KR101804211B1 - Manufacturing method of anode active material powder for lithium secondary battery - Google Patents

Abstract

The present invention relates to a powder of a core-shell structure, which comprises a powder forming a core as a source of a solid electrolyte for a lithium secondary battery, and a metal oxide surrounding the surface of the powder and forming a shell, And more particularly to a method for producing a solid electrolyte powder for a lithium secondary battery. According to the present invention, a metal oxide is coated on a powder used as a solid electrolyte for a lithium secondary battery, thereby suppressing a chemical reaction between the electrolyte and the electrode, thereby achieving high safety of the battery.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solid electrolyte powder for a lithium secondary battery,

The present invention relates to a method for producing a solid electrolyte powder for a lithium secondary battery, and more particularly, to a method for manufacturing a solid electrolyte powder for a lithium secondary battery, which comprises coating a metal oxide on a powder used as a solid electrolyte for a lithium secondary battery to inhibit a chemical reaction between the electrolyte and the electrode, And more particularly, to a method for producing a solid electrolyte powder for a lithium secondary battery.

Conventional coating techniques, such as sol-gel or chemical vapor deposition, are difficult to control the coating rate on the surface of the material, resulting in non-uniform coatings throughout the particle, resulting in a greater amount of coating precursor than is actually needed to form a uniform coating There is a problem that it must be input. In addition, since it is difficult to control the thickness of the coating layer, it is difficult to form a coating having a uniform thickness for each coating process, and there is a problem that micro-coating with a thickness of several nm is difficult. If the thickness of the coating is not constant or thick due to such a problem, the coating permeability of the lithium ion becomes remarkably low. As a result, there is a problem that the efficiency is slightly increased or dropped rather than when the coating is not performed. In addition, when the particles are coated, it is likely that each of the particles is cohered or completely covered by the conventional coating method. Therefore, there is a need for a method that can completely coat the surface of the particle and coat it to a certain thickness.

Korean Patent Publication No. 10-1100029

The object of the present invention is to provide a method for producing a solid electrolyte powder for a lithium secondary battery, in which a metal oxide is coated on a powder used as a solid electrolyte for a lithium secondary battery to suppress a chemical reaction between the electrolyte and the electrode, .

The present invention relates to a vacuum processing apparatus comprising a vacuum chamber, a reactor rotatably installed in the vacuum chamber for coating a powder, a rotation unit for controlling the rotation of the reactor, a process gas supply unit for supplying a process gas into the reactor, A heater unit installed around the reactor to provide a temperature required for the process, and a vacuum coating / discharging unit including a vacuum / exhaust unit for evacuating the inside of the vacuum chamber or discharging the process gas from the vacuum chamber A method for producing a powder for use in a solid electrolyte for a lithium secondary battery, comprising the steps of: (a) placing a powder as a source of a solid electrolyte for a lithium secondary battery into a reactor; (b) The pressure is maintained at a vacuum state so as to be lower than the atmospheric pressure, and the heater control means of the heater unit Controlling the reactor to set the temperature in the vacuum chamber to a process temperature and operating the rotating unit to cause the reactor to periodically rotate; and (c) (D) injecting a purge gas into the reactor through the process gas supply unit to remove a remaining coating source; and (e) supplying an oxidant into the reactor through the process gas supply unit, And (f) injecting a purge gas into the reactor through the process gas supply unit to remove residual oxidizing agent, wherein the atomic layer deposition sequence of steps (c) through (f) Cycle to produce a powder coated with a metal oxide, wherein the coating source comprises a metal component of the metal oxide Sphere, and provides a method for producing a lithium secondary battery, the solid electrolyte powder, characterized in that the metal oxide is coated to achieve a thickness of 0.1~10nm.

The method for producing a solid electrolyte powder for a lithium secondary battery according to any one of the preceding claims, further comprising, between the step (c) and the step (d), interrupting supply of the coating source to prevent the coating source from flowing backward, Inducing pumping to cause the coating source to remain in the reactor with the pumping valve closed and allowing the coating source to be adsorbed onto the surface of the powder.

The vacuum / exhaust unit is always on during atomic layer deposition, and the pumping is controlled through the opening and closing of the pumping valve, and the step (c) Wherein the pumping valve is controlled to be open and the step of causing the coating source to be adsorbed to the surface of the powder is performed by closing the pumping valve Is preferably controlled.

Preferably, the injection induction pumping causes pumping for 0.1 to 2 seconds even after shutting off the supply of the coating source while the vacuum / evacuation unit is on to induce the introduction of the coating source into the reactor.

The method of manufacturing the solid electrolyte powder for a lithium secondary battery according to the present invention may further comprise the step of causing the coating source to be adsorbed on the surface of the powder and then pumping the pumping valve in a state where the pumping valve is opened before the step (d) The method may further include the step of removing purge gas remaining in the reactor after pumping with the pumping valve open after step (d) after step (d) ) Step, pumping with the pumping valve open may remove the purge gas remaining in the reactor.

In the step (c), the injection time of the coating source is preferably set to 0.1 to 20 seconds. In the step of causing the coating source to be adsorbed on the surface of the powder, the time for maintaining the coating source in the reactor is 5 to 120 Sec, and the step of removing the coating source remaining in the reactor by pumping is preferably set to 5 to 30 seconds, and in the step (d), the injection time of the purge gas is set to 1 to 120 seconds The purge gas remaining after purging in the state where the pumping valve is opened after the step (d) after the step (d) is preferably set to 5 to 30 seconds, In the step (f), the injection time of the oxidizing agent is set to 0.1 to 20 seconds, and in the step (f), the injection time of the purge gas is set to 1 to 120 seconds , And the step of purging the purge gas remaining in the reactor while the pumping valve is opened after the step (f) is preferably set to 5 to 30 seconds.

The method for producing a solid electrolyte powder for a lithium secondary battery according to the present invention may further comprise, between the step (e) and the step (f), interrupting the supply of the oxidant to prevent the oxidant from flowing backward, Inducing pumping to cause the oxidizing agent to enter into the reactor while maintaining the oxidant in the reactor with the pumping valve closed and allowing the coating source adsorbed on the surface of the powder to react with the oxidant to cause oxidation have.

Wherein the vacuum / evacuation unit is always on during atomic layer deposition and the pumping is controlled through open and close of the pumping valve, wherein steps (c) through (e) Wherein the pumping valve is controlled to be open and the oxidation step is controlled to be closed so that the pumping valve is closed, .

Preferably, the injection-induced pumping causes pumping for 0.1 to 2 seconds even after shutting off the supply of the oxidant in a state where the vacuum / exhaust unit is turned on to induce the introduction of the oxidant into the reactor.

Further, the method for manufacturing a solid electrolyte powder for a lithium secondary battery may further include a step of purging the purging gas remaining in the reactor after the step (d) in a state where the pumping valve is opened before the step (e) The method may further include, after step (f), removing the oxidizing agent remaining in the reactor by pumping with the pumping valve open before step (f), wherein after step (f) And pumping in an open state to remove purge gas remaining in the reactor.

In the step (c), the injection time of the coating source may be set to 0.1 to 20 seconds. In the step (d), the injection time of the purge gas may be set to 1 to 120 seconds, The purge gas remaining in the reactor is purged in a state where the pumping valve is opened before the step (e), and the purge gas remaining in the reactor is preferably set to 5 to 30 seconds, and in the step (e) And the oxidizing step is preferably set to 5 to 120 seconds, and the step of pumping and removing the oxidizing agent remaining in the reactor is preferably set to 10 to 50 seconds, In the step (f), the purge gas injection time is preferably set to 1 to 120 seconds, and after the step (f), the pumping valve is pumped And removing the purge gas remaining in the actor is preferably set from 5 to 30 seconds.

The powder that is a source of the solid electrolyte for a lithium secondary battery includes Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te ₂ O ₁₂ , Li ₃ Lu ₃ Te ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Sb ₂ O ₁₂ , Li _{5 . 5} La ₃ Nb _{1 . 75} In _{0 . 25} O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _0.5 Ta _1.5 O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _0.5 Ba _0.5 La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₇ La ₃ Ta ₂ O ₁₃ and Li ₇ La ₃ Ta ₂ O ₁₃ . Or more species.

In the step (a), the bead may be introduced into the reactor together with the powder that is the source of the solid electrolyte for the lithium secondary battery. Preferably, the bead having a diameter in the range of 0.01 to 1 mm is used. In the reactor Preferably, the beads and the powder as a source of the solid electrolyte for the lithium secondary battery have a weight ratio of 3 to 20: 1, and the process temperature is preferably higher than normal temperature and set at a temperature of 300 ° C or less.

The present invention also provides a powder of a core-shell structure produced by the method for producing a solid electrolyte powder for a lithium secondary battery, comprising: a powder forming a core as a source of a solid electrolyte for a lithium secondary battery; Wherein the metal oxide has a thickness of 0.1 to 10 nm. The solid electrolyte powder for a lithium secondary battery according to claim 1, wherein the metal oxide has a thickness of 0.1 to 10 nm.

The core may be selected from the group consisting of Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te ₂ O ₁₂ , Li ₃ Lu ₃ Te ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Sb ₂ O ₁₂ , Li _5.5 La ₃ Nb _1.75 In _0.25 O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _{0 . 5} Ta _{1 . 5} O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _{0 . 5} Ba _{0 . 5} La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₇ La ₃ Ta ₂ O _13, and Li ₇ La ₃ Ta ₂ O ₁₃ .

According to the method for producing a solid electrolyte powder for a lithium secondary battery according to the present invention, unlike an uneven coating of a conventional coating technique, a powder coating apparatus is used to form a uniformly precise coating thickness through atomic layer deposition sequence recipe A solid electrolyte for a secondary battery can be obtained.

The fine coating layer (metal oxide) of several nm can be formed on the surface of the solid electrolyte powder by controlling the thickness of the precise coating layer by using the powder coating apparatus, and the performance of the solid electrolyte material for the lithium secondary battery can be improved by forming the uniform coating Can be expected. Solid electrolytes for lithium secondary batteries can expect higher battery performance through coating.

