KR20190036271A - The preparation method of multi-layer core-shell nano particles comprising porous carbon shell and core-shell nano particles thereby - Google Patents

Abstract

Disclosed is a method for manufacturing a porous carbon shell-contained core-shell nanoparticle having two or more layers of a shell, which comprises steps of: supplying a core nanoparticle and a primary coating source to a high-temperature and high-pressure sealed reactor; sealing the reactor; firstly heating the reactor in an inert gas atmosphere; supplying a secondary coating source to the reactor; and secondarily heating the reactor in the inert gas atmosphere. When an electrode material is manufactured by using the core-shell nanoparticle according to the present invention as an electrode active material, it is possible to increase the charging amount and maintain an excellent charging amount even when charging and discharging are repeated many times.

Description

The present invention relates to a method of preparing multi-layer core-shell nanoparticles comprising porous carbon shells and core-shell nanoparticles prepared thereby. }

The present invention relates to a method for producing core-shell nanoparticles, and more particularly to a method for producing multilayer core-shell nanoparticles comprising at least one porous carbon shell and core-shell nanoparticles prepared thereby .

Most materials exhibit different characteristics when they are present in the nano-sized state and when they are not. In some cases, they exhibit better electrical and physical characteristics, and may experience more fatal chemical changes. The most commonly observed change is a phenomenon in which oxygen is easily oxidized or the melting point is lowered. In addition, there is a phenomenon that its shape and crystal structure are easily changed by excessive volume expansion during adsorption process of ions or gases. These changes can act as a limiting factor for the use of nanoparticles. Therefore, it is very important to develop a surface coating material and its method that can maintain its characteristics even in a nano-sized state or exhibit better characteristics.

Nano carbon materials such as carbon nanotubes and graphene have attracted much attention in recent years due to their excellent properties. The main advantages of carbon materials are their excellent elasticity, electrical conductivity, corrosion resistance and chemical resistance. Therefore, the coating of nanoparticles using nanocarbon materials can not only prevent nanoparticles from being easily changed in harsh physical and chemical environments, but also adds to the inherent properties of carbon, thereby providing better and more specific properties. .

Carbon-coated nanoparticles are also used in various fields such as electrode materials, catalytic materials, heat storage materials, gas and liquid adsorption materials, environmental materials such as photoreactive materials, drug delivery and diagnosis, magnetic fields and electric conductivity Or shielding materials. The application range is very wide. Therefore, the development of a technology for uniformly mass-producing carbon coatings of these nanoparticles in a simple and inexpensive manner is very important for the commercialization of nanoparticles.

CVD (Chemical Vapor Deposition) method and thermal decomposition method are widely known as methods for forming carbon-coated nanoparticles known to date.

According to a CVD method according to CNHe et al. (2006, 44, 2330-2333), a supported metal catalyst is coated on a support metal The carbon source or the organic metal source is pyrolyzed at the reaction temperature so that the metal surface is coated with the carbon at the reaction temperature by supplying the source or directly supplying the organometallic source in the form of a precursor onto the evaporation plate in the reactor. However, in general CVD methods, it is impossible to produce carbon coated nanoparticles at a time in several tens of kilograms, and since the coating source is difficult to be supplied uniformly between the pores of the nanoparticles, The thickness of the coating layer may be non-uniformly formed depending on the position.

A method of carbon coating a nanoparticle by applying a fluidized bed and a supercritical antisolvent has been proposed (Coating of nanoparticle agglomerates via gas in fluidized bed, 2104, 14 ^th European meeting on supercritical fluids ). Although this method can be applied to mass production, surface reaction

It is difficult to control the condition and it is difficult to make micro-coating.

As a thermal decomposition method, a method of using an organometallic material having a metal-carbon bond as a precursor (Sn78Ge22, Carbon Core-Shell Nanowires as Fast and High Capacity Lithium Storage Media. Nanoletters 2007 , 7, 2638-2641 and Stabilization of Metastable Face-Centered Cubic Cobalt and the Tetragonal Phase of Zirconia by a Carbon Shell: Reaction under Autogenic Pressure at Elevated Temperature of CoZr2 (acac) 2 (OiPr) 8 Chem. , 1793-1798). These methods utilize the phenomenon that the metal is crystallized while the metal (CxHy) or salt (Metal / metal oxide-OCOCH3) is pyrolyzed and the decomposed carbon is coated on the metal surface. However, according to this method, since the metal-containing organometallic material is used as a source, the thickness of the carbon coating layer is determined according to the atomic ratio of the metal and carbon components contained in the organometallic material, . In addition, most of the organometallic sources are expensive raw materials and are not mass-produced and economical. Furthermore, since the type of the core material is determined depending on the kind of the organic metal source, the kind of carbon-coated metal nanoparticles that can be produced is limited.

The nitrate (NO3) or chloride (Cl) series salts are the cheapest salts among the salts that can be used in the thermal decomposition method. However, since most of the stainless steel type metal reactors are used to withstand high pressure conditions, Reactor corrosive salts are difficult to use. Instead, it uses a slightly more expensive acetate (-OCOCH3) salt. However, when an acetate metal precursor is used, the core is formed in a mostly metal oxide form except for noble metals (Ag, Pt, Au) having oxidation resistance characteristics because of the oxygen contained in the acetate group.

Accordingly, the inventors of the present invention have been studying a method for manufacturing core-shell nanoparticles which can overcome the disadvantages of the existing core-shell manufacturing method and have excellent economic efficiency and mass production, It is possible to constitute a manufacturing method capable of mass production while reducing the loss rate of the used coating source when the shell nanoparticle manufacturing process is constituted, thus completing the present invention.

SUMMARY OF THE INVENTION The present invention provides a method for producing core-shell nanoparticles.

Another object of the present invention is to provide core-shell nanoparticles.

Furthermore, another object of the present invention is to provide an electrode material comprising core-shell nanoparticles.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a method of manufacturing a reactor comprising the steps of: supplying core nanoparticles and a first coating source to a high-temperature high-pressure hermetically sealed reactor; sealing the reactor; firstly heating the reactor in an inert gas atmosphere; Providing a core-shell nanoparticle having two or more shells including a porous carbon shell including a step of supplying a secondary coating source to the reactor and a step of secondarily heating the reactor in an inert gas atmosphere do.

At this time, the porous carbon shell may have a pore size of 0.3 to 1.0 nm.

Also, when the primary coating source is a carbon source, the secondary coating source may be a phosphide source or a chalcogenide source, and the primary coating source may be a phosphide source or a chalcogenide source , The secondary coating source may be a carbon source.

The carbon source is benzene _{(Benzene, C 6 H 6)} , toluene _{(Toluene, C 7 H 8)} , styrene _{(Styrene, C 8 H 8)} , indene _{(Indene, C 9 H 8)} , hexane (Hexane, C ₆ H ₁₄ ), octane (C ₈ H ₁₈ ), paraffin oil (C _x H _y ), naphthalene (C ₁₀ H ₈ ), anthracene (C ₁₄ H ₁₀ ) Fluorene, C ₁₃ H _10), solid paraffin (paraffin,, pyrene _{C x H y) (pyrene,} C 16 H 10), having 2 to 8 carbon atoms polymer consisting of monomers, acetylene (acetylene, C ₂ H _2), And any one selected from the group consisting of ethylene, C ₂ H ₄ , propane, C ₃ H ₈ , methane, CH ₄ , polyethylene, polystyrene and polypropylene. And may be a carbon source containing at least one doping element selected from the group consisting of N, P and B, and may be melamine (C ₃ H ₆ N ₆ ), pyridine (C ₅ H ₅ N), an arc Lilo nitrile _{(acrylonitrile, C 3 H 3 N} ), pyrrole _{(Pyrrole, C 4 H 5 N} ), ammonia (NH ₃₎ and a mixed gas of hydrocarbon gas, tributylphosphine _{(tributylphosphine, [CH 3 (CH} 2) 3 ] ₃ P), phosphorine (C ₅ H ₅ P), triphenylborane (C ₆ H ₅ ) ₃ B), borinine (C ₅ H ₅ B), triethylborane ((C ₂ H ₅ ) ₃ B), trimethylboron, B (CH ₃ ) ₃ , trimethylboron-d 9, B (CD ₃ ) ₃ , borane dimethylamine, Borane pyridine, borane trimethylamine, borane-ammonia, tetrabutylammonium cyanoborohydride, ammonium tetraphenylborate, tetrabutylammonium borohydride, tetrabutylammonium borohydride, Tetrabutylammonium borohydride, tetramethylammonium triacetoxyborate, tetramethylammonium triacetoxyborohydride, and borane diphenylphosphine. In the present invention, it is also possible to use at least one compound selected from the group consisting of 2,4,6-triphenylborazine, 2,4,6-triphenylborazine and borane diphenylphosphine.

Further, the phosphide source _{P, Ni (CO) 6,} Fe 2 (CO) 9, Zn (CH 3) 2, Zn (C 2 H 5) 2, In (CH 3) 3, Mo (CO) 6 , Ga (CH ₃ ) ₃ and Ga (C ₂ H ₅ ) ₃ , and the chalcogenide source may be at least one selected from the group consisting of a sulfide source, a selenide source, a telluride ) Source or a polonide source, wherein the chalcogenide source is selected from the group consisting of S, H ₂ S, C ₆ H ₅ SeH, C ₁₂ H ₁₀ Se, Se (CH ₃ ) ₂ , Se (C ₂ H _{5 ) 2 Mo (CO) 6,} Ni (CO) 6, Fe 2 (CO) 9, W (CO) 6, _{Cr (CO) 6, Mn 2} (CO) 10, Ru 3 (CO) 12, Rh 4 (CO) 12, Re 2 (CO) 10, and can be one or more which is Co ₂ (CO) selected from the group consisting of ₈ have.

