WO2016052981A1

WO2016052981A1 - Hollow carbon capsule manufacturing method

Info

Publication number: WO2016052981A1
Application number: PCT/KR2015/010295
Authority: WO
Inventors: 김인영; 이진영; 손권남; 황의용; 권원종
Original assignee: 주식회사 엘지화학
Priority date: 2014-09-30
Filing date: 2015-09-30
Publication date: 2016-04-07

Abstract

The present invention relates to a hollow carbon capsule manufacturing method using polymer particles as a soft template and uses a spray-drying method, thereby simply and effectively manufacturing the hollow carbon capsules.

Description

【Specification】

[Name of invention]

Method for producing hollow carbon capsule

[Cross Citation with Related Application (s)]

This application is filed with Korean Patent Application No. 10-2014-0131859, filed on September 30, 2014.

Claims the benefit of priority based on Korean Patent Application No. 10-2014-0131860 filed on September 30, 2014 and Korean Patent Application No. 10-2015-0137058 filed on September 25, 2015, and is disclosed in the literature of such Korean patent applications. All content is included as part of this specification.

Technical Field

The present invention relates to a production method capable of mass production of hollow carbon capsules.

Background Art

Hoi low carbon capsule refers to particles in which the shell having a pore inside and forming a p _0re is made of carbon. Due to the internal pore of the hollow carbon capsule, the surface area is wide, and the pore can serve as a storage space. The hollow carbon capsulum has various uses such as adsorbents, hydrogen storage materials, additives, catalyst supports, and lubricants. The manufacturing principle of the hollow carbon capsule is to form the structure of the template core and the carbon precursor shell, and then remove the template. At this time, it is divided into a method of using a hard template and a method of using a sof t template according to the type of template used. The method of using a hard template is a method of using an inorganic material of silica or metal oxide film as a template. Hard template is easy to maintain the pore structure because there is almost no change in shape during carbonization, there is an advantage that the shape of the pore can be easily adjusted by adjusting the shape of the hard template. However, the carbonization process requires the formation of a carbon shell and then the removal of the hard template. The shell formation and the pore formation are divided into two stages. In general, the removal of the hard template with toxic acidic or basic materials causes environmental problems. have. The method of using a soft template is a method of using an organic material capable of thermal decomposition such as a polymer as a template. In the carbonization process, the polymer used as a template is thermally decomposed and removed, and at the same time, carbonization of the carbon precursor proceeds at the same time, so the process is simple and no toxic substance is used. However, since the pyrolysis and carbonization of the polymer proceed simultaneously and the form of the formed pore is likely to collapse, care must be taken in selecting the material compared to the method using a hard template. The method of using a soft template has two main considerations, one is to prepare particles of the core part of the soft template and the shell part of the carbon precursor before the carbonization process, and the other is the material of the soft template and the carbon precursor. Conventionally, a method of sulfonating the surface of polystyrene particles and allowing aniline to be modified therein, and then polymerizing aniline to form the structure of the core (polystyrene) / shell (polyaniline) and heat-treating them to produce the vaporized carbon particles It has been reported (DAI Xiao-ying et al., New Carbon Materials, 2011, 26 (5): 389-395). However, since the sulfuric acid should be used because the sulfonation method is used, there is an environmental problem and is not suitable for mass production. In addition, the material selection of the soft template and the carbon precursor is also important. If the thermal properties of the two materials are similar, an additional process is required because the shape of the formed pore is likely to collapse. For example, a method of carbon-coating the surface of polystyrene particles with glucose having similar thermal properties to form a core (polystyrene) / shell (carbon) structure and heat-treating the same has been reported (Robin J). White et al., J. Am. Chem. Soc., 2010, 132: 17360-17363). However, this method requires about 24 hours of glucose pretreatment in the autoclave to form carbon shells, which is not suitable for mass production because of the long process time. not. Therefore, the thermal properties of the soft template and the carbon precursor must be distinguished. In addition, since the carbon precursor forms the carbon shell, a material that can maintain the structure of the carbon shell to be formed must be selected. Therefore, there is a need for a method for producing hollow carbon capsules that are suitable for mass production while using soft templates and that can maintain the shape of pore well. Therefore, the inventors of the present invention while studying a method for mass production of hollow carbon capsules, using the polymer particles as a soft template, spray and drying (spray-drying) method, using a simple and effective production of hollow carbon capsules It was confirmed that the present invention was completed.