FIG. 1 is a conceptual view schematically showing a configuration of a powder coating apparatus used for manufacturing a solid electrolyte for a lithium secondary battery according to a preferred embodiment of the present invention.
2 is a configuration diagram showing a configuration of a chamber part of the powder coating apparatus.
3 is a configuration diagram showing a configuration of a part of one side of the powder coating apparatus.
4 is a view sequentially showing a state in which the powder is stirred in the powder coating apparatus.
FIG. 5 is a view illustrating an atomic layer deposition sequence for coating a metal oxide on a powder according to a second embodiment of the present invention.
FIG. 6 is a view illustrating an atomic layer deposition sequence for coating a metal oxide on a powder according to a third embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not. Wherein like reference numerals refer to like elements throughout.

Hereinafter, the term " nano " refers to a size in nanometers (nm), which means a size of 1 to 1,000 nm. In the present invention, the term 'powder coating apparatus' refers to a powder coating system using an atomic layer deposition technique.

A method of manufacturing a solid electrolyte powder for a lithium secondary battery according to a preferred embodiment of the present invention includes a vacuum chamber, a reactor rotatably installed in the vacuum chamber for coating the powder, a rotation unit for controlling the rotation of the reactor, A heater unit disposed around the reactor to provide a temperature necessary for the process, and a heater unit for supplying a process gas from the vacuum chamber to the vacuum chamber, wherein the process gas is supplied to the reactor, (A) a step of inserting a powder, which is a source of a solid electrolyte for a lithium secondary battery, into a reactor; and (c) a step of putting a powder as a source of a solid electrolyte for a lithium secondary battery into a reactor , (b) the pressure in the vacuum chamber is less than the atmospheric pressure by the vacuum / Controlling the heater through the heater control means of the heater unit to set the temperature in the vacuum chamber at a process temperature and operating the rotation unit to make the reactor periodically rotate; (c) supplying a coating source into the reactor through the process gas supply unit; (d) injecting a purge gas into the reactor through the process gas supply unit to remove a remaining coating source; (e) supplying an oxidant into the reactor through the process gas supply unit, and (f) injecting a purge gas into the reactor through the process gas supply unit to remove residual oxidant, The atomic layer deposition sequence of the step (c) to the step (f) is carried out a plurality of cycles, and the metal oxide coated powder Production, and the coating source is a precursor containing the metal component of the metal oxide, the metal oxide is coated to achieve a thickness of 0.1~10nm.

The method for producing a solid electrolyte powder for a lithium secondary battery according to any one of the preceding claims, further comprising, between the step (c) and the step (d), interrupting supply of the coating source to prevent the coating source from flowing backward, Inducing pumping to cause the coating source to remain in the reactor with the pumping valve closed and allowing the coating source to be adsorbed onto the surface of the powder.

The vacuum / exhaust unit is always on during atomic layer deposition, and the pumping is controlled through the opening and closing of the pumping valve, and the step (c) Wherein the pumping valve is controlled to be open and the step of causing the coating source to be adsorbed to the surface of the powder is performed by closing the pumping valve Is preferably controlled.

Preferably, the injection induction pumping causes pumping for 0.1 to 2 seconds even after shutting off the supply of the coating source while the vacuum / evacuation unit is on to induce the introduction of the coating source into the reactor.

The method of manufacturing the solid electrolyte powder for a lithium secondary battery according to the present invention may further comprise the step of causing the coating source to be adsorbed on the surface of the powder and then pumping the pumping valve in a state where the pumping valve is opened before the step (d) The method may further include the step of removing purge gas remaining in the reactor after pumping with the pumping valve open after step (d) after step (d) ) Step, pumping with the pumping valve open may remove the purge gas remaining in the reactor.

In the step (c), the injection time of the coating source is preferably set to 0.1 to 20 seconds. In the step of causing the coating source to be adsorbed on the surface of the powder, the time for maintaining the coating source in the reactor is 5 to 120 Sec, and the step of removing the coating source remaining in the reactor by pumping is preferably set to 5 to 30 seconds, and in the step (d), the injection time of the purge gas is set to 1 to 120 seconds The purge gas remaining after purging in the state where the pumping valve is opened after the step (d) after the step (d) is preferably set to 5 to 30 seconds, In the step (f), the injection time of the oxidizing agent is set to 0.1 to 20 seconds, and in the step (f), the injection time of the purge gas is set to 1 to 120 seconds , And the step of purging the purge gas remaining in the reactor while the pumping valve is opened after the step (f) is preferably set to 5 to 30 seconds.

The method for producing a solid electrolyte powder for a lithium secondary battery according to the present invention may further comprise, between the step (e) and the step (f), interrupting the supply of the oxidant to prevent the oxidant from flowing backward, Inducing pumping to cause the oxidizing agent to enter into the reactor while maintaining the oxidant in the reactor with the pumping valve closed and allowing the coating source adsorbed on the surface of the powder to react with the oxidant to cause oxidation have.

Wherein the vacuum / evacuation unit is always on during atomic layer deposition and the pumping is controlled through open and close of the pumping valve, wherein steps (c) through (e) Wherein the pumping valve is controlled to be open and the oxidation step is controlled to be closed so that the pumping valve is closed, .

Preferably, the injection-induced pumping causes pumping for 0.1 to 2 seconds even after shutting off the supply of the oxidant in a state where the vacuum / exhaust unit is turned on to induce the introduction of the oxidant into the reactor.

Further, the method for manufacturing a solid electrolyte powder for a lithium secondary battery may further include a step of purging the purging gas remaining in the reactor after the step (d) in a state where the pumping valve is opened before the step (e) The method may further include, after step (f), removing the oxidizing agent remaining in the reactor by pumping with the pumping valve open before step (f), wherein after step (f) And pumping in an open state to remove purge gas remaining in the reactor.

In the step (c), the injection time of the coating source may be set to 0.1 to 20 seconds. In the step (d), the injection time of the purge gas may be set to 1 to 120 seconds, The purge gas remaining in the reactor is purged in a state where the pumping valve is opened before the step (e), and the purge gas remaining in the reactor is preferably set to 5 to 30 seconds, and in the step (e) And the oxidizing step is preferably set to 5 to 120 seconds, and the step of pumping and removing the oxidizing agent remaining in the reactor is preferably set to 10 to 50 seconds, In the step (f), the purge gas injection time is preferably set to 1 to 120 seconds, and after the step (f), the pumping valve is pumped And removing the purge gas remaining in the actor is preferably set from 5 to 30 seconds.

The powder that is a source of the solid electrolyte for a lithium secondary battery includes Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te ₂ O ₁₂ , Li ₃ Lu ₃ Te ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Sb ₂ O ₁₂ , Li _{5 . 5} La ₃ Nb _{1 . 75} In _{0 . 25} O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _0.5 Ta _1.5 O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _0.5 Ba _0.5 La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₇ La ₃ Ta ₂ O ₁₃ and Li ₇ La ₃ Ta ₂ O ₁₃ . Or more species.

In the step (a), the bead may be introduced into the reactor together with the powder that is the source of the solid electrolyte for the lithium secondary battery. Preferably, the bead having a diameter in the range of 0.01 to 1 mm is used. In the reactor Preferably, the beads and the powder as a source of the solid electrolyte for the lithium secondary battery have a weight ratio of 3 to 20: 1, and the process temperature is preferably higher than normal temperature and set at a temperature of 300 ° C or less.

A solid electrolyte powder for a lithium secondary battery according to a preferred embodiment of the present invention is a powder of a core-shell structure produced by the above-described method, comprising: a powder forming a core as a source of a solid electrolyte for a lithium secondary battery; And a metal oxide which surrounds and forms a shell, and the metal oxide has a thickness of 0.1 to 10 nm.

The core may be selected from the group consisting of Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te ₂ O ₁₂ , Li ₃ Lu ₃ Te ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Sb ₂ O ₁₂ , Li _5.5 La ₃ Nb _1.75 In _0.25 O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _{0 . 5} Ta _{1 . 5} O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _{0 . 5} Ba _{0 . 5} La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₇ La ₃ Ta ₂ O _13, and Li ₇ La ₃ Ta ₂ O ₁₃ .

Hereinafter, a solid electrolyte powder for a lithium secondary battery according to a preferred embodiment of the present invention and a method for producing the same will be described in more detail.

FIG. 1 is a conceptual diagram schematically showing the configuration of a powder coating apparatus used for manufacturing a solid electrolyte powder for a lithium secondary battery according to a preferred embodiment of the present invention, and FIG. 2 is a configuration diagram showing the configuration of a chamber portion of a powder coating apparatus. 3 is a configuration diagram showing a configuration of a part of one side of the powder coating apparatus. FIG. 4 is an explanatory view showing a state in which the powder is stirred in the powder coating apparatus. FIG.

1 to 4, a powder coating apparatus used for manufacturing a solid electrolyte powder for a lithium secondary battery according to a preferred embodiment of the present invention includes a vacuum chamber 100, A rotating unit 300 for controlling the rotation of the reactor 200, a process gas supply unit 400 for supplying a process gas into the reactor 200, A heater unit 500 installed around the reactor 200 to provide a temperature required for the process and a heater unit 500 for supplying a process gas from the vacuum chamber 100 into the vacuum chamber 100 And a vacuum / exhaust unit 700 for exhausting the exhaust gas.

Such a powder coating apparatus is patent-pending and patent registered by the applicant of the present invention (Korean Patent Registration No. 10-1452262, entitled Powder Coating Apparatus and Coating Method).

The reactor 200 may be provided with an agitating means 600. The agitating means 600 may be configured such that when the reactor 200 is rotated, the internal powder is pulled so as to rotate together and the powder is agitated through self-falling It plays a role.

The vacuum chamber 100 rotatably supports both sides of the reactor 200 through a shaft and includes a first shaft 110a and a second shaft 120b, The penetration of the vacuum chamber 100 of the shaft 120 to be connected is kept airtight by the hermetic means 130 and thereby maintains the vacuum state when the vacuum chamber 100 is in a vacuum state.