Also, when the primary coating source is a carbon source, the primary heating temperature may be 550 ° C to 850 ° C, and when the primary coating source is a phosphide source or a chalcogenide source, the primary heating temperature May be from 400 ° C to 850 ° C, and when the secondary coating source is a carbon source, the secondary heating temperature may be 550 ° C to 850 ° C, and the secondary coating source may be a phosphide source or a chalcogenide source , The secondary heating temperature may be 400 ° C to 850 ° C.

Further, when the primary coating source is a carbon source, the primary heating time may be 10 to 120 minutes, and when the primary coating source is a phosphide source or a chalcogenide source, the primary heating time is 10 To 60 minutes, and when the secondary coating source is a carbon source, the secondary heating time may be 10 to 120 minutes, and when the secondary coating source is a phosphide source or a chalcogenide source, The heating time may be 10 to 60 minutes.

Furthermore, the core-shell nanoparticle manufacturing method may be characterized in that the primary coating source and the secondary coating source, which are supplied regardless of the type of the core nanoparticles, are used for coating the core nanoparticles without loss , The supply amount of the primary coating source and the secondary coating source is controlled so that uncoated core nanoparticles or micro-sized core-shell nanoparticles are not formed.

Meanwhile, the core nanoparticles may be a metal, a metal oxide, a semiconductor material, or a semiconductor oxide.

The method for manufacturing core-shell nanoparticles may further include, after the primary heating, stabilizing the inside of the reactor by releasing the internal pressure of the reactor and removing residual gas, and after the secondary heating, releasing the internal pressure of the reactor And stabilizing the inside of the reactor by removing residual gas, wherein after the secondary heating, supplying a third coating source to the reactor, sealing the reactor, and sealing the reactor in an inert gas atmosphere And the third heating step.

When the second coating source is a carbon source, the third coating source may be a phosphide source or a chalcogenide source, and when the second coating source is a phosphide source or a chalcogenide source, The tea coating source may be a carbon source.

When the third coating source is a carbon source, the tertiary heating temperature may be 550 ° C to 850 ° C, and when the third coating source is a phosphide source or a chalcogenide source, the tertiary heating temperature is 400 And when the third coating source is a carbon source, the third heating time may be 10 to 120 minutes, and when the third coating source is a phosphide source or a chalcogenide source, The third heating time may be 10 to 60 minutes.

The method may further include, after the third heating, stabilizing the inside of the reactor by releasing the internal pressure of the reactor and removing the residual gas.

In order to achieve the above object, the present invention provides a nanoparticle core comprising a nanoparticle core, a first shell surrounding the nanoparticle core, and a second shell surrounding the first shell, wherein the first shell or the second shell comprises Shell carbon or phosphide and chalcogenide, wherein the first shell and the second shell provide core-shell nanoparticles which are different materials from each other.

The core-shell nanoparticles may further include a third shell surrounding the second shell, wherein the third shell is any one selected from the group consisting of porous carbon or phosphide and chalcogenide, The two shells and the third shells can be different materials.

In the core-shell nanoparticles, the porous carbon may have a pore size of 0.3 to 1.0 nm. The phosphide may be MoP, Ni ₂ P, Fe ₂ P, Fe ₃ P, Zn ₃ P ₂ , InP and GaP, and the chalcogenide may be at least one selected from the group consisting of MoS ₂ , NiS, FeS, WS ₂ , Cr ₂ S ₃ , MnS, RuS ₂ , Re ₂ S ₇ , CoS, The nanoparticle core may be at least one selected from the group consisting of MoSe ₂ , NiSe, FeSe, WSe ₂ , CrSe, MnSe, RuSe, RhSe ₂ , ReSe _2, and CoSe, Lt; / RTI >

Furthermore, in order to accomplish the above object, the present invention provides an electrode active material comprising the core-shell nanoparticles.

In the method of manufacturing core-shell nanoparticles according to an embodiment of the present invention, 99% or more of the coating sources are used for coating the core nanoparticles regardless of the type of the core nanoparticles used, thereby minimizing the amount of the coating source can do.

In addition, the amount of the coating source to be supplied can be controlled so that uncoated core nanoparticles or micro-sized core-shell nanoparticles are not formed.

Furthermore, the method for manufacturing core-shell nanoparticles according to an embodiment of the present invention can provide a more economical process than the conventional method for manufacturing core-shell nanoparticles by providing an efficient process than the prior art. Specifically, the process can be simplified by including only a heat treatment process using a reactor, and mass production of core-shell particles is possible by supplying a large amount of core nanoparticles and a coating source to the reactor.

Furthermore, when the electrode material is manufactured using the core-shell nanoparticles according to an embodiment of the present invention as an electrode active material, the charged amount of the battery increases, and an excellent charge amount can be maintained even when charging and discharging are repeated several times.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 (a) is a high magnification TEM (HRTEM) photograph of Si core-MoS ₂ (0 wt%) shell nanoparticles prepared according to Example 1-1.
1 (b) is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 1-2.
1 (c) is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (38 wt%) shell nanoparticles prepared according to Example 1-3.
1 (d) is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (56 wt%) shell nanoparticles prepared according to Example 1-4.
2 is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (38 wt%) shell-carbon shell nanoparticles prepared according to Example 2. FIG.
3 (a) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1.
3 (b) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.
3 (c) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (38 wt%) shell nanoparticles prepared according to Example 3-3.
3 (d) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (56 wt%) shell nanoparticles prepared according to Example 3-4.
4 (a) is a photograph of the Si component distribution of Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1.
4 (b) is a photograph of the C component distribution of the Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1.
4 (c) is a photograph of the N component distribution of Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1.
5 (a) is a photograph of the Si component distribution of Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.
5 (b) is a photograph of the C component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.
5 (c) is a photograph of the N component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.
5 (d) is a photograph of the Mo component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.
5 (e) is a photograph of the S component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.
6 is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (38 wt%) shell-carbon shell nanoparticles prepared according to Example 4-3.
7 is a schematic diagram illustrating a process for preparing core-shell nanoparticles according to the present invention when the primary coating source and the tertiary coating source are carbon sources and the secondary coating source is a MoS ₂ source.
8 is a schematic diagram illustrating a process for preparing core-shell nanoparticles according to the present invention when the primary coating source and the tertiary coating source are MoS ₂ sources and the secondary coating source is a carbon source.
FIG. 9 is a graph showing a capacity and a coulombic efficiency of a coin type half cell manufactured in Production Examples 1 to 3 when the cyclic cycling test was repeated 50 times.

Hereinafter, the present invention will be described in detail.

According to an aspect of the present invention, there is provided a method for producing a nanoparticle, comprising the steps of: supplying a core nanoparticle and a primary coating source to a high-temperature high-pressure sealed reactor; sealing the reactor; firstly heating the reactor in an inert gas atmosphere; A method for manufacturing a core-shell nanoparticle having two or more layers of shells including a porous carbon shell including a step of supplying a secondary coating source to the reactor and a step of secondary heating the reactor in an inert gas atmosphere to provide.

Hereinafter, the core-shell nanoparticle production method will be described in detail.

First, the core-shell nanoparticle manufacturing method includes supplying core nanoparticles and a primary coating source to a high-temperature high-pressure hermetically sealed reactor.

Here, the high-temperature high-pressure sealed reactor means a reactor which can be completely sealed under the temperature and pressure at which the reaction occurs.

At this time, the high temperature may be a temperature of 200 ° C or more, a temperature of 300 ° C or more, a temperature of 400 ° C or more, or a temperature of 500 ° C or more. The high pressure means a pressure higher than the atmospheric pressure and may be a pressure of 1 atm or more, a pressure of 10 atm or more, a pressure of 20 atm or more, a pressure of 30 atm or more, or a pressure of 40 atm or more.

As a simplest form of the high-temperature high-pressure sealed reactor, a stainless steel Swagelok-typereactor can be mentioned. However, the reactor is not limited to the above-mentioned examples but may be variously modified according to reaction materials, .

The capacity of the reactor can be from 1 cc to less, and the maximum capacity can be changed according to the reaction conditions to be carried out without particular limitation.

As the core nanoparticles, a metal, a metal oxide, a semiconductor material, or a semiconductor oxide may be used.

The metal is selected from the group consisting of alkali metal elements (Li, Na, K, Rb, Cs and Fr), alkaline earth metal elements (Ca, Sr, Ba and Ra) (Sc, Y, element Nos. 57 to 71), a titanium group element (Ti, Zr (Zr), and a rare earth element (Fe, Co, Ni), a platinum group element (Cr, Mo, W), Hf, a vanadium group element (V, Nb, Ta), a chromium group element (Ni, Cu, Ni, Co, Fe, Mn, Zr, Mo, Al, Rh, Pd, Os, Ir, Pt) or an actinide group element (element number 89 to 103) Pt, Ag, Ru, Rh, Ir, Au, or the like. However, any metallic material conventionally used in the field can be used without limitation.

The metal oxide may be Fe ₃ O ₄ , ZnO, ZrO ₂ , NiO, Al ₂ O ₃ , or the like, and may be any semiconductor material conventionally used in the field.

