .

The gas (G) supplied through the outlet conduit 120 and the silicone capsule 200 flow in the inside 301 of the tube part 300 .

In this case, the gas (G) and the silicon capsule 200 are supplied to the tube portion ( The interior 301 of 300 can be continuously flowed.

The light source unit 400 provides light energy 401 to the tube unit 300, and in the case of the present embodiment, as shown in FIG. can

In this case, the position of the light source unit 400 is not limited, and it is sufficient if the light energy 401 can be provided to the silicon capsule 200 passing through the tube unit 300 .

In addition, as shown, the light chamber 410 covers the outside where the light source unit 400 is located to prevent the light energy provided from the light source unit 400 from being scattered to the outside, and to provide the light energy. Efficiency can be further improved.

The light source unit 400 may be, for example, an intense pulsed light (IPL), but is not limited thereto.

In this case, the light energy 401 provided from the light source unit 400 is continuously provided toward the tube unit 300, according to the continuous provision of light and the continuous flow of the silicone capsule 200, The silicon capsule 200 can receive constant light energy 401 while passing through the tube part 300 .

Thus, in the case of the present embodiment, there is an advantage in that the nanocomposite 250 described later can be continuously manufactured through continuous supply of light energy to the silicon capsule 200 .

On the other hand, the transformation of the silicon capsule 200 occurs intensively in the area (C) where the light energy 401 is directly provided by the light source unit 400. The area (C) where the light energy 401 is directly provided A temperature of about 700° C. can be formed.

In contrast, in the case of the surrounding areas B and D, which are covered by the light chamber 410 but do not directly provide light energy from the light source unit 400, a temperature of about 200 to 600° C. can be formed. In the case of the outer regions A and E that are not covered by the light chamber 410, a temperature of about 50 to 100° C. may be formed.

As the light energy 401 is received while passing through the tube part 300 , the silicon capsule 200 changes into a so-called nanocomposite 250 .

Specifically, as shown in FIG. 3, in the silicon capsule 200, the low-molecular-weight material 202, which was primarily coated on the outside of the silicon particle 201, transmits the light energy to the silicon particle 201. is absorbed, and as the temperature around the silicon particle 201 increases, it is thermally decomposed and removed.

Thus, in the silicon capsule 200, the portion where the low molecular weight material 202 is located becomes a void 252.

In contrast, in the silicone capsule 200, the high molecular material 203 additionally coated on the outside of the low molecular material 202 is carbonized as the light energy is provided, forming a so-called carbon shell 253. ) change to

As a result, in the case of the nanocomposite 250, at least one silicon particle 201 is located in the center of the inside, forms a predetermined space, and a carbon shell 252 is formed on the outside, a so-called yolk-shell -shell) structure.

The collection unit 500 is connected to and positioned through the collection conduit 510 connected to the other end of the tube part 300, and the nanocomposite of the yoke-shell structure generated in the tube part 300 ( 250) is recovered.

The collection unit 500 may be in the form of a container having a predetermined storage space, and its size or shape is not limited.

Meanwhile, although not shown, the cleaning unit may be additionally provided on the collection unit 500 or on the front end of the collection unit 500, that is, on the collection conduit 510.

The cleaning unit performs cleaning of the nanocomposite 250 generated according to the supply of the light energy 401, and removes impurities or remaining low-molecular substances on the nanocomposite 250.

In this case, cleaning in the cleaning unit may be performed using an acid or an organic solvent.

4 is a flowchart illustrating a method of manufacturing a nanocomposite using the nanocomposite manufacturing system of FIG. 2 . FIG. 5 is a flow diagram illustrating the steps of encapsulating the silicon particles of FIG. 4;

Referring to FIGS. 5 and 6 , in the nanocomposite manufacturing method, first, at least one silicon particle 201 is encapsulated to manufacture a silicon capsule 200 (step S10).

In this case, the production of the silicone capsules 200 is performed in the mixing unit 150. First, at least one silicon particle 201 is mixed with a low molecular weight material 202, and the silicon particles 201 ) is coated with the low molecular weight material 202 on the outside (step S11).

Thereafter, the high molecular material 203 is mixed with the silicon particles 201 coated with the low molecular weight material 202 to additionally coat the high molecular material 203 (step S12).

Since the coating through mixing of the low molecular weight material 202 and the high molecular weight material 203 in the mixing unit 150 is the same as described above, duplicate description will be omitted.

As described above, when the silicone capsule 200 is manufactured, the silicone capsule 200 is supplied to the droplet chamber 100, and in the droplet chamber 100, provided to the inside of the droplet chamber 100 The gas (G) and the silicon capsule 200 are scattered upward in the form of liquid droplets by the ultrasonic wave 131 provided from the lower part, and are allowed to flow into the tube part 300 (step S20).

Thereafter, the light energy 401 is provided from the light source unit 400 to the silicon capsule 200 flowing in the tube part 300 (step S30), and by the light energy thus provided, the silicon The capsule 200 is changed into a so-called nanocomposite 250 .