[Content of invention]

[Problem to solve]

The present invention is to provide a manufacturing method capable of producing a hollow carbon capsule simply and effectively.

In addition, the present invention is to provide a vacuum-type carbon capsule produced by the above production method.

[Measures of problem]

In order to solve the above problems, the present invention provides a method of manufacturing a hollow carbon capsule comprising the following steps:

Preparing a spray solution comprising a carbon precursor, polymer particles, and a solvent (step 1);

Spraying and drying the spray solution to prepare particles (step 2); And heat treating the particles to carbonize the carbon precursor and remove the polymer particles (step 3). As used herein, the term "hol low carbon capsule" refers to a particle having a core / shell structure in which the core portion is a pore and the shell portion is made of carbon. . In addition, the hollow carbon capsule prepared in the present invention may be prepared in a form in which they are aggregated together. When manufactured in a clustered form, each shell has a structure that connects to another shell. An example of a hollow carbon capsule according to the present invention is shown in FIG. 6. Since a large number of pore is present in the hollow carbon capsule, and the pore has a large surface area and a storage space therein, the pore can be used as an adsorbent, a hydrogen storage material, an additive, a catalyst support, a lubricant, and the like. The principle of producing hollow carbon capsules according to the invention is to produce particles of the core / shell structure and then to remove the material of the core while maintaining the structure of the shell. In other words, removal of the core material and formation of the carbon shell must occur simultaneously through the heat treatment. Accordingly, in the present invention, the carbon precursor is used as the shell material and the polymer particles are used as the core material, and the core / shell structured particles are prepared by spraying and spray-drying, and then the ^' heat-treated hollow carbon capsule is used. It is characterized by manufacturing. First, step 1 is a step of preparing a spray solution for spraying and drying, the step of preparing a spray solution containing a carbon precursor, polymer particles and a solvent. The polymer of the polymer particles may be used one or more, and may be polystyrene, poly (methyl methacrylate), polypropylene, polyethylene, polyurethane, polyvinyl alcohol, polyvinylacetate or ethylene-vinyl acetate. Preferably, the polymer of the polymer particles is polystyrene. The polymer particles can be easily purchased commercially, in the case of polystyrene particles can be easily prepared by the emulsion polymerization method. The emulsion polymerization process comprises the steps of adding to a polystyrene monomer and an emulsifier * solvent; And it can be prepared by the step of polymerization by adding an initiator. Water may be used as the solvent, and SDS (sodium dodecyl sul fate) may be used as the emulsifier. The emulsion polymerization method has the advantage of controlling the size of the polystyrene particles by controlling the content of the emulsifier and monomer. The carbon precursor is characterized in that it crosslinks at a temperature lower than the thermal decomposition temperature of the polymer particles. That is, the carbon precursor and the polymer particles have different thermal behavior depending on temperature. For example, as shown in FIG. 2 (Experimental Example 1), polystyrene particles are pyrolyzed at 400-450 ^° C., but lignosulfonate, an example of a carbon precursor that can be used in the present invention, is about 45% by weight of carbon. You can see that is left. Accordingly, in the case where the two materials have a core / shell structure, as shown in FIG. 3 (Experimental Example 2), the carbon precursor is crosslinked in the vicinity of 200 ^° C. to form a shell first, and then thermal decomposition of the polymer particles occurs at 400-450 ^° C. . Through this, all polymers in the core portion may be thermally decomposed to form empty spaces occupying the space, and carbon precursors in the shell portion may be carbonized to form carbon shells. In addition, as the carbon precursor is carbonized, mesopores may be formed in the cell. In addition, the carbon precursor may be used one or more, preferably a substance having aromaticity and soluble in water. Examples of carbon precursors having the above characteristics include lignosulfonate, tannic acid, gallic acid, vanillic acid, dopamine, folic acid, and caffe. Acids (caffeic acid, rosmarinic acid, chlorogenic acid, ferulic acid, sinapinic acid, ellagic acid and ellagitannins). Can be. Examples of the ellagitannin-based compounds include castalazine, castal in, casuarictin, grandinin, punicalagin and punicalin, Roburin A, telimagrandin, and terflavin B. Preferably, lignosulfonate may be used as the carbon precursor. The diameter of the polymer particles corresponds to the pore diameter of the hollow carbon capsule to be finally produced, and may be appropriately selected depending on the intended use. Preferably, polymer particles having a diameter of 10 nm to 20,000 nm may be used. Water may be used as the solvent of the spray solution. The weight ratio of the carbon precursor and the polymer particles in the spray solution is preferably 0.07: 3 to 70: 3. The thickness of the carbon shell can be controlled by adjusting the content of the carbon precursor, and the higher the content of the carbon precursor, the thicker the carbon shell. In addition, it is preferable to stir the spray solution so that the carbon precursor can be adsorbed well on the surface of the polymer particles. In addition, in step 1, the spray solution may further include carbon nanotubes. When the carbon nanotubes are used together, the carbon nanotubes remain during the heat treatment to be described later, so that the structure of the carbon shell can be stably maintained, and the electrical conductivity and the mechanical properties can be improved by the inherent characteristics of the carbon nanotubes. The carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes. The length of the carbon nanotubes is preferably 0.5 μ ιτι to 50 μ ιτι. It is preferable to sonicate the spray solution containing the carbon nanotubes so that the carbon nanotubes may be well dispersed in the spray solution. The weight ratio of the carbon nanotubes and the carbon precursor in the spray solution is preferably 1.5: 1 to 10: 1. Step 2 is a step of preparing particles of the core / shell structure, the step of preparing the particles by spraying and drying the spray solution prepared in step 1. The spray-drying method is a method widely used in the manufacture of foods, medicines, ceramics, and the like. Since the spherical particles of the desired size are uniformly produced, no additional processing is required, and thus the method is suitable for mass production. to be. When spraying the spray solution prepared in step 1, the surface area of the polymer A carbon precursor is adsorbed on the surface of the particles, and dried to prepare particles having a core / shell structure. As a result, the polymer particles form the core portion, and the carbon precursor forms the shell portion. In addition, the particles of a plurality of core / shell structures are aggregated, and the overall shape is close to a spherical shape. Step 3 is a step of finally manufacturing the hollow carbon capsule, and heat treating the particles prepared in step 2 to carbonize the carbon precursor and remove the polymer particles. The polymer particles are thermally removed through the heat treatment to form pores, and the carbon precursors are carbonized to form carbon shells. The heat treatment temperature is controlled to a temperature that pyrolyzes the polymer particles and carbonizes the carbon precursor, preferably 200-35 (first treatment at C and second treatment at 400-60CTC. thermal polymer i zat ion,