An insulating plate (not shown) may be provided on the inner surface of the vacuum chamber 100 to prevent heat generated by the heater unit 500 from being radiated to the outside.

One shaft 110 connected to the process gas supply unit 400 has a hollow shape so that gas provided from the process gas supply unit 400 is supplied to the reactor 200, It also functions as a gas inflow line.

In addition, the vacuum chamber 100 is formed with an openable and closable configuration so that the reactor 200 can be separated and assembled therein. For example, one side is openable and closable through a cap.

The rotation unit 300 is for rotating the reactor 200 at a predetermined process speed and controlling the rotation speed of the reactor 200. The rotation unit 300 includes a rotation driving member 310 such as a motor and a rotation control unit 330 for controlling rotation of the rotation driving member 310. [ (320). The powder is rotated by the rotation unit 300 and the powder aggregates are dispersed by the beads, so that the coating can be effectively performed.

The process gas supply unit 400 supplies and blocks the process gases necessary for the process, that is, the coating source, the oxidizer, the purge gas, and the like into the reactor 200. The operation of the process gas supply unit 400 is controlled by a controller Lt; / RTI > As the process gas supply unit 400, those used in known deposition units included in an ALD (Atomic Layer Deposition), a CVD (Chemical Vapor Deposition), a sputter, or the like can be employed.

The heater unit 500 is for raising the temperature of the reactor 200 to a temperature required for the process during powder coating in the reactor 200. The heater unit 500 includes a heater control unit 520 for controlling the heater 510 and the heater 510, .

The vacuum / exhaust unit 700 serves to evacuate the inside of the vacuum chamber 100 (reactor 200) and exhaust the process gas provided by the process gas supply unit 400. The vacuum / exhaust unit 700 is always kept on during atomic layer deposition. A pumping valve (not shown) may be provided to block pumping between the reactor 200 and the vacuum / exhaust unit 700. The pumping is controlled through the opening and closing of the pumping valve.

The reactor 200 is formed in a hollow cylindrical shape, and each of the lengthwise end portions (i.e., the supply gas inlet portion and the discharge portion) is filled with a gas by a process gas supply unit 400, A filter member 210 is provided to prevent the powder from flowing out to the outside (see FIG. 3). Accordingly, the filter member 210 prevents the powder from flowing out and allows smooth flow of the precursor and the process gas.

A discharge port 220 for discharging the process gas passing through the filter member 210 to the outside of the reactor 200 is provided on the downstream surface (surface orthogonal to the longitudinal direction) of the reactor 200 with respect to the flow of the process gas, , Preferably two or more (see Fig. 3).

The stirring means 600 may be formed of one or more blades 600 extending in the longitudinal direction of the reactor 200, protruding a predetermined length from the inner surface, and formed at intervals in the circumferential direction.

FIG. 4 is an explanatory view showing a state in which the powder is stirred in the powder coating apparatus. FIG. 4 shows a case where the stirring means 600 is formed of four blades 610.

The solid electrolyte for a lithium secondary battery can be manufactured using the powder coating apparatus described above. In the chemical coating method such as the sol-gel method in which a metal oxide is coated using an atomic layer deposition technique, It is difficult to coat uniformly, but the above-described powder coating apparatus is possible.

A solid electrolyte powder for a lithium secondary battery is manufactured including a constitution of a process recipe for a powder different from a recipe of a general atomic layer deposition technique.

The inventors of the present invention have developed a solid electrolyte coating method for a lithium secondary battery using the above powder coating apparatus. The advantage of this coating method is that it can be applied to various powders regardless of specific powders. As the coating source, various sources necessary for coating can be used, and the purge step can also use a gas such as nitrogen or argon.

Hereinafter, a method for producing a solid electrolyte powder for a lithium secondary battery according to a preferred embodiment of the present invention will be described in detail.

The inventors of the present invention have studied and developed a coating process sequence of a solid electrolyte suitable for use in a lithium secondary battery.

The solid electrolyte for a lithium secondary battery is manufactured by using the powder coating apparatus described above and the rotation speed of the reactor 200, the bead input amount, the temperature in the vacuum chamber 100 during the coating process, the atomic layer deposition (ALD) cycle , Atomic layer deposition sequence, time, and the like can be suitably controlled to coat a metal oxide having a desired thickness on a powder that is a source of a solid electrolyte for a lithium secondary battery.

After the vacuum chamber 100 is opened to separate the reactor 200 from the reactor 200 and powder is put into the reactor 200, the reactor 200 is coupled to the vacuum chamber 100, and the vacuum chamber 100 is closed do.

The powder may be selected from the group consisting of Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te ₂ O ₁₂ , Li ₃ Lu ₃ Te ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Sb ₂ O ₁₂ , Li _5.5 La ₃ Nb _1.75 In _0.25 O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _0.5 Ta _1.5 O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _0.5 Ba _0.5 La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₇ La ₃ Ta ₂ O _13, and Li ₇ La ₃ Ta ₂ O ₁₃ .

Considering that the powder is used as a solid electrolyte of a lithium secondary battery, it is preferable to use a powder having an average particle diameter of 100 nm to 900 m. The powder may have one or more forms selected from a nanowire, a porous material, a nanorod, a nanotube, a nanosheet, a hollow, and a yoke-shell.

The beads (agitating balls) may be placed in the reactor 200 together with the powder. By putting the beads together with the powder in the reactor 200, the effect of stirring by dropping of the powder by self-weight can be improved, and uniform coating on the surface of the powder can be achieved. The weight ratio of the beads supplied to the reactor and the powder to be coated is preferably in the range of about 3 to 20: 1 (bead: powder), and the beads may be put together at an appropriate ratio based on the volume of the powder. It is preferable that the bead is made of a material having strong strength such as zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), and stainless steel and having no reactivity with the powder to be coated. It is preferable to use the bead having a diameter in the range of 0.01 to 1 mm so as to be suitable for agitation of the powder. The beads may be all of the same size or beads having two or more sizes may be used together. By using beads having different diameters, the effect of stirring the fine powder can be enhanced. The bead content, the bead size, the agitation time, the rotation speed per minute, and the like are appropriately controlled. By stirring, the powder is pulverized to a fine size and has a uniform particle size distribution.

And the inside of the vacuum chamber 100 (reactor 200) is kept in a vacuum state by the vacuum / exhaust unit 700. The pressure in the vacuum chamber 100 is kept under vacuum such that the pressure in the vacuum chamber 100 is lower than the atmospheric pressure (for example, 1 to 700 mtorr).

The heater 510 is controlled through the heater control unit 520 of the heater unit 500 to set the temperature in the vacuum chamber 100 to the process temperature required in the process. It is preferable that the process temperature is set to a range in which the atomic layer surface reaction of the powder can occur.

The rotation drive member 310 of the rotation unit 300 is operated to periodically rotate the reactor 200 as shown in FIG.

4 (b) to 4 (c), the blade 610 pulls the powder and the bead in the rotating direction, and as the reactor 200 rotates, At the time when the blade 610 is positioned almost vertically, the powder and the bead fall down as shown in the figure, and this process is repeated, whereby the powder is uniformly stirred. The rotational speed of the reactor 200 is preferably set to about 10 to 200 rpm.

A process gas such as a coating source, a purge gas, and an oxidizer (reaction gas) is supplied through a process gas supply unit 400 and a process gas is supplied into the reactor 200 through the one shaft 110.

The process gas is discharged from the one shaft 110 at one end of the reactor 200 through a plurality of outlets 220 at the other end. The powder is positioned between both ends of the path through which the process gas is discharged, . In addition, since the filter member 210 is positioned at both ends of the reactor 200, the interference between the filter member and the powder can be minimized by the filter member 210, thereby preventing reduction in coating efficiency.

Hereinafter, the atomic layer deposition sequence for coating the metal oxide on the powder will be described in detail.

≪ Example 1 >

An atomic layer deposition sequence is applied to coat the metal oxide on the powder, and the solid electrolyte for a lithium secondary battery manufactured through the atomic layer deposition sequence has properties suitable for use in a lithium secondary battery.