Further, the semiconductor material may be Si, Ge, Sn, In, Ga, or the like, and any semiconductor material conventionally used in the field may be used without limitation.

The semiconductor oxide may be SiO _x , GeO ₂ , SnO ₂ , In ₂ O _3, Ga ₂ O ₃ , or the like, and may be any semiconductor material conventionally used in the field.

Furthermore, the core nanoparticles may be nanoparticle complexes combining the proposed nanoparticle species.

The core nanoparticles may have a size of 1 nm to 1000 nm in diameter, 1 nm to 500 nm, and 10 nm to 200 nm, but the core nanoparticles may be used without particular limitation depending on the intended use of the particles to be produced.

The primary coating source may be any one selected from the group consisting of a carbon source or a phosphide source and a chalcogenide source.

At this time, the carbon source is not limited to the hydrocarbon material used in the conventional carbon layer formation, but can be used.

For example, benzene _{(Benzene, C 6 H 6)} , toluene _{(Toluene, C 7 H 8)} , styrene _{(Styrene, C 8 H 8)} , indene _{(Indene, C 9 H 8)} , hexane (Hexane, C ₆ H ₁₄ ), octane (C ₈ H ₁₈ ), paraffin oil (C _x H _y ), naphthalene (C ₁₀ H ₈ ), anthracene (C ₁₄ H ₁₀ ) Fluorene, C ₁₃ H _10), solid paraffin (paraffin,, pyrene _{C x H y) (pyrene,} C 16 H 10), having 2 to 8 carbon atoms polymer consisting of monomers, acetylene (acetylene, C ₂ H _2), It is possible to use ethylene, C ₂ H ₄ , propane, C ₃ H ₈ , methane, CH ₄ , polyethylene, polystyrene or polypropylene, If the layer formation is not affected, a mixture of the carbon sources may also be used.

Furthermore, a carbon source containing at least one doping element selected from the group consisting of N, P and B may be used as the carbon source.

At this time, the carbon source containing the doping element is not limited to the N, P or B-doped hydrocarbon species used in the carbon layer in the related art.

For example, the carbon source is melamine _{(melamin, C 3 H 6 N} 6), pyridine _{(pyridine, C 5 H 5 N} ), acrylonitrile _{(acrylonitrile, C 3 H 3 N} ), pyrrole (Pyrrole, C ₄ H ₅ N), a mixed gas of ammonia (NH ₃ ) and a hydrocarbon gas, tributylphosphine [CH ₃ (CH ₂ ) ₃ ] ₃ P, phosphorine (C ₅ H ₅ P) (C ₆ H ₅ ) ₃ B), borinine (C ₅ H ₅ B), triethylborane ((C ₂ H ₅ ) ₃ B), trimethylboron CH ₃ ) ₃ or trimethylboron-d 9, B (CD ₃ ) ₃ ), borane dimethylamine, borane pyridine, borane trimethylamine, borane ammonia borane-ammonia, tetrabutylammonium cyanoborohydride, ammonium tetraphenylborate, tetrabutylammonium borohydride, tetrabutylammonium borohydride, tetramethylammonium triacetoxyborohydride, 2,4,6-triphenylborazine or borane diphenylphosphine, etc. may be used, for example, And if it does not affect the carbon layer formation, a mixture of the carbon sources may also be used.

In addition, the phosphide (phosphide) source _{P, Ni (CO) 6,} Fe 2 (CO) 9, Zn (CH 3) 2, Zn (C 2 H 5) 2, In (CH 3) 3, Mo ( CO) ₆ , Ga (CH ₃ ) ₃ and Ga (C ₂ H ₅ ) ₃ .

Further, the chalcogenide source may be a sulfide source, a selenide source, a telluride source, or a polonide source, wherein the chalcogenide source is selected from the group consisting of S, H ₂ S _{, C 6 H 5 SeH, C} 12 H 10 Se, Se (CH 3) 2, Se (C 2 H 5) 2 Mo (CO) 6, Ni (CO) 6, Fe 2 (CO) 9, W (CO ) ₆ , _{Cr (CO) 6, Mn 2} (CO) 10, Ru 3 (CO) 12, Rh 4 (CO) 12, Re 2 (CO) 10, and can be one or more which is Co ₂ (CO) selected from the group consisting of ₈ have.

Further, the material state of the primary coating source may be divided into solid, liquid, and gas, and may be supplied to the high-temperature high-pressure sealed reactor in a suitable manner according to the material state of the primary coating source to be supplied.

When the primary coating source is a solid, the core nanoparticles and the primary coating source may be supplied together in the closed reactor. The amount of the primary coating source to be supplied may be a weight ratio of the primary coating source to the supply weight of the core nanoparticles As shown in FIG.

If the primary coating source is a liquid, the core nanoparticles and the primary coating source may be fed together in a closed reactor, or the core nanoparticles may be first fed into the reactor and then the primary coating source may be further fed to the reactor using an external pump . At this time, when the primary coating source is a harmful substance, it is supplied through an external pump, and thus the process can be performed without discharging harmful substances. Also, the feed rate of the primary coating source can be controlled by adjusting the volume ratio of the primary coating source to the reactor volume.

If the primary coating source is a gas, the core nanoparticles may first be fed into the reactor and then the primary coating source may be additionally supplied to the reactor using an external pump or high pressure gas supply equipment. At this time, the supply amount of the primary coating source can be controlled by adjusting the pressure of the primary coating source gas to be injected.

The core-shell nanoparticle manufacturing method can select the desired thickness of the coated shell by controlling the amount of supply as described above when supplying the primary coating source.

For example, the thickness of the chalcogenide shell layer can be selected within the range of 0 nm to 100 nm by controlling the amount of the chalcogenide source to be supplied when the supplied coating source is a chalcogenide source. (Example 1 However, the thickness range of the shell shown above is only exemplified in accordance with the thickness range required in the manufacturing of core-shell nanoparticles, and the thickness of the shell required in the technical field for controlling the supply amount of the carbon source Can be formed.

Therefore, by controlling the supply amount of the coating source, it is possible to variously control the shell thickness of the nanoparticle-carbon core-shell, and the diameter of the core nanoparticles to be supplied can be freely selected. Therefore, Can be produced by optimizing the particle size.

In addition, controlling the supply amount of the primary coating source can prevent uncoated core nanoparticles or micro-sized core-shell nanoparticles from being formed.

If the supply amount of the primary coating source is too low, core nanoparticles with little carbon coating, phosphide coating or chalcogenide coating may be present. On the other hand, if the supply amount of the primary coating source is too high, micro-sized core-shell nanoparticles, carbon spheres, phosphated spheres or chalcogenide spheres are formed together with the core-shell nanoparticle structure as a byproduct, . Therefore, it is preferable to control the supply amount of the primary coating source within the range that the core nanoparticles, the micro-sized carbon spheres, the phosphated spheres or the chalcogenide spheres are not generated in the core-shell nanoparticle production method .

In addition, the core-shell nanoparticle manufacturing method can be used for coating the core nanoparticles with a primary coating source of 90% or more or 99% or more without loss regardless of the kind of the core nanoparticles.

Next, the core-shell nanoparticle manufacturing method includes sealing the high-temperature high-pressure hermetically sealed reactor supplied with the core nanoparticles and the primary coating source.

It is possible to coat core nanoparticles without loss of coating source by completely sealing the high-temperature high-pressure sealed reactor and to coat the core nanoparticles with a simple process more than the prior art by controlling only the temperature condition through the pressure- .

Next, the core-shell nanoparticle manufacturing method includes a step of firstly heating the sealed high-temperature high-pressure sealed reactor in an inert gas atmosphere.

Here, the inert gas may be helium, neon, argon, krypton, xenon, radon, nitrogen, or the like, and any inert gas having low reactivity with other substances may be used.

In addition, when the primary coating source is a carbon source, the primary heating temperature may be 550 캜 to 850 캜, 500 캜 to 900 캜, and 400 캜 to 1000 캜.

If the primary heating temperature is less than 400 ° C, the reaction temperature may be too low to allow some carbon sources to be coated on the core nanoparticles, and the uncoated carbon source residue may be generated as a by-product to cause non-uniformity of the product have.

Also, when the primary heating temperature is higher than 1000 ° C, the reaction temperature is too high, so that the phase deformation or physical and chemical properties of the core nanoparticles may be deformed. For example, when core nanoparticles such as Al, Zn, Sn, and In having low melting points are used, secondary by-products may be generated due to a side reaction between the molecules vaporized from the core nanoparticles and the thermal decomposition molecules of the carbon source. Furthermore, there is a difficulty in selecting a material for the deformation of the reactor, etc., and the production cost of the reactor is increased and the production cost is increased.

In addition, when the primary coating source is a phosphide source or a chalcogenide source, the primary heating temperature may be 400 ° C. to 850 ° C., 350 ° C. to 900 ° C., and may be 300 ° C. to 1000 ° C. have.

If the primary heating temperature is less than 300 ° C, the reaction temperature is too low to allow coating of the phosphide source or the chalcogenide source on the core nanoparticles, and the uncoated phosphide source or residual chalcogenide source Water can be generated as a by-product and result in product non-uniformity.