The shell-shaped solid carbon through a primary _treatment, it is possible to generate. The secondary treatment temperature is a temperature at which the polymer particles are pyrolyzed, and the polymer particles may be removed through the secondary treatment to form pores. The primary silver and the secondary temperature may be applied respectively, or a method of gradually increasing the temperature in a range including both the primary temperature and the secondary temperature may be applied. Preferably, the temperature was raised from room temperature (25 ^° C) to 400 ~ 600 ^° C, it is preferred to heat treatment for 2 hours at 400 ~ 600 ^° C. The temperature is preferably raised to 10 ^° C / min. In addition, as described above, when the carbon nanotubes are additionally used in the step 1, since the carbon nanotubes are maintained as they are, the structure of the intertwined carbon nanotubes is maintained, and the polymer particles are removed by pyrolysis. It is possible to maintain the formed empty space (pore) stably. In addition, the carbon nanotubes can impart electrical conductivity and mechanical strength to the hollow carbon capsule, and thus, the shape can be stably maintained even when the hollow carbon capsule is used under severe conditions. The method for producing the hollow carbon capsule according to the present invention has the advantage of using a spraying and drying method to form a core / shell structure, using no toxic substances, reducing environmental problems, and being suitable for mass production. In addition, since the spray solution is an aqueous solution, a material that is well dispersed in water may be applied to change the properties of the hollow carbon capsule to be manufactured. In addition, by using polymer particles which are soft templates, pore formation and carbon shell formation are possible at the same time, and there is an advantage that the process is simple. In addition, as a carbon precursor, a material that is inexpensive and easy to handle may be used, and thus, the process may be easy and manufacturing cost may be reduced. In addition, the present invention provides a hollow carbon capsule prepared by the above production method. An example of a hollow carbon capsule made in accordance with the present invention is shown in FIG. 6. In the hollow carbon capsul, the diameter of the inner pore is 10 nm to 20, 000 mm 3. In addition, the carbon shell has a thickness of 1 nm to 1,000 nm. In addition, when the hollow carbon capsule is manufactured in the form of agglomeration with each other, the diameter of the entire hollow carbon capsule is 12 nm to 22,000 nm. Hollow carbon capsules produced according to the present invention is characterized in that the pore is uniformly formed as a rigid shell, and the shape of the shell is well maintained without being broken. Accordingly, the hollow carbon capsule manufactured according to the present invention can be used as an adsorbent, a hydrogen storage material, an additive, a catalyst support, a lubricant, and the like by utilizing a large surface area and an inner space.