The coating source is supplied into the reactor 200 through which the powder is loaded through the process gas supply unit 400 (S1). The coating source is appropriately selected depending on the kind of metal oxide to be coated on the powder surface. The metal oxide is a material of a component different from the powder component, and the coating source is a precursor including a metal component of a metal oxide. The metal oxide may be a transition metal oxide, an oxide including Mg or Ca, and examples of the metal oxide include Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZnO, MgO, and ZrO ₂ . It is not. For example, if you want to coat the aluminum (Al ₂ O ₃₎ oxide powder surface, trimethyl aluminum _{(Al (CH 3) 3)} , ethylpiperidine trimethylaluminum _{(Al (CH 3) 3 N} (CH 2) 5 C 2 H _5), methylpyrrolidine trimethylaluminum _{(Al (CH 3) 3 N} (CH 2) 4 CH 3), butyl-pyrrolidin-trimethyl aluminum _{(Al (CH 3) 3 N} (CH 2) 4 C 4 H 9 ), methylpyrrolidine triethylaluminum _{(Al (C 2 H 5)} 3 N (CH 2) 4 CH 3), butyl-pyrrolidin-triethyl aluminum _{(Al (C 2 H 5)} 3 N (CH 2) 4 C ₄ H ₉ ) and ethylpiperidine triethyl aluminum (Al (C ₂ H ₅ ) ₃ N (CH ₂ ) ₅ C ₂ H ₅ ) can be used as the coating source, and titanium dioxide If you want to coat the TiO _2), the titanium isopropoxide _{(Ti (OCH (CH 3)} 2) 4, titanium chloride (TiCl _4), titanium tetra-iodide (TiI _4), titanium ethoxide (Ti ₄ (OCH ₂ CH ₃ ) ₁₆ ), tetrakis (diethylamino) titanium (Ti (N (C ₂ H ₅ ) _{2) 4),} tetrakis (dimethylamino) titanium (Ti (N (CH _{3) 2) 4),} titanium n- butoxide (Ti (C ₄ H _{9) 4)} and tetrakis (ethylmethylamino) titanium _{(((CH 3 C 2 H} 5) N) 4 Ti) if you want among the one or more materials that are selected can be used as coating source, the coating of silica (SiO ₂₎ is tetrakis (ethylmethylamino) silane (Si ( _{N (CH 3) (C 2} H 5)) 4), tris (ethylmethylamino) silane _{(HSi ((N (CH 3} ) C 2 H 2)) 2), tris (dimethylamino) silane (HSi (( _{N (CH 3) 2) 3} ), bis (ethylmethylamino) silane _{(H 2 Si ((N (} CH 3) C 2 H 5)) 2), bis (diethylamino) silane (H ₂ Si (( _{N (C 2 H 5) 2} ) 2), tetrakis (diethylamino) silane _{(Si (NH (C 2 H} 5)) 4), tris (pyrrolidino) silane _{(SiH (NC 4 H 8)} 3) And hexachlorodisilane (Si ₂ Cl ₆ ) may be used as a coating source. In case of coating zinc oxide (ZnO), diethyl zinc (Zn (C ₂ H ₅ ) ₂ ) And dimethyl zinc _{(Zn (CH 3) 2)} , zinc chloride (ZnCl _2), methyl zinc isopropoxide _{((CH 3) Zn (OCH} (CH 3) 2) and zinc acetate (Zn (CH ₃ COO) ₂ ) May be used as a coating source. The injection time of the coating source is appropriately set in consideration of the surface area, weight, coating source species, etc. of the powder to be coated. For example, the injection time of the coating source is preferably set to about 0.1 to 20 seconds. If the injection time of the coating source is too short, a sufficient amount of the coating source is not injected and metal oxide particles not coated per atomic layer deposition cycle And if the injection time of the coating source is too long, the amount of the unreacted coating source (which remains uncoated on the powder surface) may increase, which may be uneconomical. The supply flow rate of the coating source is preferably about 1 to 1000 sccm.

The supply of the coating source is blocked, and the purge gas is injected into the reactor 200 to remove the non-adsorbed remaining coating source (S5). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar) which does not chemically react with the powder can be used. The injection time of the purge gas is set in consideration of the content of the coating source staying in the reactor 200, and is suitably about 1 to 120 seconds, for example. If the injection time of the purge gas is too short, it may be difficult to sufficiently remove the coating source. If the injection time of the coating source is too long, sufficient removal of the coating source may be performed. However, It is possible that the amount of consumption is large and it is uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

The supply of the purge gas is interrupted, and the oxidant is supplied into the reactor 200 (S7). The oxidizing agent is supplied into the reactor 200 through the process gas supply unit 400. Examples of the oxidizing agent include water vapor (H ₂ O), ozone (O ₃ ), and the like, which react with the coating source to cause oxidation. The time for injecting the oxidizing agent is set in consideration of the content of the coating source adsorbed on the surface of the powder, and is suitably about 0.1 to 20 seconds, for example. If the injection time of the oxidizing agent is too short, sufficient oxidation reaction can not occur. If the injection time of the oxidizing agent is too long, sufficient oxidation reaction may occur. However, since it is not economical due to a lot of time consuming and consumes the oxidizing agent, have. The supply flow rate of the oxidizing agent is preferably about 1 to 1000 sccm.

The supply of the oxidizing agent is interrupted, and the purge gas is injected into the reactor 200 to remove the unreacted remaining oxidizing agent (S11). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar), which does not chemically react with the powder and the coating source, may be used. The injection time of the purge gas is set in consideration of the content of the oxidizing agent remaining in the reactor 200 and the like, and is suitably about 1 to 120 seconds, for example. If the purge gas injection time is too short, it may be difficult to sufficiently remove the oxidizer. If the purge gas injection time is too long, sufficient removal of the oxidizer may be performed. However, Can be uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

In the above-described atomic layer deposition sequence, S1, S5, S7, and S11 are performed once, which is referred to as a one-atom layer deposition cycle, and the process time for each step can be set flexibly according to the surface area of the powder to be used, have.

≪ Example 2 >

FIG. 5 is a view illustrating an atomic layer deposition sequence for coating a metal oxide on a powder according to a second embodiment of the present invention. Referring to FIG. 5, a coating source injection, an oxidant injection, And in the vacuum chamber 100 over time for purge gas injection. In FIG. 5, pumping is based on whether the pumping valve is open or closed.

Referring to FIG. 5, a characteristic atomic layer deposition sequence different from a general atomic layer deposition sequence is applied in order to coat a metal oxide on a powder, and the solid electrolyte for a lithium secondary battery manufactured by the method is used for a lithium secondary battery And have suitable properties.

The coating source is supplied into the reactor 200 through which the powder is loaded through the process gas supply unit 400 (S1). The coating source is appropriately selected depending on the kind of metal oxide to be coated on the powder surface. The metal oxide is a material of a component different from the powder component, and the coating source is a precursor including a metal component of a metal oxide. The metal oxide is _{Al 2 O 3, SiO 2,} TiO 2, ZnO, MgO, ZrO _2, and the like, and the like. The injection time of the coating source is appropriately set in consideration of the surface area, weight, coating source species, etc. of the powder to be coated. For example, the injection time of the coating source is preferably set to about 0.1 to 20 seconds. If the injection time of the coating source is too short, a sufficient amount of the coating source is not injected and metal oxide particles not coated per atomic layer deposition cycle And if the injection time of the coating source is too long, the amount of the unreacted coating source (which remains uncoated on the powder surface) may increase, which may be uneconomical. The supply flow rate of the coating source is preferably about 1 to 1000 sccm.

The supply of the coating source is cut off, and injection induction pumping is performed so that the coating source can be completely injected into the reactor 200 (S2). The injection induction pumping is performed by the vacuum / exhaust unit 700 for a very short time (e.g., within 2 seconds) to allow the coating source supplied through the process gas supply unit 400 to be fully injected into the reactor 200 Pumping is effected. Preferably, the injection-induced pumping is performed at a rate of 0.1 < RTI ID = 0.0 > (%) < / RTI & Allow pumping for ~ 2 seconds. The injection induction pumping is performed, so that the coating source is completely injected into the reactor 200 and remains in sufficient quantities, and the amount of unreacted coating source can be minimized, which is economical. Injection-induced pumping functions to prevent the coating source from flowing backward, and in the absence of such injection-induced pumping, the coating source may be countercurrent, resulting in poor coating efficiency and also problems with the powder coating apparatus. This injection-induced pumping is one of the characteristic features of the present invention which is not present in a typical atomic layer deposition step. If the time of the injection induction pumping is too long, the coating source can not sufficiently stay in the reactor 200, but may be vented through the outlet 220 to cause loss of the coating source. Taking this into consideration, the time of the injection induction pumping is set to a time (for example, 0.1 to 2 seconds) required for the coating source to reach the inside of the reactor 200 in consideration of the operation capability of the control unit of the vacuum / It is good.

The coating source is held in the reactor 200 so that the coating source is adsorbed on the surface of the powder (S3). The coating source in the reactor 200 is adsorbed on the surface of the powder, and the diffusion also occurs inside the powder. The holding time (reaction time) for adsorbing to the surface of the powder is set in consideration of the content of the coating source staying in the reactor 200 and the like, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, the time for the coating source to diffuse into the powder agglomerate is insufficient and only the particles located on the surface of the agglomerate can be coated, which is undesirable. If the retention time is too long, sufficient adsorption may occur Time consuming may not be economical.

A purge gas is injected into the reactor 200 to remove the remaining adsorbed coating source (S5). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar) which does not chemically react with the powder can be used. The injection time of the purge gas is set in consideration of the content of the coating source staying in the reactor 200, and is suitably about 1 to 120 seconds, for example. If the injection time of the purge gas is too short, it may be difficult to sufficiently remove the coating source. If the injection time of the coating source is too long, sufficient removal of the coating source may be performed. However, It is possible that the amount of consumption is large and it is uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

The oxidant is supplied into the reactor 200 (S7). The oxidizing agent is supplied into the reactor 200 through the process gas supply unit 400. Examples of the oxidizing agent include water vapor (H ₂ O), ozone (O ₃ ), and the like, which react with the coating source to cause oxidation. The time for injecting the oxidizing agent is set in consideration of the content of the coating source adsorbed on the surface of the powder, and is suitably about 0.1 to 20 seconds, for example. If the injection time of the oxidizing agent is too short, sufficient oxidation reaction can not occur. If the injection time of the oxidizing agent is too long, sufficient oxidation reaction may occur. However, since it is not economical due to a lot of time consuming and consumes the oxidizing agent, have. The supply flow rate of the oxidizing agent is preferably about 1 to 1000 sccm.

The supply of the oxidant is shut off, and injection induction pumping is performed so that the oxidant can be completely injected into the reactor 200 (S8). The injection induction pumping is pumped by the vacuum / exhaust unit 700 for a very short time (e.g., within 2 seconds) to allow the oxidant fed through the process gas supply unit 400 to be fully injected into the reactor 200 And preferably the injection-induced pumping is performed in a state where the vacuum / exhaust unit 700 is turned on to induce the introduction of the oxidizing agent into the reactor 200, Pumping for a second. The introduction of the induction pumping allows the oxidant to be fully injected into the reactor 200 to remain in sufficient quantities and is economical because it minimizes the amount of oxidant that does not participate in the reaction. Injection-induced pumping functions to prevent the oxidant from flowing backward, and in the absence of such injection-induced pumping, the oxidant may flow backward, resulting in poor coating efficiency and problems with the powder coating apparatus. This injection-induced pumping is one of the characteristic features of the present invention which is not present in a typical atomic layer deposition step. If the time of the injection induction pumping is too long, the oxidant may not sufficiently stay in the reactor 200, but may be exhausted through the exhaust port 220 to cause the loss of the oxidant. Taking this into consideration, the time for the injection induction pumping is set to a time (for example, 0.1 to 2 seconds) required for the oxidant to reach the interior of the reactor 200 in consideration of the operation capability of the control unit of the vacuum / good.