Also, when the primary heating temperature is higher than 1000 ° C, the reaction temperature is too high, so that the phase deformation or physical and chemical properties of the core nanoparticles may be deformed. As an example, when using core nanoparticles such as Al, Zn, Sn, and In having a low melting point, a secondary by-product due to a side reaction between a molecule vaporized from the core nanoparticle and a pyrolyzing source of a phosphide source or a chalcogenide source Lt; / RTI > Furthermore, there is a difficulty in selecting a material for the deformation of the reactor, etc., and the production cost of the reactor is increased and the production cost is increased.

In this step, when the primary coating source is a carbon source, the primary heating time may be from 10 minutes to 120 minutes, from 5 minutes to 130 minutes, and from 1 minute to 140 minutes.

At this time, the reaction time may vary depending on the size of the core nanoparticles to be used, the thickness of the carbon shell to be formed, and the like.

On the other hand, when the first heating time is less than 1 minute, the reaction time is too short, so that some carbon sources may not be coated on the core nanoparticles, and uncoated phosphide sources or chalcogenide source residues are generated as byproducts Resulting in non-uniformity of the product.

In addition, when the primary coating source is a phosphide source or a chalcogenide source, the primary heating time may be from 10 minutes to 60 minutes, from 5 minutes to 70 minutes, and from 1 minute to 80 minutes.

At this time, the reaction time may vary depending on the size of core nanoparticles to be used, the thickness of the phosphide or the chalcogenide shell to be formed, and the like.

On the other hand, when the first heating time is less than 1 minute, the reaction time is too short, so that some carbon sources may not be coated on the core nanoparticles, and uncoated phosphide sources or chalcogenide source residues are generated as byproducts Resulting in non-uniformity of the product.

Further, in the method for manufacturing core-shell nanoparticles, after the primary heating, releasing the internal pressure of the reactor and removing residual gas may stabilize the inside of the reactor.

Specifically, the pressure regulating valve can be gradually opened to lower the internal temperature and pressure of the reactor to room temperature and normal pressure. When the internal temperature and pressure of the reactor reach room temperature and pressure, an inert gas such as argon or nitrogen is used to purge the inside of the reactor and open the reactor to obtain core-shell nanoparticles.

Next, the method for producing the core-shell nanoparticles comprises supplying a secondary coating source to the reactor after the primary heating.

Here, the secondary coating source may be a phosphide source or a chalcogenide source when the primary coating source is a carbon source, and may be a carbon source when the primary coating source is a phosphide source or a chalcogenide source have.

At this time, the types and supply methods of the carbon source, the phosphide source or the chalcogenide source are as described above.

The core-shell nanoparticle manufacturing method can select the desired thickness of the coated shell by controlling the amount of supply as described above when supplying the secondary coating source.

For example, the thickness of the chalcogenide shell layer can be selected within the range of 0 nm to 100 nm by controlling the amount of the chalcogenide source to be supplied when the supplied coating source is a chalcogenide source. (Example 1 However, the thickness range of the shell shown above is only exemplified in accordance with the thickness range required in the manufacturing of core-shell nanoparticles, and the thickness of the shell required in the technical field for controlling the supply amount of the carbon source Can be formed.

Therefore, by controlling the supply amount of the coating source, it is possible to variously control the shell thickness of the nanoparticle-carbon core-shell, and the diameter of the core nanoparticles to be supplied can be freely selected. Therefore, Can be produced by optimizing the particle size.

In addition, the amount of the secondary coating source can be controlled so that uncoated core nanoparticles or micro-sized core-shell nanoparticles are not formed.

If the supply amount of the secondary coating source is too low, core nanoparticles with little carbon coating or phosphide or chalcogenide coating may be present. On the other hand, if the supply amount of the secondary coating source is too large, micro-sized core-shell nanoparticles, carbon spheres, phosphated spheres or chalcogenide spheres are formed together with the core-shell nanoparticle structure as a byproduct, . Therefore, it is preferable to control the supply amount of the secondary coating source within the range that the core nanoparticles, the micro-sized carbon spheres, the phosphated spheres or the chalcogenide spheres are not generated in the core-shell nanoparticle production method .

In addition, the core-shell nanoparticle production method can be used for coating the core nanoparticles with 90% or more of 99% or more of the supplied secondary coating source without loss, irrespective of the kind of the core nanoparticles.

Next, the core-shell nanoparticle manufacturing method may further include sealing the high-temperature high-pressure hermetically closed reactor supplied with the secondary coating source.

It is possible to coat core nanoparticles without loss of coating source by completely sealing the high-temperature high-pressure sealed reactor and to coat core nanoparticles with simple process than the prior art by controlling only temperature condition through the pressure- .

Next, the core-shell nanoparticle manufacturing method includes a step of secondarily heating the sealed high-temperature high-pressure sealed reactor in an inert gas atmosphere.

Here, the inert gas may be helium, neon, argon, krypton, xenon, radon, nitrogen, or the like, and any inert gas that is relatively difficult to react with other substances may be used.

Further, when the secondary coating source is a carbon source, the secondary heating temperature may be 550 캜 to 850 캜, 500 캜 to 900 캜, and 400 캜 to 1000 캜.

If the secondary heating temperature is lower than 400 ° C., the reaction temperature may be too low to allow the carbon nanotubes to be coated on some of the carbon nanotubes, and uncoated carbon source residues may be generated as byproducts, have.

Furthermore, when the secondary heating temperature is higher than 1000 ° C., the reaction temperature may be too high to deform the phase distortion or physical and chemical properties of the core nanoparticles. For example, when core nanoparticles such as Al, Zn, Sn, and In have low melting points, second byproducts may be generated due to side reactions between molecules vaporized from the core nanoparticles and thermal decomposition molecules of the carbon source. Furthermore, there is a difficulty in selecting a material for the deformation of the reactor, etc., and the production cost of the reactor is increased and the production cost is increased.

When the secondary coating source is a phosphide source or a chalcogenide source, the secondary heating temperature may be 400 ° C to 850 ° C, 350 ° C to 900 ° C, and 300 ° C to 1000 ° C.

If the secondary heating temperature is less than 300 ° C, the reaction temperature is too low to allow coating of the phosphide source or the chalcogenide source on the core nanoparticles, and an uncoated phosphide source or residual chalcogenide source Water can be generated as a by-product and result in product non-uniformity.

If the secondary heating temperature is higher than 1000 ° C, the reaction temperature may be excessively high, which may result in deformation of the core nanoparticles or deformation of the physical and chemical properties of the core nanoparticles. As an example, when using core nanoparticles such as Al, Zn, Sn, and In having a low melting point, a secondary by-product due to a side reaction between a molecule vaporized from the core nanoparticle and a pyrolyzing source of a phosphide source or a chalcogenide source Lt; / RTI > Furthermore, there is a difficulty in selecting a material for the deformation of the reactor, etc., and the production cost of the reactor is increased and the production cost is increased.

Further, when the secondary coating source is a carbon source, the secondary heating time can be 10 minutes to 120 minutes, 5 minutes to 130 minutes, and 1 minute to 140 minutes.

At this time, the reaction time may vary depending on the size of the core nanoparticles to be used, the thickness of the carbon shell to be formed, and the like.

On the other hand, if the second heating time is less than 1 minute, the reaction time is too short, so that some carbon sources may not be coated on the core nanoparticles, and uncoated phosphide sources or chalcogenide source residues are generated as byproducts Resulting in non-uniformity of the product.

Also, when the secondary coating source is a phosphide source or a chalcogenide source, the secondary heating time can be 10 minutes to 60 minutes, 5 minutes to 70 minutes, and 1 minute to 80 minutes.

At this time, the reaction time may vary depending on the size of the core nanoparticles to be used, the thickness of the phosphide or the chalcogenide shell layer to be formed, and the like.

On the other hand, if the second heating time is less than 1 minute, the reaction time is too short, so that some carbon sources may not be coated on the core nanoparticles, and uncoated phosphide sources or chalcogenide source residues are generated as byproducts Resulting in non-uniformity of the product.

Further, in the method for manufacturing core-shell nanoparticles, after the secondary heating, releasing the internal pressure of the reactor and removing residual gas may stabilize the inside of the reactor.

Specifically, the pressure regulating valve can be gradually opened to lower the internal temperature and pressure of the reactor to room temperature and normal pressure. When the internal temperature and pressure of the reactor reach room temperature and pressure, an inert gas such as argon or nitrogen is used to purge the inside of the reactor and open the reactor to obtain core-shell nanoparticles.

Furthermore, the method for producing the core-shell nanoparticles may further include, after the secondary heating, supplying a tertiary coating source to the reactor and heating the reactor in a tertiary atmosphere in an inert gas atmosphere.

Wherein when the secondary coating source is a carbon source, the tertiary coating source is a phosphide source or a chalcogenide source,

When the secondary coating source is a phosphide source or a chalcogenide source, the tertiary coating source may be a carbon source.

At this time, the types and supply methods of the carbon source, the phosphide source, or the chalcogenide source are the same as those described above.

The core-shell nanoparticle manufacturing method can select the desired thickness of the coated shell by controlling the amount of supply as described above when supplying the third coating source.

For example, the thickness of the chalcogenide shell layer can be selected within the range of 0 nm to 100 nm by controlling the amount of the chalcogenide source to be supplied when the supplied coating source is a chalcogenide source. (Example 1 However, the thickness range of the shell shown above is only exemplified in accordance with the thickness range required in the manufacturing of core-shell nanoparticles, and the thickness of the shell required in the technical field for controlling the supply amount of the carbon source Can be formed.

In addition, by controlling the amount of the third coating source to be supplied, it is possible to prevent the formation of uncoated core nanoparticles or micro-sized core-shell nanoparticles.