【Effects of the Invention】

In the method for producing a vaporized carbon capsule according to the present invention, the hollow carbon capsule can be produced simply and effectively by using the polymer particles as a soft template and by using a spray-drying method. [Brief Description of Drawings]

1 schematically shows a method of manufacturing the hollow carbon capsule of the present invention. ^{^} FIG. 2 graphically shows the TGA results of polystyrene (PS) and lignosulfonate (LS). ^'

Figure 3 is a graph showing the TGA results with the increased carbon capsule according to an embodiment of the present invention.

4 is a graph showing the BET surface area and the pore distribution (FIG. 4A) and the Isotherm dot result (FIG. 4B) of the hollow carbon capsule according to the embodiment of the present invention.

FIG. 5A shows polystyrene particles, FIG. 5B shows particles of PS core / LS shell before heat treatment, and FIG. 5C shows particles of PS core / LS shell after heat treatment.

Figure 6 shows the pore and carbon shell of the hollow carbon capsule according to an embodiment of the present invention.

Figure 7 shows an SEM image of a hollow carbon capsule according to an embodiment of the present invention.

Figure 8 shows a TEM image of a hollow carbon capsule according to an embodiment of the present invention.

9 is a graph showing the BET surface area (FIG. 9A) and the pore distribution (FIG. 9B) of the vaporized carbon capsule according to the embodiment of the present invention.

Figure 10 shows the powder resistance measurement results of the hollow carbon capsule according to an embodiment of the present invention.

[Specific contents to carry out invention]

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto. Preparation Example: Preparation of Polystyrene Particles

Prior to the preparation of the hollow carbon capsules according to the invention, polystyrene particles used as soft templates were prepared. Specifically, 0.1 g of sodium dodecyl sulfate (SDS) was added to 90 mL of distilled water, followed by stirring (300 rpm) while raising the temperature to 80 ^° C. to dissolve SDS. 10 g of styrene was added to the solution and mixed for 10 minutes. 0.1 g of the initiator KPSCpotassium persulfate) was completely dissolved in 10 mL of distilled water, which was then added to the styrene-dissolved solution and polymerized for 6 hours to prepare the polystyrene particles in a sol state (10 wt% PS sol.) . The prepared polystyrene particles are shown in Figure 5 (a), the diameter of the particles was about 200 nm. Example 1 Preparation of Hollow Carbon Capsule

1) Preparation of hollow carbon capsul

The manufacturing method of the hollow carbon capsule according to the present invention is schematically illustrated in FIG. 1. Specifically, 1 g of lignosulfonate was added to 200 mL of distilled water, and completely dissolved using bath sonication. 10 wt PS sol prepared in Preparation Example in the solution. 30 mL was added and mixed with a homogenizer to prepare a spray solution. Spray and dry the spray solution with a Spray-dryer (Outlet temp .: 180 ^° C, aspirator: 95%, feeding rate: 15%), and heat the temperature up to 600 ^° C at a rate of 10 ^° C / min in a tube furnace. After raising for 2 hours at 600 ^° C. (Ar condition), a hollow carbon capsule was prepared.

2) Thermogravimetric Analysis

Thermogravimetric analysis was performed to confirm the temperature-dependent behavior of lignosulfonate and polystyrene in the heat treatment process. Specifically, the weight according to temperature was measured for each of the used lignosulfonate (LS) and the polystyrene particles, and the results are shown in FIG. 2. As shown in FIG. 2, the lignosulfonate (LS) exhibited a constant mass loss with increasing temperature, and thermal polymerization occurred at about 200-35 CTC, indicating that about 45 wt% of carbon remained after the entire process. On the other hand, Polystyrene (PS) was found that no mass loss occurs with increasing temperature, but sudden mass loss occurs at about 400-450 ^° C., and almost all polystyrene is pyrolyzed above about 45 CTC. From the above results, it was confirmed that the thermal characteristics of lignosulfonate and polystyrene are different, and that lignosulfonate may be thermal polymer i zat i on before silver, in which all of polystyrene is pyrolyzed.