In this case, since the details of the change to the nanocomposite 250 are the same as described above, overlapping descriptions will be omitted.

Thereafter, the nanocomposite 250 in the cleaning unit is subjected to a cleaning process to remove impurities or remaining low-molecular substances (step S40), and then the nanocomposite 250 is removed through the collection unit 500. is recovered (step S50).

As described above, through a relatively simple yet continuous process, it is possible to continuously produce a yolk-shell structured nanocomposite having a sophisticated structure.

According to the embodiments of the present invention as described above, as light energy is provided to the silicone capsule, the low-molecular material of the silicone capsule is thermally decomposed to form voids, and the high-molecular material is carbonized to form a shell, so-called yoke-shell ( A yolk-shell structured nanocomposite can be easily prepared.

That is, a nanocomposite having a relatively sophisticated structure can be manufactured using a relatively simple process of providing light to a silicon capsule flowing into a tube part.

In particular, as the silicone capsule continuously flows and passes through the tube portion and light energy is continuously provided by a light source such as IPL, the nanocomposite material can be continuously manufactured and productivity can be improved.

In this case, as the silicon capsule is supplied with a gas serving as a carrier in a state of being scattered by ultrasonic waves formed inside the droplet chamber, it is possible to naturally flow to the tube part.

In particular, the gas may simultaneously serve as a carrier and at the same time serve as a carbon source when supplying the light energy or form a reducing atmosphere.

Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention described in the claims below. You will understand that you can.

10: Nanocomposite manufacturing system
100: droplet chamber 130: ultrasonic generator
150: mixing unit 200: silicone capsule
201: silicon particle 202: low molecular weight polymer
203: polymer polymer 250: nanocomposite
252: void 253: carbon shell
300: tube part 400: light source part
410: light chamber 500: collection unit

Claims (13)

A mixing unit for manufacturing a silicone capsule by encapsulating at least one or more silicon particles;
a droplet chamber dispersing the silicon capsule with gas;
a tube portion through which the dispersed silicone capsules flow in one direction;
a light source unit providing light energy to the silicon capsule flowing in the tube unit; and
And a collection unit for recovering the nanocomposite formed according to the provision of the light energy,
The tube part includes a transparent material, the light source part is IPL (intense pulsed light),
The light source unit intensively and continuously provides IPL to a certain area of the tube unit, and as the silicone capsule continuously flows inside the tube unit, the silicone capsule receives constant light energy while passing through the tube unit. A nanocomposite manufacturing system to be. The method of claim 1, wherein the mixing unit,
A nanocomposite manufacturing system, characterized by firstly coating at least one silicon particle with a surfactant or polymer, and then secondarily coating the surface active agent or polymer-coated silicon particle with a polymer. The method of claim 2, as the light energy is provided,
The surfactant or polymer primarily coated around the silicon particle is thermally decomposed and removed to form a void, and the secondary coated polymer is carbonized to form a shell. Characterized in that Nanocomposite manufacturing system. The method of claim 2, wherein the firstly coated surfactant is,
Preparation of a nanocomposite characterized by being any one of sodium dodecylsulfate (SDS), cetrimonium bromide (CTAB), triton X-100, and ethoxylate system. The method of claim 2, wherein the firstly coated polymer,
A nanocomposite manufacturing system, characterized in that any one of polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), and polystyrene (PS). The method of claim 2, wherein the secondly coated polymer,
Any one of polyacrylonitrile (PAN), cellulose, lignin, phenolic resin (RF), polyimide (PI), and polybenzimidazole (PBI) A nanocomposite manufacturing system, characterized in that. The method of claim 1, wherein the gas,
A nanocomposite manufacturing system, characterized in that the mixed gas of hydrogen (H ₂ ) and an inert gas forming a carbon source gas such as acetylene or toluene, or a reducing atmosphere. The method of claim 1, wherein the droplet chamber,
And a nanocomposite manufacturing system comprising an ultrasonic generator for providing ultrasonic waves to the silicon capsule stored inside the droplet chamber and scattering them upward. The method of claim 8, wherein the silicone capsule,
The nanocomposite manufacturing system, characterized in that scattered with the application of the ultrasonic wave, transported by the gas supplied to the inside of the droplet chamber, and supplied to the tube unit. delete According to claim 1,
The nanocomposite manufacturing system further comprises a cleaning unit for cleaning the silicon capsule provided with the light energy. encapsulating at least one silicon particle to produce a silicone capsule;
dispersing the silicone capsules together with gas and flowing them into a tube part extending in one direction;
providing light energy to the silicon capsule flowing in the tube through a light source; and
Recovering a nanocomposite formed by providing the light energy;
The tube part includes a transparent material, the light source part is IPL (intense pulsed light),
The light source unit intensively and continuously provides IPL to a certain area of the tube unit, and as the silicone capsule continuously flows inside the tube unit, the silicone capsule receives constant light energy while passing through the tube unit. A method for manufacturing a nanocomposite. According to claim 12,
The nanocomposite manufacturing method further comprising the step of cleaning the nanocomposite produced by receiving the light energy to the silicon capsule.

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