In this step, if the supply amount of the third coating source is too small, core nanoparticles having almost no carbon coating and phosphide or chalcogenide coating may be present. On the other hand, if the supply amount of the third coating source is too high, micro-sized core-shell nanoparticles, carbon spheres, phosphide spheres or chalcogenide spheres are formed together with the core-shell nanoparticle structure as a byproduct, . Therefore, it is preferable to control the supply amount of the third coating source within the range that the core nanoparticles, the micro-sized carbon spheres, the phosphated spheres or the chalcogenide spheres are not generated in the core-shell nanoparticle production method .

In addition, the core-shell nanoparticle production method can be used for coating the core-shell nanoparticles with 90% or more of 99% or more of the supplied third coating source, regardless of the kind of the core nanoparticles.

Next, the core-shell nanoparticle manufacturing method may further include sealing the high-temperature high-pressure hermetically closed reactor supplied with the third coating source.

It is possible to coat core nanoparticles without loss of coating source by completely sealing the high-temperature high-pressure sealed reactor and to coat the core nanoparticles with a simple process more than the prior art by controlling only the temperature condition through the pressure- .

Next, the method for manufacturing the core-shell nanoparticles may include a third step of heating the sealed high-temperature high-pressure sealed reactor in an inert gas atmosphere.

In this step, the inert gas may be helium, neon, argon, krypton, xenon, radon, nitrogen, or the like, and any inert gas which is relatively difficult to react with other substances may be used.

When the third coating source is a carbon source, the tertiary heating temperature may be 550 캜 to 850 캜, 500 캜 to 900 캜, and 400 캜 to 1000 캜.

If the tertiary heating temperature is less than 400 ° C, the reaction temperature may be too low to allow the carbon nanotubes to be coated on some of the carbon nanotubes, and uncoated carbon source residues may be generated as byproducts, have.

If the tertiary heating temperature is higher than 1000 ° C, the reaction temperature may be too high to deform the phase distortion or physical and chemical properties of the core nanoparticles. For example, when core nanoparticles such as Al, Zn, Sn, and In have low melting points, second byproducts may be generated due to side reactions between molecules vaporized from the core nanoparticles and thermal decomposition molecules of the carbon source. Further, there is a difficulty in selecting a material for the deformation of the reactor, etc., and the manufacturing cost of the reactor is increased and the production cost is increased.

In addition, when the third coating source is a phosphide source or a chalcogenide source, the tertiary heating temperature may be 400 캜 to 850 캜, may be 350 캜 to 900 캜, may be 300 캜 to 1000 캜 have.

If the tertiary heating temperature is less than 300 ° C, the reaction temperature is too low to allow coating of the phosphide source or the chalcogenide source on the core nanoparticles, and an uncoated phosphide source or residual chalcogenide source Water can be generated as a by-product and result in product non-uniformity.

If the tertiary heating temperature is higher than 1000 ° C, the reaction temperature may be too high to deform the phase distortion or physical and chemical properties of the core nanoparticles. As an example, when using core nanoparticles such as Al, Zn, Sn, and In, which have low melting points, tertiary by-products due to side reactions between molecules vaporized from core nanoparticles and pyrolysis sources of phosphide or chalcogenide sources Lt; / RTI > Furthermore, there is a difficulty in selecting a material for the deformation of the reactor, etc., and the production cost of the reactor is increased and the production cost is increased.

In addition, when the third coating source is a carbon source, the third heating time may be from 10 minutes to 120 minutes, from 5 minutes to 130 minutes, and from 1 minute to 140 minutes.

At this time, the reaction time may vary depending on the size of the core nanoparticles to be used, the thickness of the carbon shell to be formed, and the like.

On the other hand, if the third heating time is less than 1 minute, the reaction time is too short, so that some carbon sources may not be coated on the core nanoparticles, and uncoated phosphide sources or chalcogenide source residues are generated as byproducts. Resulting in non-uniformity of the product.

In addition, when the third coating source is a phosphide source or a chalcogenide source, the tertiary heating time may be 10 minutes to 60 minutes, 5 minutes to 70 minutes, and 1 minute to 80 minutes.

At this time, the reaction time may vary depending on the size of core nanoparticles to be used, the thickness of the phosphide or the chalcogenide shell to be formed, and the like.

On the other hand, if the third heating time is less than 1 minute, the reaction time is too short, so that some carbon sources may not be coated on the core nanoparticles, and uncoated phosphide sources or chalcogenide source residues are generated as byproducts. Resulting in non-uniformity of the product.

Further, in the method for manufacturing core-shell nanoparticles, after the third heating, the step of releasing the internal pressure of the reactor and removing the residual gas may stabilize the inside of the reactor.

Specifically, the pressure regulating valve can be gradually opened to lower the internal temperature and pressure of the reactor to room temperature and normal pressure. When the internal temperature and pressure of the reactor reach room temperature and pressure, an inert gas such as argon or nitrogen is used to purge the inside of the reactor and open the reactor to obtain core-shell nanoparticles.

FIGS. 7 and 8 are schematic diagrams showing one embodiment of a process for manufacturing core-shell nanoparticles according to the above-described method.

Figure 7 is a manufacturing process when the primary coating source and the tertiary coating source are carbon sources and the secondary coating source is a MoS ₂ source, Figure 8 shows that the primary coating source and the tertiary coating source are MoS ₂ sources and the secondary It is a manufacturing process when the coating source is a carbon source.

In the method for manufacturing the core-shell nanoparticles, the pore size of the porous carbon shell may be 0.3 to 1.0 nm, may be 0.2 to 1.1 nm, and may be 0.1 to 1.2 nm. By adjusting the pore size of the porous carbon shell to 0.3 to 1.0 nm, it is possible to smoothly penetrate the core of the external reactant through the pore structure of the carbon layer. The penetration of the reaction material into the core can be facilitated, thereby enhancing the reaction activity between the reactant and the core nanoparticles.

According to another aspect of the present invention, there is provided a nanoparticle core comprising a nanoparticle core, a first shell surrounding the nanoparticle core, and a second shell surrounding the first shell, Shell nanoparticles are any one selected from the group consisting of porous carbon or phosphides and chalcogenides, and the first shell and the second shell provide a core-shell nanoparticle which is a material that is different from each other.

At this time, the porous carbon may have a pore size of 0.3 to 1.0 nm, may be 0.2 to 1.1 nm, and may be 0.1 to 1.2 nm.

By adjusting the pore size of the porous carbon shell to 0.3 to 1.0 nm, the core-shell nanoparticles can smoothly penetrate the core of the external reaction material through the pore structure of the carbon layer. The penetration of the reaction material into the core can be facilitated, thereby enhancing the reaction activity between the reactant and the core nanoparticles.

Further, the phosphide may be at least one selected from the group consisting of MoP, Ni ₂ P, Fe ₂ P, Fe ₃ P, Zn ₃ P ₂ , InP and GaP.

The chalcogenide may be selected from the group consisting of MoS ₂ , NiS, FeS, WS ₂ , Cr ₂ S ₃ , MnS, RuS ₂ , Re ₂ S ₇ , CoS, MoSe ₂ , NiSe, FeSe, WSe ₂ , CrSe, MnSe, RuSe, RhSe ₂ , ReSe _2, and CoSe.

The nanoparticle core may be a metal, a metal oxide, a semiconductor material, or a semiconductor oxide.

The metal is selected from the group consisting of alkali metal elements (Li, Na, K, Rb, Cs and Fr), alkaline earth metal elements (Ca, Sr, Ba and Ra) (Sc, Y, element Nos. 57 to 71), a titanium group element (Ti, Zr (Zr), and a rare earth element (Fe, Co, Ni), a platinum group element (Cr, Mo, W), Hf, a vanadium group element (V, Nb, Ta), a chromium group element (Ni, Cu, Ni, Co, Fe, Mn, Zr, Mo, Al, Rh, Pd, Os, Ir, Pt) or an actinide group element (element number 89 to 103) Pt, Ag, Ru, Rh, Ir, Au, or the like. However, any semiconductor material conventionally used in the field can be used without limitation.

The metal oxide may be Fe ₃ O ₄ , ZnO, ZrO ₂ , NiO, Al ₂ O ₃ , or the like, and may be any semiconductor material conventionally used in the field.

Further, the semiconductor material may be Si, Ge, Sn, In, Ga, or the like, and any semiconductor material conventionally used in the field may be used without limitation.

The semiconductor oxide may be SiO _x , GeO ₂ , SnO ₂ , In ₂ O _3, Ga ₂ O ₃ , or the like, and may be any semiconductor material conventionally used in the field.

Furthermore, the nanoparticle core may be a nanoparticle complex in which the proposed nanoparticle species are combined.

The size of the nanoparticle core may be from 1 to 900 nm in diameter, from 1 to 500 nm, and from 10 nm to 200 nm, but the size of the core nanoparticles may be used without any particular limitation depending on the intended use of the particles to be produced .

The core-shell nanoparticles may further include a third shell that surrounds the second shell, and the third shell may be formed of porous carbon or a mixture of a phosphide and a chalcogenide And the second shell and the third shell may be materials different from each other.

At this time, the porous carbon may have a pore size of 0.3 to 1.0 nm, may be 0.2 to 1.1 nm, and may be 0.1 to 1.2 nm.

Further, the phosphide may be at least one selected from the group consisting of MoP, Ni ₂ P, Fe ₂ P, Fe ₃ P, Zn ₃ P ₂ , InP and GaP.