3) Thermogravimetric Analysis

The experiment was carried out in the same manner as the thermogravimetric analysis, using the particles prepared by spraying and drying in the above example to determine the weight according to the degree of silver, the results are shown in FIG. As shown in FIG. 3, a sharp mass loss was observed around 4 C C due to the polystyrene core. However, it was confirmed that lignosulfonate was not thermally decomposed due to thermal polymer i zat ion, and about 11% by weight was finally left. Thus, the remaining material formed a shell of hollow carbon capsul. It was confirmed. In addition, the result is also consistent with the result of FIG. Specifically, the particles prepared by spraying and drying in the above example contains lignosulfonate at 25 weight ¾ (PS / LS = 3/1), and according to FIG. 2, all polystyrene is removed after the whole process, The lignosulfonate can be assumed to have about 45% by weight of carbon remaining. Therefore, the content of lignosulfonate in the final hollow carbon capsule is theoretically about 11% by weight (0.25 X 0.45), which is consistent with the result of FIG.

4) Measurement of specific surface area and pore volume of hollow carbon capsule

The specific surface area and pore volume of the prepared hollow carbon capsule were measured as shown in FIG. 4. As a result, the BET surface area was measured to be 126.9483 m ² / g and the pore volume was 0.328744 cmVg. 5) Observation of hollow carbon capsule

The prepared hollow carbon capsule was observed in a microscope as shown in FIG. 5, and polystyrene particles and core / shell particles before the heat treatment process were also observed for comparison. Fig. 5 (a) shows the polystyrene particles before spraying, which are spherical particles having a diameter of about 200 nm. Figure 5 (b) shows the core / shell particles before the heat treatment process, the total diameter is about 1000-3000 nm and polystyrene particles were observed inside. 5 (c) shows the hollow carbon capsule after the heat treatment process, where pore was observed in the place where the polystyrene was removed, and it was observed that the carbon shell did not collapse and maintained its shape well. 6, the hollow carbon capsule was observed in more detail with a microscope. As shown in FIG. 6a, a spherical hollow carbon capsule was observed as a whole, and it was confirmed that pore was present therein. In addition, as shown in Figure 6b, it was confirmed that the thickness of the shell is about 20 mn. Example 2 Preparation of Hollow Carbon Capsules Containing Carbon Nanotubes

1) Preparation of hollow carbon caps containing carbon nanotubes

1.5 g of CNT (Hyosung, 10-30 μτη) and 2.5 g of PSS-Li aqueous solution (Aldrich, 30 wt%) were added to 125 mL of distilled water, followed by sonication three times for 10 minutes to prepare an aqueous carbon nanotube dispersion. It was. 1 g of lignosulfonate was added to 150 mL of distilled water, completely dissolved by bath sonication, and then added to the aqueous carbon nanotube dispersion. Here, 10 wt% PS sol. 30 mL was added and mixed with a homogenizer to prepare a spray solution. The spray solution Spray-dryer (Out 1 et temp .: 180 ° C, aspirator · '95%, feeding rate: 15%) by spraying and drying, in a tube furnace at a rate of TC / min to a temperature 600 ^° C After raising and calcining at 600 ^° C. for 2 hours (Ar conditions), hollow carbon capsules were prepared. 2) Observation of the hollow carbon cap

The hollow carbon capsule prepared in Example was observed under a microscope.

SEM images are shown in FIG. 7 and TEM images are shown in FIG. 8. As shown in FIG. 7, it was confirmed that the form of pore was well maintained after carbonization, and the pore diameter was about 20C 220 nm, which was almost the same as the diameter of the polystyrene particles prepared in Preparation Example. From this, it was confirmed that the space in which the polystyrene particles were removed was well maintained as a pore. In addition, as shown in Figure 8, it was confirmed that the carbon nanotubes in the form of entangled in the hollow carbon capsule maintains the pore structure.

3) Measurement of specific surface area and pore volume of hollow carbon capsule

The specific surface area and pore volume of the hollow carbon capsule prepared in the above example

9, the BET surface area was 133.5264 m ² / g, the pore volume was 0.309500 cm ³ / g.