The oxidizing agent is held in the reactor 200 so that the coating source adsorbed on the surface of the powder reacts with the oxidizing agent to cause oxidation (S9). The oxidant in the reactor 200 serves to oxidize the coating source adsorbed on the surface of the powder, and the coating source adsorbed on the surface of the powder is oxidized and transformed into metal oxide. The holding time (reaction time) for the oxidation reaction is set in consideration of the content of the oxidizing agent remaining in the reactor 200, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, sufficient oxidation reaction may not occur. If the retention time is too long, sufficient oxidation reaction may occur but it may not be economical due to a long time consumption.

The purge gas is injected into the reactor 200 to remove the unreacted remaining oxidizing agent (S11). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar), which does not chemically react with the powder and the coating source, may be used. The injection time of the purge gas is set in consideration of the content of the oxidizing agent remaining in the reactor 200 and the like, and is suitably about 1 to 120 seconds, for example. If the purge gas injection time is too short, it may be difficult to sufficiently remove the oxidizer. If the purge gas injection time is too long, sufficient removal of the oxidizer may be performed. However, Can be uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

When the steps S1, S2, S3, S5, S7, S8, S9 and S11 are performed once in the atomic layer deposition sequence described above, this is referred to as a one atomic layer deposition cycle, and the process time for each step depends on the surface area of the powder used, It can be set flexibly according to the type and the like.

≪ Example 3 >

FIG. 6 is a view illustrating an atomic layer deposition sequence for coating a metal oxide on a powder according to a third embodiment of the present invention. FIG. 6 shows a process performed in the vacuum chamber 100 over time for a coating source injection, an oxidant injection, a reaction process, a pumping and a purge gas injection. In FIG. 6, the pumping is based on whether the pumping valve is open or closed.

Referring to FIG. 6, a characteristic atomic layer deposition sequence different from the general atomic layer deposition sequence is applied in order to coat the metal oxide on the powder, and the solid electrolyte for a lithium secondary battery manufactured through the process is used for a lithium secondary battery And have suitable properties.

The coating source is supplied into the reactor 200 through which the powder is loaded through the process gas supply unit 400 (S1). The coating source is appropriately selected depending on the kind of metal oxide to be coated on the powder surface. The metal oxide is a material of a component different from the powder component, and the coating source is a precursor including a metal component of a metal oxide. The metal oxide is _{Al 2 O 3, SiO 2,} TiO 2, ZnO, MgO, ZrO _2, and the like, and the like. The injection time of the coating source is appropriately set in consideration of the surface area, weight, coating source species, etc. of the powder to be coated. For example, the injection time of the coating source is preferably set to about 0.1 to 20 seconds. If the injection time of the coating source is too short, a sufficient amount of the coating source is not injected and metal oxide particles not coated per atomic layer deposition cycle And if the injection time of the coating source is too long, the amount of the unreacted coating source (which remains uncoated on the powder surface) may increase, which may be uneconomical. The supply flow rate of the coating source is preferably about 1 to 1000 sccm.

The supply of the coating source is cut off, and injection induction pumping is performed so that the coating source can be completely injected into the reactor 200 (S2). The injection induction pumping is performed by the vacuum / exhaust unit 700 for a very short time (e.g., within 2 seconds) to allow the coating source supplied through the process gas supply unit 400 to be fully injected into the reactor 200 Pumping is effected. Preferably, the injection-induced pumping is performed at a rate of 0.1 < RTI ID = 0.0 > (%) < / RTI & Allow pumping for ~ 2 seconds. The injection induction pumping is performed, so that the coating source is completely injected into the reactor 200 and remains in sufficient quantities, and the amount of unreacted coating source can be minimized, which is economical. Injection-induced pumping functions to prevent the coating source from flowing backward, and in the absence of such injection-induced pumping, the coating source may be countercurrent, resulting in poor coating efficiency and also problems with the powder coating apparatus. This injection-induced pumping is one of the characteristic features of the present invention which is not present in a typical atomic layer deposition step. If the time of the injection induction pumping is too long, the coating source can not sufficiently stay in the reactor 200, but may be vented through the outlet 220 to cause loss of the coating source. Taking this into consideration, the time of the injection induction pumping is set to a time (for example, 0.1 to 2 seconds) required for the coating source to reach the inside of the reactor 200 in consideration of the operation capability of the control unit of the vacuum / It is good.

The coating source is held in the reactor 200 so that the coating source is adsorbed on the surface of the powder (S3). The coating source in the reactor 200 is adsorbed on the surface of the powder, and the diffusion also occurs inside the powder. The holding time (reaction time) for adsorbing to the surface of the powder is set in consideration of the content of the coating source staying in the reactor 200 and the like, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, the time for the coating source to diffuse into the powder agglomerate is insufficient and only the particles located on the surface of the agglomerate can be coated, which is undesirable. If the retention time is too long, sufficient adsorption may occur Time consuming may not be economical.

The process of pumping and removing the coating source remaining in the reactor 200 may be performed (S4). By allowing pumping by the vacuum / exhaust unit 700, the coating source that is not adsorbed to the powder surface and remains in the reactor 200 can be exhausted through the outlet 220. Since the vacuum / exhaust unit 700 is always on, the pumping valve may be opened when the coating source is to be pumped and removed. The pumping time is set in consideration of the amount of the coating source remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, sufficient removal of the coating source may be difficult, and if the pumping time is too long, sufficient removal of the coating source may be accomplished, but it may not be economical due to time consuming.

A purge gas is injected into the reactor 200 to remove the remaining adsorbed coating source (S5). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar) which does not chemically react with the powder can be used. The injection time of the purge gas is set in consideration of the content of the coating source staying in the reactor 200, and is suitably about 1 to 120 seconds, for example. If the injection time of the purge gas is too short, it may be difficult to sufficiently remove the coating source. If the injection time of the coating source is too long, sufficient removal of the coating source may be performed. However, It is possible that the amount of consumption is large and it is uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

After the supply of the purge gas is stopped, the purge gas remaining in the reactor 200 may be pumped and removed (S6). The purging gas remaining in the reactor 200 by pumping by the vacuum / exhaust unit 700 can be exhausted through the exhaust port 220. When the purge gas is to be pumped and removed by the vacuum / exhaust unit 700, the pumping valve may be kept open even after the purge gas is shut off. The pumping time is set in consideration of the amount of the purge gas remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the purge gas. If the pumping time is too long, the purge gas may be sufficiently removed, but it may not be economical due to a long time consumption.

The oxidant is supplied into the reactor 200 (S7). The oxidizing agent is supplied into the reactor 200 through the process gas supply unit 400. Examples of the oxidizing agent include water vapor (H ₂ O), ozone (O ₃ ), and the like, which react with the coating source to cause oxidation. The time for injecting the oxidizing agent is set in consideration of the content of the coating source adsorbed on the surface of the powder, and is suitably about 0.1 to 20 seconds, for example. If the injection time of the oxidizing agent is too short, sufficient oxidation reaction can not occur. If the injection time of the oxidizing agent is too long, sufficient oxidation reaction may occur. However, since it is not economical due to a lot of time consuming and consumes the oxidizing agent, have. The supply flow rate of the oxidizing agent is preferably about 1 to 1000 sccm.

The supply of the oxidant is shut off, and injection induction pumping is performed so that the oxidant can be completely injected into the reactor 200 (S8). The injection induction pumping is pumped by the vacuum / exhaust unit 700 for a very short time (e.g., within 2 seconds) to allow the oxidant fed through the process gas supply unit 400 to be fully injected into the reactor 200 And preferably the injection-induced pumping is performed in a state where the vacuum / exhaust unit 700 is turned on to induce the introduction of the oxidizing agent into the reactor 200, Pumping for a second. The introduction of the induction pumping allows the oxidant to be fully injected into the reactor 200 to remain in sufficient quantities and is economical because it minimizes the amount of oxidant that does not participate in the reaction. Injection-induced pumping functions to prevent the oxidant from flowing backward, and in the absence of such injection-induced pumping, the oxidant may flow backward, resulting in poor coating efficiency and problems with the powder coating apparatus. This injection-induced pumping is one of the characteristic features of the present invention which is not present in a typical atomic layer deposition step. If the time of the injection induction pumping is too long, the oxidant may not sufficiently stay in the reactor 200, but may be exhausted through the exhaust port 220 to cause the loss of the oxidant. Taking this into consideration, the time for the injection induction pumping is set to a time (for example, 0.1 to 2 seconds) required for the oxidant to reach the interior of the reactor 200 in consideration of the operation capability of the control unit of the vacuum / good.

The oxidizing agent is held in the reactor 200 so that the coating source adsorbed on the surface of the powder reacts with the oxidizing agent to cause oxidation (S9). The oxidant in the reactor 200 serves to oxidize the coating source adsorbed on the surface of the powder, and the coating source adsorbed on the surface of the powder is oxidized and transformed into metal oxide. The holding time (reaction time) for the oxidation reaction is set in consideration of the content of the oxidizing agent remaining in the reactor 200, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, sufficient oxidation reaction may not occur. If the retention time is too long, sufficient oxidation reaction may occur but it may not be economical due to a long time consumption.

A process of pumping and removing the oxidizing agent remaining in the reactor 200 may be performed (S10). By pumping by the vacuum / vent unit 700, the oxidizing agent that does not react with the coating source and remains in the reactor 200 can be vented through the outlet 220. The vacuum / exhaust unit 700 is always on, so if the oxidant is to be removed by pumping, the pumping valve may be opened. The pumping time is set in consideration of the amount of the oxidizing agent remaining in the reactor 200, and it is suitably about 10 to 50 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the oxidizing agent. If the pumping time is too long, sufficient removal of the oxidizing agent may be accomplished, but it may not be economical due to a large amount of time.