The chalcogenide may be selected from the group consisting of MoS ₂ , NiS, FeS, WS ₂ , Cr ₂ S ₃ , MnS, RuS ₂ , Re ₂ S ₇ , CoS, MoSe ₂ , NiSe, FeSe, WSe ₂ , CrSe, MnSe, RuSe, RhSe ₂ , ReSe _2, and CoSe.

The present invention also provides an electrode material comprising the core-shell nanoparticles.

The electrode material may be a fluorine resin binding polymer including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE), a styrene-butadiene rubber, an acrylonitrile-butadiene rubber, a styrene-isoprene rubber Cellulose-based binding polymers including carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyalcohol-based binding polymers, polyethylene, polypropylene, A polyimide-based binding polymer, a polyolefin-based binding polymer, a polyimide-based binding polymer, or a polyester-based binding polymer, and is not limited to the above-described type. Any other component of the electrode material commonly used in the related art may be used.

Furthermore, the core-shell nanoparticles according to the present invention can be used as a catalyst and electrode for reverse electrodialysis salt generation, a catalyst and electrode for hydrogen production through electrolysis, a catalyst electrode for photoelectrochemical reaction, an electrode for sodium battery or an electrode for lithium battery And the like.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

However, the following examples and experimental examples are illustrative of the present invention, and the scope of the present invention is not limited thereto.

Example 1: Preparation of core-shell nanoparticles 1

In order to confirm the shell formation effect of the core-shell nanoparticle manufacturing method according to the present invention, the amount of MoS ₂ was changed to 20 wt%, 38 wt% and 56 wt%, respectively, and Si core-MoS ₂ shell nanoparticles were prepared .

Example 1-1: Si core-MoS ₂ (20 wt%) shell nanoparticles

First, Si nanoparticles were supplied to a high-temperature and high-pressure sealed reactor, and hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur were supplied so that the content of MoS ₂ was 20 wt%.

Next, 100% argon gas was supplied to the high-temperature high-pressure sealed reactor, and the reactor was completely closed. The sealed high-temperature high-pressure reactor was heated to 500 DEG C under an argon gas atmosphere to react the Si nanoparticles, hexacarbonyl molybdenum and sulfur for 30 minutes.

After the completion of the reaction, the pressure inside the reactor was released and the argon gas supply was stabilized. Thereafter, the temperature was lowered to room temperature to obtain Si core-MoS ₂ (20 wt%) shell nanoparticles.

1 (b) is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (20 wt%) shell nanoparticles prepared according to the present embodiment.

1 (b), a native oxide (SiO _x ) layer having a thickness of 1-2 nm is formed between the Si core and the MoS ₂ layer, and MoS ₂ surrounds the Si core surface, It can be seen that the shell is formed on the horizontal structure layer of thickness.

Example 1-2: Si core-MoS ₂ (38 wt%) Preparation of shell nanoparticles

The amount of MoS ₂ to be 38 wt%, Hexacarbonyl Molybdenum (Mo (CO) 6) , and sulfur and with the same manufacturing method as that of Example 1-1 except that the supply (S) Si core - MoS ₂ (38 wt%) shell nanoparticles.

1 (c) is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (38 wt%) shell nanoparticles prepared according to this example.

1 (c), it can be seen that a native oxide (SiO _x ) layer with a thickness of 1-2 nm is formed between the Si core and the MoS ₂ layer, while MoS ₂ surrounds the Si core surface, It can be seen that the shell is formed on layers of horizontal and vertical structures of thickness.

Example 1-3: Si core-MoS ₂ (56 wt%) Preparation of shell nanoparticles

The amount of MoS ₂ to be 56 wt%, Hexacarbonyl Molybdenum (Mo (CO) 6) , and sulfur Si-core and with the same manufacturing method as that of Example 1-1 except that the supply (S) - MoS ₂ (56 wt%) shell nanoparticles.

1 (d) is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (56 wt%) shell nanoparticles prepared according to this example.

1 (d), it can be seen that a native oxide (SiO _x ) layer of 1-2 nm thickness is formed between the Si core and the MoS ₂ layer, and MoS ₂ surrounds the Si core surface, It can be seen that the shell is formed on layers of horizontal and vertical structures of thickness.

In the sealing structure according to the invention through the reaction of Example 1-1 to 1-3 increase the amount of MoS ₂ As can be confirmed to be a layered structure in the form of MoS ₂ layer gradually switched to the vertical structure from the horizontal structure .

Example 2: Preparation of core-shell nanoparticles 2

Si core-MoS ₂ shell (38 wt%) -carbon shell nanoparticles were prepared using the core-shell nanoparticle manufacturing method according to the present invention.

First, Si nanoparticles were supplied to a high-temperature and high-pressure sealed reactor, and hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur (S) were supplied so that the MoS ₂ content was 38 wt%.

Next, 100% argon gas was supplied to the high-temperature high-pressure sealed reactor, and the reactor was completely closed. The sealed high-temperature high-pressure reactor was heated to 500 DEG C under an argon gas atmosphere to react the Si nanoparticles, hexacarbonyl molybdenum and sulfur for 30 minutes.

After the completion of the reaction, the pressure inside the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-MoS ₂ (38 wt%) shell nanoparticles.

The obtained Si core-MoS ₂ (38 wt%) shell nanoparticles and pyridine (g) were fed to a high-temperature and high-pressure sealed reactor, and 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 ° C under an argon gas atmosphere to react the Si core-MoS ₂ (38 wt%) shell nanoparticles with pyridine for 60 minutes.

After the completion of the reaction, the inside pressure of the reactor was released and the argon gas supply was stabilized, and then the temperature was lowered to room temperature to finally obtain Si core-MoS ₂ (38 wt%) shell-carbon shell nanoparticles.

2 is a high-resolution TEM (HRTEM) photograph of the Si core-MoS ₂ (38 wt%) shell-carbon shell nanoparticles prepared according to this example.

As can be seen in FIG. 2, it can be seen that MoS ₂ surrounds the surface of the Si core and forms a shell on a horizontal structure layer of about 6-8 nm thickness. It can also be seen that the carbon layer surrounds the surface of the MoS ₂ layer and forms a shell of about 8-10 nm in thickness.

Example 3: Preparation of core-shell nanoparticles 3

The amount of MoS ₂ was changed to 0 wt%, 20 wt%, 38 wt%, and 56 wt%, respectively, using the core-shell nanoparticle manufacturing method according to the present invention, and Si core-carbon shell-MoS ₂ shell nanoparticles .

Example 3-1: Si core-carbon shell-MoS ₂  Preparation of shell (0 wt%)

First, Si nanoparticles and pyridine were fed to a high-temperature and high-pressure sealed reactor, and 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 ° C under an argon gas atmosphere to react the Si nanoparticles with pyridine for 60 minutes.

After the completion of the reaction, the inside pressure of the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell nanoparticles.

Next, the Si core-carbon shell nanoparticles and 100% argon gas were supplied to a high-temperature high-pressure hermetically sealed reactor and completely sealed. The sealed high-temperature high-pressure reactor was heated to 500 DEG C under an argon gas atmosphere and reacted for 30 minutes.

After the completion of the reaction, the pressure inside the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell-MoS ₂ (0 wt%) shell nanoparticles.

3 (a) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1.

As can be seen in FIG. 3 (a), it can be seen that the carbon layer surrounds the surface of the Si core and forms a shell of about 8-10 nm in thickness.

4 (a) is a photograph of the Si component distribution of Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1,

4 (b) is a photograph of the C component distribution of the Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1,

4 (c) is a photograph of the N component distribution of Si core-carbon shell-MoS ₂ (0 wt%) shell-nanoparticles prepared according to Example 3-1.

As can be seen from Figs. 4 (a) to 4 (c), it can be seen that the Si component is concentrated in the core of the nanoparticles and is not distributed in the outer shell layer of the nanoparticles. In addition, it can be seen that C and N are uniformly distributed on the entire surface of the nanoparticles, and are distributed densely in the outer region of the nanoparticles.

Example 3-2: Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles

First, Si nanoparticles and pyridine were fed to a high-temperature and high-pressure sealed reactor, and 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 ° C under an argon gas atmosphere to react the Si nanoparticles with pyridine for 60 minutes.

After the completion of the reaction, the inside pressure of the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell nanoparticles.

Next, the Si core-carbon shell nanoparticles were supplied to a high-temperature and high-pressure sealed reactor, and hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur (S) were supplied so that the content of MoS ₂ was 20 wt%.

Next, 100% argon gas was supplied to the high-temperature high-pressure sealed reactor, and the reactor was completely closed. The sealed high-temperature high-pressure reactor was heated to 500 DEG C under an argon gas atmosphere to react the Si core-carbon shell nanoparticles, Hexacarbonyl Molybdenum and sulfur for 30 minutes.

After the completion of the reaction, the pressure inside the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles.

3 (b) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to this example.

As shown in FIG. 3 (b), a carbon shell having a thickness of 8-10 nm is formed surrounding the surface of the Si core, and MoS ₂ surrounds the carbon shell surface to form a shell on a horizontal structure layer having a thickness of about 2 nm Able to know.

5 (a) is a photograph of the Si component distribution of Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2,

5 (b) is a photograph of the C component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2,

5 (c) is a photograph of the N component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2,

5 (d) is a photograph of the Mo component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2,

5 (e) is a photograph of the S component distribution of the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles prepared according to Example 3-2.