4) Powder Resistance Measurement of Hollow Carbon Cap

The powder resistance of the hollow carbon capsule prepared in the above example was measured. In addition, the powder resistance of the hollow carbon capsule prepared in Example 1 was also measured for comparison. Specifically, 1 g of each hollow carbon capsule was placed in a powder holder, and a bar was added. This was mounted on a powder resistance measuring device (HPRM-1000, Hantech Co., Ltd.), and then the sheet resistance, electrical conductivity, and packing density were measured while pressing the cylindrical bar at a constant pressure. The results are shown in FIG. 10 and Table 1 below.

Table 1 Example 1 Example 2

Load Press Packing Packing

Conductivity Conduct ivity

(kg) (Mpa) densi ty densi ty

(S / cm) (S / cm)

(g / cc) (g / cc)

400 0.13 5.42X10 ^"5 3.26X10 ^{" 1} 2.57 3.92X10— ¹

800 0.25 1.08 10 ^"4 4.44X10 ^{" 1} . _ 5.21 5.57X10— ¹

1200 0.37 1.56X10— ⁴ 5,44X10— ¹ 7.93 7.33X10 ^"1

1600 0.5 2.00X10 ^"4 6.26ΧΚΓ ¹ 10.3 8.79X10— ¹

2000 0.62 2.52X10— ⁴ 7.24X10— ¹ 12.8 1.03

As shown in Figure 10 and Table 1, the hollow carbon kaepseul of Example 2 containing the carbon nanotubes, showing a high electric conductivity of approximately 10 ⁵ times greater than that in Example 1. The carbon nanotubes that do not contain . Through this, when the carbon nanotubes are used, the hollow carbon capsule according to the present invention can be confirmed that the conductive pathways are formed internally and externally due to the carbon nanotubes, thereby significantly improving the electrical conductivity. In addition, it could be seen that in both Examples 1 and 2, the conductivity increased as the measured pressure increased.

Claims

[Patent Claims]

[Claim 1]

Preparing a spray solution comprising a carbon precursor, polymer particles, and a solvent;

Spraying and drying the spray solution to produce particles; And

Heat treating the particles to carbonize a carbon precursor and remove polymer particles;

Method for producing hollow carbon capsules.

[Claim 2]

The method of claim 1, wherein the spray solution comprises carbon nanotubes.

[Claim 3]

The method of claim 1,

The carbon precursor is crosslinked at a temperature lower than the thermal decomposition temperature of the polymer particles,

Method for producing hollow carbon capsules.

[Claim 4]

The method of claim 1, wherein the carbon precursor, lignosulfonate, tannic acid, gallic acid, vanillic acid, dopamine, folic acid, caffeic acid, rosemary acid, chlorogenic acid, perlic acid, cinafinic acid, ellagic acid, castalazine, car Stalin, casuaritin, grandinin, punicalgin, punicalin, lobulin A, tellimagrandin and terflavin B, at least one member selected from the group consisting of.

[Claim 5]

The method of claim 1, wherein the polymer of the polymer particles is selected from the group consisting of polystyrene, poly (methyl methacrylate), polypropylene, polyethylene, polyurethane, polyvinyl alcohol, polyvinylacetate and ethylene-vinyl acetate. The production method characterized by one or more

[Claim 6]

The method of claim 5, wherein the polymer particles have a diameter of 10 nm to 20 μ ^η ι.

[Claim 7]

The method of claim 2, wherein the carbon nanotube has a length of 0.5 ym to 50 μιη.

[Claim 8]

The method according to claim 1, wherein the solvent is water.

[Claim 9]

The method of claim 1, wherein the weight ratio of the carbon precursor and the polymer particles is 0.07: 3 to 70: 3.

[Claim 10]

The method of claim 2, wherein the weight ratio of the carbon nanotubes and the carbon precursor is 1.5: 1 to 10: 1.

[Claim 11]

The method of claim 1, wherein the weight ratio of the carbon precursor and the polymer particles is 1: 3 to 1:45.

[Claim 12] _^

The method of claim 1, wherein the heat treatment is first performed at 200-350 ^° C., and secondly at 400 ^° C.-600 ^° C.

[Claim 13] According to claim U, The heat treatment is characterized in that to raise the silver to 400 ~ 600 ^° C, manufacturing method.

[Claim 14]

The method of claim 1, wherein the hollow carbon capsule has a pore diameter of 10 nm to 20 μηι.

[Claim 15]

The method of claim 1, wherein the shell thickness of the hollow carbon capsule is 1 nm to 1,000 nm.

[Claim 16]

A hollow carbon capsule prepared by the method of any one of claims 1 to 15.