The purge gas is injected into the reactor 200 to remove the unreacted remaining oxidizing agent (S11). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar), which does not chemically react with the powder and the coating source, may be used. The injection time of the purge gas is set in consideration of the content of the oxidizing agent remaining in the reactor 200 and the like, and is suitably about 1 to 120 seconds, for example. If the purge gas injection time is too short, it may be difficult to sufficiently remove the oxidizer. If the purge gas injection time is too long, sufficient removal of the oxidizer may be performed. However, Can be uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

After the supply of the purge gas is stopped, the purge gas remaining in the reactor 200 may be pumped and removed (S12). The purging gas remaining in the reactor 200 by pumping by the vacuum / exhaust unit 700 can be exhausted through the exhaust port 220. When the purge gas is to be pumped and removed by the vacuum / exhaust unit 700, the pumping valve may be kept open even after the purge gas is shut off. The pumping time is set in consideration of the amount of the purge gas remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the purge gas. If the pumping time is too long, the purge gas may be sufficiently removed, but it may not be economical due to a long time consumption.

The above steps S1 to S12 are performed once, and this is referred to as a one-atom layer deposition cycle. The processing time for each step in steps S1 to S12 can be set flexibly according to the surface area, powder type, etc. of the powder to be used.

<Example 4>

In order to coat the metal oxide on the powder, a characteristic atomic layer deposition sequence different from the sequence of general atomic layer deposition is applied, and the solid electrolyte for a lithium secondary battery manufactured by the method has properties suitable for use in a lithium secondary battery.

The coating source is supplied into the reactor 200 through which the powder is loaded through the process gas supply unit 400 (S1). The coating source is appropriately selected depending on the kind of metal oxide to be coated on the powder surface. The metal oxide is a material of a component different from the powder component, and the coating source is a precursor including a metal component of a metal oxide. The metal oxide is _{Al 2 O 3, SiO 2,} TiO 2, ZnO, MgO, ZrO _2, and the like, and the like. The injection time of the coating source is appropriately set in consideration of the surface area, weight, coating source species, etc. of the powder to be coated. For example, the injection time of the coating source is preferably set to about 0.1 to 20 seconds. If the injection time of the coating source is too short, a sufficient amount of the coating source is not injected and metal oxide particles not coated per atomic layer deposition cycle And if the injection time of the coating source is too long, the amount of the unreacted coating source (which remains uncoated on the powder surface) may increase, which may be uneconomical. The supply flow rate of the coating source is preferably about 1 to 1000 sccm.

The supply of the coating source is cut off, and injection induction pumping is performed so that the coating source can be completely injected into the reactor 200 (S2). The injection induction pumping is performed by the vacuum / exhaust unit 700 for a very short time (e.g., within 2 seconds) to allow the coating source supplied through the process gas supply unit 400 to be fully injected into the reactor 200 Pumping is effected. Preferably, the injection-induced pumping is performed at a rate of 0.1 &lt; RTI ID = 0.0 &gt; (%) &lt; / RTI & Allow pumping for ~ 2 seconds. The injection induction pumping is performed, so that the coating source is completely injected into the reactor 200 and remains in sufficient quantities, and the amount of unreacted coating source can be minimized, which is economical. Injection-induced pumping functions to prevent the coating source from flowing backward, and in the absence of such injection-induced pumping, the coating source may be countercurrent, resulting in poor coating efficiency and also problems with the powder coating apparatus. This injection-induced pumping is one of the characteristic features of the present invention which is not present in a typical atomic layer deposition step. If the time of the injection induction pumping is too long, the coating source can not sufficiently stay in the reactor 200, but may be vented through the outlet 220 to cause loss of the coating source. Taking this into consideration, the time of the injection induction pumping is set to a time (for example, 0.1 to 2 seconds) required for the coating source to reach the inside of the reactor 200 in consideration of the operation capability of the control unit of the vacuum / It is good.

The coating source is held in the reactor 200 so that the coating source is adsorbed on the surface of the powder (S3). The coating source in the reactor 200 is adsorbed on the surface of the powder, and the diffusion also occurs inside the powder. The holding time (reaction time) for adsorbing to the surface of the powder is set in consideration of the content of the coating source staying in the reactor 200 and the like, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, the time for the coating source to diffuse into the powder agglomerate is insufficient and only the particles located on the surface of the agglomerate can be coated, which is undesirable. If the retention time is too long, sufficient adsorption may occur Time consuming may not be economical.

The process of pumping and removing the coating source remaining in the reactor 200 may be performed (S4). By allowing pumping by the vacuum / exhaust unit 700, the coating source that is not adsorbed to the powder surface and remains in the reactor 200 can be exhausted through the outlet 220. Since the vacuum / exhaust unit 700 is always on, the pumping valve may be opened when the coating source is to be pumped and removed. The pumping time is set in consideration of the amount of the coating source remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, sufficient removal of the coating source may be difficult, and if the pumping time is too long, sufficient removal of the coating source may be accomplished, but it may not be economical due to time consuming.

A purge gas is injected into the reactor 200 to remove the remaining adsorbed coating source (S5). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar) which does not chemically react with the powder can be used. The injection time of the purge gas is set in consideration of the content of the coating source staying in the reactor 200, and is suitably about 1 to 120 seconds, for example. If the injection time of the purge gas is too short, it may be difficult to sufficiently remove the coating source. If the injection time of the coating source is too long, sufficient removal of the coating source may be performed. However, It is possible that the amount of consumption is large and it is uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

After the supply of the purge gas is stopped, the purge gas remaining in the reactor 200 may be pumped and removed (S6). The purging gas remaining in the reactor 200 by pumping by the vacuum / exhaust unit 700 can be exhausted through the exhaust port 220. When the purge gas is to be pumped and removed by the vacuum / exhaust unit 700, the pumping valve may be kept open even after the purge gas is shut off. The pumping time is set in consideration of the amount of the purge gas remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the purge gas. If the pumping time is too long, the purge gas may be sufficiently removed, but it may not be economical due to a long time consumption.

The oxidant is supplied into the reactor 200 (S7). The oxidizing agent is supplied into the reactor 200 through the process gas supply unit 400. Examples of the oxidizing agent include water vapor (H ₂ O), ozone (O ₃ ), and the like, which react with the coating source to cause oxidation. The time for injecting the oxidizing agent is set in consideration of the content of the coating source adsorbed on the surface of the powder, and is suitably about 0.1 to 20 seconds, for example. If the injection time of the oxidizing agent is too short, sufficient oxidation reaction can not occur. If the injection time of the oxidizing agent is too long, sufficient oxidation reaction may occur. However, since it is not economical due to a lot of time consuming and consumes the oxidizing agent, have. The supply flow rate of the oxidizing agent is preferably about 1 to 1000 sccm.

The oxidizing agent is held in the reactor 200 so that the coating source adsorbed on the surface of the powder reacts with the oxidizing agent to cause oxidation (S9). The oxidant in the reactor 200 serves to oxidize the coating source adsorbed on the surface of the powder, and the coating source adsorbed on the surface of the powder is oxidized and transformed into metal oxide. The holding time (reaction time) for the oxidation reaction is set in consideration of the content of the oxidizing agent remaining in the reactor 200, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, sufficient oxidation reaction may not occur. If the retention time is too long, sufficient oxidation reaction may occur but it may not be economical due to a long time consumption.

A process of pumping and removing the oxidizing agent remaining in the reactor 200 may be performed (S10). By pumping by the vacuum / vent unit 700, the oxidizing agent that does not react with the coating source and remains in the reactor 200 can be vented through the outlet 220. The vacuum / exhaust unit 700 is always on, so if the oxidant is to be removed by pumping, the pumping valve may be opened. The pumping time is set in consideration of the amount of the oxidizing agent remaining in the reactor 200, and it is suitably about 10 to 50 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the oxidizing agent. If the pumping time is too long, sufficient removal of the oxidizing agent may be accomplished, but it may not be economical due to a large amount of time.

The purge gas is injected into the reactor 200 to remove the unreacted remaining oxidizing agent (S11). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar), which does not chemically react with the powder and the coating source, may be used. The injection time of the purge gas is set in consideration of the content of the oxidizing agent remaining in the reactor 200 and the like, and is suitably about 1 to 120 seconds, for example. If the purge gas injection time is too short, it may be difficult to sufficiently remove the oxidizer. If the purge gas injection time is too long, sufficient removal of the oxidizer may be performed. However, Can be uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

After the supply of the purge gas is stopped, the purge gas remaining in the reactor 200 may be pumped and removed (S12). The purging gas remaining in the reactor 200 by pumping by the vacuum / exhaust unit 700 can be exhausted through the exhaust port 220. When the purge gas is to be pumped and removed by the vacuum / exhaust unit 700, the pumping valve may be kept open even after the purge gas is shut off. The pumping time is set in consideration of the amount of the purge gas remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the purge gas. If the pumping time is too long, the purge gas may be sufficiently removed, but it may not be economical due to a long time consumption.

The above steps S1 to S7 and S9 to S12 are performed once, and this is referred to as a one-atom layer deposition cycle. The process time for each step of S1 to S7 and S9 to S12 is determined according to the surface area of the powder, . &Lt; / RTI &gt;

&Lt; Example 5 >

In order to coat the metal oxide on the powder, a characteristic atomic layer deposition sequence different from the sequence of general atomic layer deposition is applied, and the solid electrolyte for a lithium secondary battery manufactured by the method has properties suitable for use in a lithium secondary battery.

The coating source is supplied into the reactor 200 through which the powder is loaded through the process gas supply unit 400 (S1). The coating source is appropriately selected depending on the kind of metal oxide to be coated on the powder surface. The metal oxide is a material of a component different from the powder component, and the coating source is a precursor including a metal component of a metal oxide. The metal oxide is _{Al 2 O 3, SiO 2,} TiO 2, ZnO, MgO, ZrO _2, and the like, and the like. The injection time of the coating source is appropriately set in consideration of the surface area, weight, coating source species, etc. of the powder to be coated. For example, the injection time of the coating source is preferably set to about 0.1 to 20 seconds. If the injection time of the coating source is too short, a sufficient amount of the coating source is not injected and metal oxide particles not coated per atomic layer deposition cycle And if the injection time of the coating source is too long, the amount of the unreacted coating source (which remains uncoated on the powder surface) may increase, which may be uneconomical. The supply flow rate of the coating source is preferably about 1 to 1000 sccm.