As can be seen from Figs. 5 (a) to 5 (e), it can be seen that the Si component is concentrated in the core of the nanoparticles and is not distributed in the outer shell layer of the nanoparticles. In addition, it can be seen that C and N are uniformly distributed on the entire surface of the nanoparticles, and are distributed densely in the outer region of the nanoparticles. Further, it can be seen that Mo and S are uniformly distributed on the entire surface of the nanoparticles, and are densely distributed in the outermost region of the nanoparticles. Thus, it can be seen that core-shell nanoparticles according to the present invention are clearly formed when core-shell nanoparticles are prepared using core-shell nanoparticles according to the present invention.

Example 3-3: Si core-carbon shell-MoS ₂ (38 wt%) Preparation of shell nanoparticles

The amount of MoS ₂ to be 38 wt%, Hexacarbonyl Molybdenum (Mo (CO) 6) , and sulfur and the Si-core prepared in the same manner as in Example 3-2 except that the supply (S) - carbonyl shell - MoS ₂ (38 wt%) shell nanoparticles were prepared.

3 (c) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (38 wt%) shell nanoparticles prepared according to this example.

As shown in FIG. 3 (c), a carbon shell having a thickness of 8-10 nm is formed surrounding the surface of the Si core, and the MoS ₂ surrounds the carbon shell surface to form a shell on a horizontal structure layer having a thickness of about 5 nm Able to know.

Example 3-4: Si core-carbon shell-MoS ₂ (56 wt%) Preparation of shell nanoparticles

Carbon core-MoS (carbon monoxide) was prepared in the same manner as in Example 3-2, except that hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur (S) were supplied so that the content of MoS ₂ was 56 wt% ₂ (56 wt%) shell nanoparticles were prepared.

3 (d) is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (56 wt%) shell nanoparticles prepared according to this embodiment.

As shown in FIG. 3 (d), a carbon shell having a thickness of 8-10 nm is formed surrounding the surface of the Si core, and the MoS ₂ surrounds the surface of the carbon shell to form a shell on a horizontally and vertically structured layer having a thickness of about 15 nm .

Example 4: Preparation of core-shell nanoparticles 4

The amount of MoS ₂ was changed to 0 wt%, 20 wt%, 38 wt% and 56 wt% respectively by using the core-shell nanoparticle manufacturing method according to the present invention, and the Si core-carbon shell-MoS ₂ shell- Nanoparticles were prepared.

Example 4-1: Si core-carbon shell-MoS ₂  Shell (0 wt%) - Preparation of carbon shell

First, Si nanoparticles and pyridine were fed to a high-temperature and high-pressure sealed reactor, and 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 ° C under an argon gas atmosphere to react the Si nanoparticles with pyridine for 60 minutes.

After the completion of the reaction, the inside pressure of the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell nanoparticles.

Next, the Si core-carbon shell nanoparticles and 100% argon gas were supplied to a high-temperature high-pressure hermetically sealed reactor and completely sealed. The sealed high-temperature high-pressure reactor was heated to 500 DEG C under an argon gas atmosphere and reacted for 30 minutes.

After the completion of the reaction, the pressure inside the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell-MoS ₂ (0 wt%) shell nanoparticles.

Next, the Si core-carbon shell-MoS ₂ (0 wt%) shell nanoparticles and pyridine were supplied to a high-temperature and high-pressure sealed reactor, and then 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 DEG C under an argon gas atmosphere and reacted for 60 minutes.

After the reaction was completed, the inside pressure of the reactor was released, and the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell-MoS ₂ (0 wt%) shell-carbon shell nanoparticles.

Example 4-2: Si core-carbon shell-MoS ₂ (20 wt%) shell-carbon shell nanoparticles

First, Si nanoparticles and pyridine were fed to a high-temperature and high-pressure sealed reactor, and 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 ° C under an argon gas atmosphere to react the Si nanoparticles with pyridine for 60 minutes.

After the completion of the reaction, the inside pressure of the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell nanoparticles.

Next, the Si core-carbon shell nanoparticles were supplied to a high-temperature and high-pressure sealed reactor, and hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur (S) were supplied so that the content of MoS ₂ was 20 wt%.

Next, 100% argon gas was supplied to the high-temperature high-pressure sealed reactor, and the reactor was completely closed. The sealed high-temperature high-pressure reactor was heated to 500 DEG C under an argon gas atmosphere to react the Si core-carbon shell nanoparticles, Hexacarbonyl Molybdenum and sulfur for 30 minutes.

After the completion of the reaction, the pressure inside the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles.

Next, the Si core-carbon shell-MoS ₂ (20 wt%) shell nanoparticles and pyridine were supplied to a high-temperature and high-pressure sealed reactor, and 100% of argon gas was supplied and completely sealed. The sealed high-temperature high-pressure reactor was heated to 700 DEG C under an argon gas atmosphere and reacted for 60 minutes.

After the completion of the reaction, the inside pressure of the reactor was released and the argon gas supply was stabilized, and then the temperature was lowered to room temperature to obtain Si core-carbon shell-MoS ₂ (20 wt%) shell-carbon shell nanoparticles.

Example 4-3: Si core-carbon shell-MoS ₂ (38 wt%) shell-carbon shell nanoparticles

Carbon core-MoS (silicon carbide) was prepared in the same manner as in Example 4-2, except that hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur (S) were supplied so that the content of MoS ₂ was 38 wt% ₂ (38 wt%) shell-carbon shell nanoparticles were prepared.

6 is a high-resolution TEM (HRTEM) photograph of the Si core-carbon shell-MoS ₂ (38 wt%) shell-carbon shell nanoparticles prepared according to this example.

6, a carbon shell having a thickness of 8-10 nm is formed to surround the surface of the Si core, a MoS ₂ surrounds the carbon shell surface, a shell is formed on a horizontal structure layer having a thickness of about 6-8 nm, It can be seen that a carbon shell having a thickness of about 2 nm is formed while surrounding the MoS2 shell.

Example 4-4: Si core-carbon shell-MoS ₂ (56 wt%) shell-carbon shell nanoparticles

Carbon core-MoS (silicon carbide) was prepared in the same manner as in Example 4-2, except that hexacarbonyl molybdenum (Mo (CO) ₆ ) and sulfur (S) were supplied so that the content of MoS ₂ was 56 wt% ₂ (56 wt%) shell-carbon shell nanoparticles were prepared.

Comparative Example 1: Preparation of nanoparticles

The Si core was heated without being coated with a shell layer to prepare nanoparticles.

First, Si nanoparticles were supplied to a high-temperature and high-pressure sealed reactor.

Next, 100% argon gas was supplied to the high-temperature high-pressure sealed reactor, and the reactor was completely closed. The sealed high-temperature high-pressure reactor was heated to 500 ° C under an argon gas atmosphere to react the Si nanoparticles for 30 minutes.

After the completion of the reaction, pressure inside the reactor was released, the argon gas supply was stabilized, and the temperature was lowered to room temperature to obtain Si nanoparticles.

1 (a) is a high-resolution TEM (HRTEM) photograph of Si core nanoparticles prepared according to Comparative Example 1. FIG.

1 (a), when only Si was heated without supplying MoS ₂ , It can be seen that a SiO _x layer of about 2-3 nm thickness is formed on the surface of the Si core.

The core shell structure of the core-shell nanoparticles prepared in Examples 1 to 4 and Comparative Example 1 is summarized in Table 1 below.

core The first shell The second shell The third shell Example 1-1 Si MoS ₂ (20 wt%) - - Examples 1-2 Si MoS ₂ (20 wt%) - - Example 1-3 Si MoS ₂ (20 wt%) - - Example 2 Si MoS ₂ (20 wt%) C - Example 3-1 Si C - - Example 3-2 Si C MoS ₂ (20 wt%) - Example 3-3 Si C MoS ₂ (20 wt%) - Example 3-4 Si C MoS ₂ (20 wt%) - Example 4-1 Si C - - Example 4-2 Si C MoS ₂ (20 wt%) C Example 4-3 Si C MoS ₂ (20 wt%) C Example 4-4 Si C MoS ₂ (20 wt%) C Comparative Example 1 Si - - -

Preparation Example 1: Preparation of a cell using core-shell nanoparticles according to the present invention 1

A core-shell half-cell was prepared using the core-shell nanoparticles prepared in Example 2-1 as an electrode active material.

First, core-shell nanoparticles, Denka black, a binder (a mixture of carboxymethyl cellulose and styrene butadiene copolymer) prepared in Example 2-1 were mixed at a ratio of 6: 2: 2, respectively, at 90 ° C Followed by vacuum drying for 30 minutes to prepare an electrode material.

Next, ethylene carbonate and diethylene carbonate 1: an electrolyte and a fluorinated ethylene carbonate was added and LiPF ₆ was added 3wt% was prepared in a solution mixed at a ratio of 1: 1 so that the solution of LiPF ₆ 1M.

A coiled half-cell was fabricated using lithium foil as the counter electrode and the electrode material and electrolyte prepared above.

Preparation Example 2: Preparation of a cell using core-shell nanoparticles according to the present invention 2

A coiled half-cell was prepared in the same manner as in Production Example 1, except that the core-shell nanoparticles prepared in Example 3-2 were used as an electrode active material.

Preparation Example 3: Preparation of a cell using nanoparticles

A coin-shaped half-cell was prepared in the same manner as in Preparation Example 1 except that the nanoparticles prepared in Comparative Example 1 were used as the electrode active material.