The coating source is held in the reactor 200 so that the coating source is adsorbed on the surface of the powder (S3). The coating source in the reactor 200 is adsorbed on the surface of the powder, and the diffusion also occurs inside the powder. The holding time (reaction time) for adsorbing to the surface of the powder is set in consideration of the content of the coating source staying in the reactor 200 and the like, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, the time for the coating source to diffuse into the powder agglomerate is insufficient and only the particles located on the surface of the agglomerate can be coated, which is undesirable. If the retention time is too long, sufficient adsorption may occur Time consuming may not be economical.

The process of pumping and removing the coating source remaining in the reactor 200 may be performed (S4). By allowing pumping by the vacuum / exhaust unit 700, the coating source that is not adsorbed to the powder surface and remains in the reactor 200 can be exhausted through the outlet 220. Since the vacuum / exhaust unit 700 is always on, the pumping valve may be opened when the coating source is to be pumped and removed. The pumping time is set in consideration of the amount of the coating source remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, sufficient removal of the coating source may be difficult, and if the pumping time is too long, sufficient removal of the coating source may be accomplished, but it may not be economical due to time consuming.

A purge gas is injected into the reactor 200 to remove the remaining adsorbed coating source (S5). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar) which does not chemically react with the powder can be used. The injection time of the purge gas is set in consideration of the content of the coating source staying in the reactor 200, and is suitably about 1 to 120 seconds, for example. If the injection time of the purge gas is too short, it may be difficult to sufficiently remove the coating source. If the injection time of the coating source is too long, sufficient removal of the coating source may be performed. However, It is possible that the amount of consumption is large and it is uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

After the supply of the purge gas is stopped, the purge gas remaining in the reactor 200 may be pumped and removed (S6). The purging gas remaining in the reactor 200 by pumping by the vacuum / exhaust unit 700 can be exhausted through the exhaust port 220. When the purge gas is to be pumped and removed by the vacuum / exhaust unit 700, the pumping valve may be kept open even after the purge gas is shut off. The pumping time is set in consideration of the amount of the purge gas remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the purge gas. If the pumping time is too long, the purge gas may be sufficiently removed, but it may not be economical due to a long time consumption.

The oxidant is supplied into the reactor 200 (S7). The oxidizing agent is supplied into the reactor 200 through the process gas supply unit 400. Examples of the oxidizing agent include water vapor (H ₂ O), ozone (O ₃ ), and the like, which react with the coating source to cause oxidation. The time for injecting the oxidizing agent is set in consideration of the content of the coating source adsorbed on the surface of the powder, and is suitably about 0.1 to 20 seconds, for example. If the injection time of the oxidizing agent is too short, sufficient oxidation reaction can not occur. If the injection time of the oxidizing agent is too long, sufficient oxidation reaction may occur. However, since it is not economical due to a lot of time consuming and consumes the oxidizing agent, have. The supply flow rate of the oxidizing agent is preferably about 1 to 1000 sccm.

The supply of the oxidant is shut off, and injection induction pumping is performed so that the oxidant can be completely injected into the reactor 200 (S8). The injection induction pumping is pumped by the vacuum / exhaust unit 700 for a very short time (e.g., within 2 seconds) to allow the oxidant fed through the process gas supply unit 400 to be fully injected into the reactor 200 And preferably the injection-induced pumping is performed in a state where the vacuum / exhaust unit 700 is turned on to induce the introduction of the oxidizing agent into the reactor 200, Pumping for a second. The introduction of the induction pumping allows the oxidant to be fully injected into the reactor 200 to remain in sufficient quantities and is economical because it minimizes the amount of oxidant that does not participate in the reaction. Injection-induced pumping functions to prevent the oxidant from flowing backward, and in the absence of such injection-induced pumping, the oxidant may flow backward, resulting in poor coating efficiency and problems with the powder coating apparatus. This injection-induced pumping is one of the characteristic features of the present invention which is not present in a typical atomic layer deposition step. If the time of the injection induction pumping is too long, the oxidant may not sufficiently stay in the reactor 200, but may be exhausted through the exhaust port 220 to cause the loss of the oxidant. Taking this into consideration, the time for the injection induction pumping is set to a time (for example, 0.1 to 2 seconds) required for the oxidant to reach the interior of the reactor 200 in consideration of the operation capability of the control unit of the vacuum / good.

The oxidizing agent is held in the reactor 200 so that the coating source adsorbed on the surface of the powder reacts with the oxidizing agent to cause oxidation (S9). The oxidant in the reactor 200 serves to oxidize the coating source adsorbed on the surface of the powder, and the coating source adsorbed on the surface of the powder is oxidized and transformed into metal oxide. The holding time (reaction time) for the oxidation reaction is set in consideration of the content of the oxidizing agent remaining in the reactor 200, and is suitably about 5 to 120 seconds, for example. If the retention time is too short, sufficient oxidation reaction may not occur. If the retention time is too long, sufficient oxidation reaction may occur but it may not be economical due to a long time consumption.

A process of pumping and removing the oxidizing agent remaining in the reactor 200 may be performed (S10). By pumping by the vacuum / vent unit 700, the oxidizing agent that does not react with the coating source and remains in the reactor 200 can be vented through the outlet 220. The vacuum / exhaust unit 700 is always on, so if the oxidant is to be removed by pumping, the pumping valve may be opened. The pumping time is set in consideration of the amount of the oxidizing agent remaining in the reactor 200, and it is suitably about 10 to 50 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the oxidizing agent. If the pumping time is too long, sufficient removal of the oxidizing agent may be accomplished, but it may not be economical due to a large amount of time.

The purge gas is injected into the reactor 200 to remove the unreacted remaining oxidizing agent (S11). The purge gas is supplied into the reactor 200 through the process gas supply unit 400. As the purge gas, an inert gas such as nitrogen (N ₂ ) or argon (Ar), which does not chemically react with the powder and the coating source, may be used. The injection time of the purge gas is set in consideration of the content of the oxidizing agent remaining in the reactor 200 and the like, and is suitably about 1 to 120 seconds, for example. If the purge gas injection time is too short, it may be difficult to sufficiently remove the oxidizer. If the purge gas injection time is too long, sufficient removal of the oxidizer may be performed. However, Can be uneconomical. The supply flow rate of the purge gas is preferably about 200 to 1000 sccm.

After the supply of the purge gas is stopped, the purge gas remaining in the reactor 200 may be pumped and removed (S12). The purging gas remaining in the reactor 200 by pumping by the vacuum / exhaust unit 700 can be exhausted through the exhaust port 220. When the purge gas is to be pumped and removed by the vacuum / exhaust unit 700, the pumping valve may be kept open even after the purge gas is shut off. The pumping time is set in consideration of the amount of the purge gas remaining in the reactor 200, and is suitably about 5 to 30 seconds, for example. If the pumping time is too short, it may be difficult to sufficiently remove the purge gas. If the pumping time is too long, the purge gas may be sufficiently removed, but it may not be economical due to a long time consumption.

The above-described steps S1 and S3 to S12 are performed once, and this is referred to as a one-atom layer deposition cycle. The processing time for each step in steps S1 and S3 to S12 can be set flexibly according to the surface area of the powder to be used, have.

The above-described atomic layer deposition sequence is performed in a plurality of cycles to obtain a core-shell structure powder. The solid electrolyte powder for a lithium secondary battery thus produced has a core and a core-shell structure in which a metal oxide surrounds the surface of the core to form a shell. For example, the solid electrolyte powder for a lithium secondary battery has a structure including a nanostructure constituting the core and a metal oxide layer different from the material forming the nanostructure in at least a part of the nanostructure. The thickness of the metal oxide forming the shell can be adjusted according to the number of cycles. It is preferable that the metal oxide is coated to have a thickness of 0.1 to 10 nm considering that it is used as a solid electrolyte of a lithium secondary battery.

The core can be made of nanostructures such as nanowires, porous materials, nanorods, nanotubes, nanosheets, hollows, and yoke-shells.

The nanostructure forming the core is a particle used as a solid electrolyte of a lithium secondary battery, and Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te ₂ O ₁₂ , Li ₃ Lu ₃ Te ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Ta ₂ O ₁₂ , Li ₅ Nd ₃ Sb ₂ O ₁₂ , Li _{5 . 5} La ₃ Nb _{1 . 75} In _{0 . 25} O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _{0 . 5} Ta _{1 . 5} O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _0.5 Ba _0.5 La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₇ La ₃ Ta ₂ O _13, and Li ₇ La ₃ Ta ₂ O ₁₃ .

The material forming the core and the material forming the shell are preferably different.

In the chemical coating method such as the sol-gel method, it is difficult to uniformly coat the 1 nm-thick polar thin film, and it is difficult to control the coating speed of the material surface, so that the coating is unevenly formed over the whole particles and a uniform coating layer is formed It is difficult to control the thickness of the coating layer, so that it is difficult to form a coating layer having a uniform thickness for each coating process and it is difficult to finely coat the coating layer with a thickness of several nanometers have. However, according to the present invention, it is possible to uniformly coat the powder with a metal oxide of 1 nm or less, to easily control the coating speed, to uniformly form the coating on the whole particles, Uniform coating is possible and the thickness of the coating layer can be controlled, so that a coating layer having a uniform thickness can be formed in each coating process. In addition, it is possible to prevent the backflow of the supplied raw material by performing the injection induction pumping after supplying the raw material such as the coating source and the oxidizing agent to the reactor 200, to improve the coating efficiency, and to reduce the raw material have.

The following measurements can be made to ascertain the performance of the solid electrolyte for a lithium secondary battery manufactured by the above-described method.

1. Test for inhibition of volume expansion due to coating on solid electrolyte.

2. Structural stability testing by measuring the component ratio present in the solid electrolyte.

3. Testing the thickness of the interface (SEI) layer produced in the solid electrolyte.

4. Impedance measurement test at solid electrolyte interface.

The volume expansion inhibition test is a test to determine how much the solid electrolyte can suppress the volume expansion when it absorbs lithium ions through charge and discharge. As a typical example, in the case of silicon, lithium tends to enter the silicon at the time of charging and expand to a volume of about 400%. As a result, the coupling between the solid electrolyte and the current collector is reduced and the battery efficiency is reduced. Thus, atomic layer deposition can form a more dense coating layer than conventional coatings to prevent volume expansion and achieve better battery performance.

Structural stability testing is an experiment to determine how to prevent the formation of structural instability by dissolving one or more of the constituents of the solid electrolyte through the coating. When a coating layer is formed by a rotary atomic layer deposition method, particles can be coated more densely and completely than by forming a coating layer through other conventional methods. Thereby ensuring structural stability and expecting better battery life.

The thickness measurement of the interface (SEI) layer is an experiment to see how thick a SEI layer is formed during repeated charge and discharge of the battery. The SEI layer is formed at the new surface created by volume expansion during charge / discharge. The SEI layer thus formed is thicker than a certain thickness, which lowers the permeability of the lithium ion, thereby reducing the overall battery performance. In order to solve this problem, it is expected that an artificial SEI layer is formed as a metal oxide film and that the film has a higher strength property than the existing SEI layer, thereby preventing a new interface from being formed, thereby preventing the increase in the thickness of the entire SEI layer. These results can be confirmed by using TEM.

Finally, there is a method of measuring the impedance of the solid electrolyte interface. Generally, when the battery is charged and discharged, a voltage drop occurs due to the impedance of the interface, resulting in a large energy loss. However, if a uniform coating film is formed using a rotary atomic layer deposition method, the performance of the battery can be improved by reducing the impedance value.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

100: vacuum chamber 110: one shaft
120: other shaft 200: reactor
210: filter member 220: outlet
300: rotation unit 310: rotation drive member
320: rotation control means 400: process gas supply unit
500: heater unit 510: heater
520: Heater control means 600: Stirring means
610: Blade 700: Vacuum / exhaust unit

Claims (15)

A process gas supply unit for supplying a process gas into the reactor; and a control unit for controlling the rotation of the reactor around the reactor, And a vacuum / exhaust unit for evacuating the inside of the vacuum chamber or for evacuating the process gas from the vacuum chamber, the method comprising the steps of: A method of producing a powder for use in a solid electrolyte for a battery,
(a) placing a powder as a source of a solid electrolyte for a lithium secondary battery into a reactor;
(b) a vacuum / exhaust unit is arranged to maintain a vacuum state in the vacuum chamber so that the pressure in the vacuum chamber is lower than an atmospheric pressure, and a heater is controlled through a heater control means of the heater unit to set a temperature in the vacuum chamber And actuating the rotating unit to cause the reactor to periodically rotate;
(c) supplying a coating source into the reactor through the process gas supply unit;
(d) injecting a purge gas into the reactor through the process gas supply unit to remove the remaining coating source;
(e) supplying an oxidant into the reactor through the process gas supply unit; And
(f) injecting a purge gas into the reactor through the process gas supply unit to remove residual oxidizing agent,
The atomic layer deposition sequence of the step (c) to the step (f) is performed a plurality of cycles to prepare a powder coated with a metal oxide,
Wherein the coating source is a precursor comprising a metal component of the metal oxide,
Wherein the metal oxide is coated to a thickness of 0.1 to 10 nm. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method of claim 1, further comprising, between step (c) and step (d)
Interrupting the supply of the coating source to prevent the coating source from flowing backward and performing injection induced pumping to induce injection into the reactor; And
Further comprising maintaining the coating source in the reactor with the pumping valve closed to cause the coating source to be adsorbed to the surface of the powder. &Lt; Desc / Clms Page number 19 &gt;
3. The method of claim 2, wherein the vacuum / exhaust unit is always on during atomic layer deposition,
Pumping is controlled through the opening and closing of the pumping valve,
Wherein the step (c), the step (d), and the step (f) are performed such that the pumping valve is controlled to be open,
Wherein the step of causing the coating source to be adsorbed on the surface of the powder is controlled so that the pumping valve is closed.
4. The method of claim 3, wherein the injection induction pumping is performed by pumping for 0.1 to 2 seconds even after shutting off the supply of the coating source while the vacuum / evacuation unit is on to induce the introduction of the coating source into the reactor Wherein the solid electrolytic powder for lithium secondary batteries is a lithium secondary battery.
4. The method of claim 3, further comprising: after the step of causing the coating source to adsorb to the surface of the powder, after the step (d), pumping with the pumping valve open before removing the coating source remaining in the reactor,
Further comprising the step of removing purging gas remaining in the reactor by pumping after the step (d) with the pumping valve open before step (e)
Further comprising the step of purging the purging gas remaining in the reactor after the step (f) with the pumping valve being open, to remove the purge gas remaining in the reactor.
[6] The method of claim 5, wherein in the step (c), the injection time of the coating source is set to 0.1 to 20 seconds,
The time to hold the coating source in the reactor in the step of causing the coating source to adsorb to the surface of the powder is in the range of 5 to 120 seconds,
The step of pumping and removing the coating source remaining in the reactor is set to 5 to 30 seconds,
In the step (d), the purge gas injection time is set to 1 to 120 seconds,
The step of purging the purging gas remaining in the reactor while the pumping valve is opened after the step (d) after the step (e) is set to 5 to 30 seconds,
In the step (e), the injection time of the oxidant is set to 0.1 to 20 seconds,
In the step (f), the purge gas injection time is set to 1 to 120 seconds,
Wherein the step of purging the purge gas remaining in the reactor while the pumping valve is opened after the step (f) is set to 5 to 30 seconds.
The method according to claim 1, further comprising, between the step (e) and the step (f)
Shutting off the supply of the oxidant to prevent the oxidant from flowing backward and performing injection-induced pumping to induce the injection into the reactor; And
Further comprising the step of holding the oxidizing agent in the reactor while the pumping valve is closed so that the coating source adsorbed on the surface of the powder reacts with the oxidizing agent to oxidize the powder. Way.
8. The method of claim 7, wherein the vacuum / exhaust unit is always on during atomic layer deposition,
Pumping is controlled through the opening and closing of the pumping valve,
Wherein the steps (c) to (e), the injection induction pumping step and the step (f) are controlled so that the pumping valve is opened,
Wherein the step of oxidizing is controlled to close the pumping valve. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
9. The method of claim 8, wherein the injection-induced pumping comprises pumping for 0.1 to 2 seconds even after shutting off the supply of the oxidant while the vacuum / exhaust unit is on to induce the introduction of the oxidant into the reactor Wherein the solid electrolytic powder for lithium secondary batteries is a lithium secondary battery.
The method as claimed in claim 8, further comprising the step of purging the purging valve after the step (d) and removing the purge gas remaining in the reactor before the step (e)
Further comprising the step of pumping with the pumping valve open prior to step (f) after the step of causing the oxidation to remove the oxidizing agent remaining in the reactor,
Further comprising the step of purging the purging gas remaining in the reactor after the step (f) with the pumping valve being open, to remove the purge gas remaining in the reactor.
11. The method of claim 10, wherein the injection time of the coating source in step (c) is set to 0.1 to 20 seconds,
In the step (d), the purge gas injection time is set to 1 to 120 seconds,
The step of purging the purging gas remaining in the reactor while the pumping valve is opened after the step (d) after the step (e) is set to 5 to 30 seconds,
In the step (e), the injection time of the oxidant is set to 0.1 to 20 seconds,
Wherein the step of performing the oxidation is set to 5 to 120 seconds,
The step of pumping and removing the oxidizing agent remaining in the reactor is set to 10 to 50 seconds,
In the step (f), the purge gas injection time is set to 1 to 120 seconds,
Wherein the step of purging the purge gas remaining in the reactor while the pumping valve is opened after the step (f) is set to 5 to 30 seconds.
The method of claim 1, wherein the powder that is a source of the solid electrolyte for the lithium secondary battery is selected from the group consisting of Li ₃ Nd ₃ Te ₂ O ₁₂ , Li ₃ Gd ₃ Te ₂ O ₁₂ , Li ₃ Tb ₃ Te ₂ O ₁₂ , Li ₃ Er ₃ Te _{2 O 12, Li 3 Lu 3 Te} 2 O 12, Li 5 La 3 Nb 2 O 12, Li 5 La 3 Ta 2 O 12, Li 5 Nd 3 Ta 2 O 12, Li 5 Nd 3 Sb 2 O 12, Li 5 _{. 5} La ₃ Nb _{1 . 75} In _{0 . 25} O ₁₂ , Li ₆ MgLa ₂ Ta ₂ O ₁₂ , Li ₆ BaLa ₂ Nb ₂ O ₁₂ , Li ₆ BaLa ₂ Nb _{0 . 5} Ta _{1 . 5} O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₆ La ₃ SnSbO ₁₂ , Li ₆ SrLa ₂ Nb ₂ O ₁₂ , Li ₆ Sr _0.5 Ba _0.5 La ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O _{12 , Li 7 La 3 Ta 2 O} 13 and Li ₇ La ₃ Ta ₂ O ₁₃ process for producing a lithium secondary battery, the solid electrolyte powder comprising the one or more materials that are selected from.
The method of claim 1, wherein in step (a), a bead is charged into the reactor together with a powder that is a source of the solid electrolyte for a lithium secondary battery,
The beads having a diameter in the range of 0.01 to 1 mm are used,
Wherein the beads and the powder as a source of the solid electrolyte for the lithium secondary battery have a weight ratio of 3 to 20: 1 in the reactor. delete delete

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