Experimental Example 1: Measurement of cycling of a coin type half cell

A 50-cycle cycling experiment of the coin-shaped half-cells prepared in Production Examples 1 to 3 was carried out.

FIG. 9 is a graph showing a capacity and a coulombic efficiency when the coin type half-cell manufactured in Production Examples 1 to 3 was subjected to 50 cycles of repeated cycling experiments.

As can be seen from FIG. 9, it can be seen that, in the case of Production Example 1 and Production Example 2, the charge amount is kept similar to the initial state even if the cycle is increased. Specifically, it can be seen that, in the case of Production Example 2, when the initial charge amount is about 2250 mAh / g and 50 cycles are carried out, the charge amount is about 1750 mAh / g. On the other hand, in the case of Production Example 3, it can be seen that as the charging cycle increases, the battery capacity sharply decreases. When 50 cycles are performed at the initial charging capacity of 2250 mAh / g, the charging amount is reduced to about 700 mAh / g have.

Therefore, the core-shell nanoparticles according to the present invention can be effectively used as an electrode active material of a battery, because the core-shell nanoparticles according to the present invention are used as an electrode active material and maintain an excellent charge amount even in repetitive charging and discharging when an electrode material and a battery are manufactured.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (27)

Supplying a core nanoparticle and a primary coating source to a high-temperature high-pressure hermetically sealed reactor;
Sealing the reactor;
Firstly heating the reactor in an inert gas atmosphere;
Supplying a secondary coating source to the reactor; And
A step of secondly heating the reactor in an inert gas atmosphere
Wherein the core-shell nanoparticles have at least two shells including a porous carbon shell comprising at least two shells.
The method according to claim 1,
Wherein the porous carbon shell has a pore size of 0.3 to 1.0 nm.
The method according to claim 1,
When the primary coating source is a carbon source, the secondary coating source is a phosphide source or a chalcogenide source,
Wherein the secondary coating source is a carbon source when the primary coating source is a phosphide source or a chalcogenide source.
The method of claim 3,
The carbon source is benzene _{(Benzene, C 6 H 6)} , toluene _{(Toluene, C 7 H 8)} , styrene _{(Styrene, C 8 H 8)} , indene _{(Indene, C 9 H 8)} , hexane (Hexane, C ₆ H ₁₄ ), octane (C ₈ H ₁₈ ), paraffin oil (C _x H _y ), naphthalene (C ₁₀ H ₈ ), anthracene (C ₁₄ H ₁₀ ) Fluorene, C ₁₃ H _10), solid paraffin (paraffin,, pyrene _{C x H y) (pyrene,} C 16 H 10), having 2 to 8 carbon atoms polymer consisting of monomers, acetylene (acetylene, C ₂ H _2), And any one selected from the group consisting of ethylene, C ₂ H ₄ , propane, C ₃ H ₈ , methane, CH ₄ , polyethylene, polystyrene and polypropylene. At least one core-shell nanoparticle.
The method of claim 3,
Wherein the carbon source is a carbon source containing at least one doping element selected from the group consisting of N, P and B. 15. The core-
The method of claim 3,
The carbon source may be melamine (C ₃ H ₆ N ₆ ), pyridine (C ₅ H ₅ N), acrylonitrile (C ₃ H ₃ N), pyrrole (C ₄ H ₅ N) , A mixed gas of ammonia (NH ₃ ) and hydrocarbon gas, tributylphosphine [CH ₃ (CH ₂ ) ₃ ] ₃ P), phosphorine (C ₅ H ₅ P), triphenylborane _{, (C 6 H 5) 3} B), barley Nin _{(Borinine, C 5 H 5 B} ), triethylborane _{(triethylborane ((C 2 H 5} ) 3 B), trimethyl borane _{(trimethylboron, B (CH 3)} 3 ), or trimethylboron -d9 (trimethylboron-d9, B ( CD 3) 3), borane-dimethyl amine (dimethylamine borane), borane pyridine (pyridine borane), borane trimethylamine (trimethylamine borane), borane ammonia (borane-ammonia) Tetrabutylammonium cyanoborohydride, ammonium tetraphenylborate, tetrabutylammonium borohydride, tetrabutylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, Which is selected from the group consisting of tetramethylammonium triacetoxyborohydride, 2,4,6-triphenylborazine, and borane diphenylphosphine. At least one core-shell nanoparticle.
The method of claim 3,
The phosphide source _{P, Ni (CO) 6,} Fe 2 (CO) 9, Zn (CH 3) 2, Zn (C 2 H 5) 2, In (CH 3) 3, Mo (CO) 6, Ga (CH ₃ ) ₃ and Ga (C ₂ H ₅ ) ₃ .
The method of claim 3,
Wherein the chalcogenide source is a sulfide source, a selenide source, a telluride source, or a polonide source.
The method of claim 3,
The chalcogenide source _{S, H 2 S, C 6} H 5 SeH, C 12 H 10 Se, Se (CH 3) 2, Se (C 2 H 5) 2 Mo (CO) 6, Ni (CO) 6 , Fe ₂ (CO) ₉ , W (CO) ₆ , _{Cr (CO) 6, Mn 2} (CO) 10, Ru 3 (CO) 12, Rh 4 (CO) 12, Re 2 (CO) 10, and the core is at least one which is Co ₂ (CO) selected from the group consisting of ₈ Method for manufacturing shell nanoparticles.
The method according to claim 1,
If the primary coating source is a carbon source, the primary heating temperature is between 550 캜 and 850 캜,
Wherein when the primary coating source is a phosphide source or a chalcogenide source, the primary heating temperature is 400 ° C. to 850 ° C.,
When the secondary coating source is a carbon source, the secondary heating temperature is 550 캜 to 850 캜,
Wherein said secondary heating temperature is 400 ° C. to 850 ° C. when said secondary coating source is a phosphide source or a chalcogenide source.
The method according to claim 1,
When the primary coating source is a carbon source, the primary heating time is 10 to 120 minutes,
When the primary coating source is a phosphide source or a chalcogenide source, the primary heating time is 10 to 60 minutes,
When the secondary coating source is a carbon source, the secondary heating time is 10 to 120 minutes,
Wherein the secondary heating time is 10 to 60 minutes when the secondary coating source is a phosphide source or a chalcogenide source.
The method according to claim 1,
Wherein the primary coating source and the secondary coating source to be supplied are used for coating the core nanoparticles without loss regardless of the type of the core nanoparticles.
The method according to claim 1,
Wherein the supply amount of the primary coating source and the secondary coating source is controlled so that uncoated core nanoparticles or micro-sized core-shell nanoparticles are not formed.
The method according to claim 1,
Wherein the core nanoparticles are a metal, a metal oxide, a semiconductor material, or a semiconductor oxide.
The method according to claim 1,
After the primary heating, releasing the internal pressure of the reactor and removing the residual gas to stabilize the inside of the reactor; And
Further comprising, after the secondary heating, releasing the internal pressure of the reactor and removing residual gas to stabilize the inside of the reactor.
The method according to claim 1,
After the secondary heating, supplying a tertiary coating source to the reactor;
Sealing the reactor; And
Further comprising a third step of heating the reactor in an inert gas atmosphere.
17. The method of claim 16,
When the secondary coating source is a carbon source, the tertiary coating source is a phosphide source or a chalcogenide source,
Wherein the second coating source is a phosphide source or a chalcogenide source, and wherein the third coating source is a carbon source.
17. The method of claim 16,
When the third coating source is a carbon source, the third heating temperature is 550 캜 to 850 캜,
Wherein the third heating temperature is 400 ° C to 850 ° C when the third coating source is a phosphide source or a chalcogenide source.
17. The method of claim 16,
When the third coating source is a carbon source, the third heating time is 10 to 120 minutes,
Wherein the third heating time is 10 to 60 minutes when the third coating source is a phosphide source or a chalcogenide source.
17. The method of claim 16,
Further comprising, after the third heating, releasing the internal pressure of the reactor and removing residual gas to stabilize the inside of the reactor.
Nanoparticle cores;
A first shell surrounding the nanoparticle core; And
A second shell surrounding the first shell,
/ RTI >
Wherein the first shell or the second shell is any one selected from the group consisting of porous carbon or phosphide and chalcogenide,
Wherein the first shell and the second shell are materials that are different from each other.
22. The method of claim 21,
A third shell surrounding the second shell,
Further comprising:
Wherein the third shell is any one selected from the group consisting of porous carbon or phosphide and chalcogenide,
Wherein the second shell and the third shell are different materials from each other.
22. The method of claim 21,
Wherein the porous carbon has a pore size of 0.3 to 1.0 nm.
22. The method of claim 21,
Wherein the phosphide is at least one selected from the group consisting of MoP, Ni ₂ P, Fe ₂ P, Fe ₃ P, Zn ₃ P ₂ , InP and GaP.
22. The method of claim 21,
The chalcogenide may be MoS ₂ , NiS, FeS, WS ₂ , Cr ₂ S ₃ , MnS, RuS ₂ , Re ₂ S ₇ , CoS, MoSe ₂ , NiSe, FeSe, WSe ₂ , CrSe, MnSe, RuSe, RhSe ₂ , ReSe _2, and CoSe.
22. The method of claim 21,
Wherein the nanoparticle core is a metal, a metal oxide, a semiconductor material, or a semiconductor oxide.
An electrode material comprising core-shell nanoparticles according to claim 21.

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