JP2019136679A - Composite particle production apparatus and production method - Google Patents

Abstract

To provide a composite particle production apparatus and production method which can synthesize composite particles of dissimilar materials by collective processing.SOLUTION: The apparatus comprises: a chamber; a plasma generator which is arranged in the chamber and generates plasma; a first material feeding device which is connected to the chamber and feeds a first material into the chamber through a first material supply port; a second material feeding device which is connected to the chamber and feeds a second material into the chamber through a second material supply port; and a recovery system which is connected to the chamber and recovers composite particles discharged from the chamber, and the apparatus produces composite particles from the first and second materials fed from the first and second material feeding devices. The plasma generator generates, at a central part of the chamber, a plasma high temperature part having plasma having a higher temperature than peripheral parts, and is installed so that the first material supply port of the first material feeding device feeds the first material to the plasma high temperature part and the second material supply port of the second material feeding device feeds the second material to a part other than the plasma high temperature part.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composite particle manufacturing apparatus and a manufacturing method in which large particles and small particles are combined.

  Conventionally, composite particles having different particle sizes have been manufactured by separately manufacturing large particles and small particles and mixing them. For example, Japanese Unexamined Patent Publication No. 2003-275281 (Patent Document 1) of Conventional Example 1 discloses a method for producing drug-containing composite particles. In Conventional Example 1, small particles (0.01 μm or more and 500 μm or less in diameter) are attached to the surfaces of large particles (1 μm or more and 500 μm or less in diameter) using a fluidized bed dry granulation method or a dry mechanical particle compounding method. I am letting.

  In addition, for example, in the method for producing spherical composite particles disclosed in Japanese Patent Application Laid-Open No. 2005-342615 (Patent Document 2) of Conventional Example 2, the raw material particles are introduced into the plasma, and the fine particles of the raw material are introduced onto the surface of the spherical particles. Spherical composite particles to be dispersed and attached are formed.

  FIG. 4 is a schematic cross-sectional view of a spherical composite particle manufacturing apparatus using the thermal plasma of Conventional Example 2. The spherical composite particle manufacturing apparatus includes a chamber 201, a plasma generation unit 203 that generates plasma in the chamber 201, and a raw material supply unit 204 that introduces raw material particles into the plasma 202. The chamber 201 has a region 210 in which small particles are dispersed and attached to the surface of the spherical particles. Furthermore, a recovery means 206 is provided for recovering spherical particles with small particles dispersed and adhered from inside the chamber 201. By introducing the raw material particles into the plasma 202 and melting and evaporating the surface thereof, the raw material particles are brought close to a spherical shape, and a field in which the raw material vapor is mixed around the spherical particles is formed. Further, a reaction / quenching gas that reacts with the raw material vapor is blown into the mixture field 220 of the spherical particles and the raw material vapor after passing through the plasma 202 while rapidly cooling the raw material vapor. As a result, the raw material vapor is condensed while reacting with the reaction / quenching gas to form small particles having a diameter smaller than that of the spherical particles, and the small particles are dispersed and adhered to the surface of the spherical particles to form spherical composite particles. ing.

JP 2003-275281 A JP 2005-342615 A

  In the method for producing composite particles of Conventional Example 1 described above, many separate processes such as a process for producing large particles, a process for producing small particles, and a process for mixing these large and small particles are required. For this reason, the manufacturing cost of a composite particle becomes high.

  Moreover, in the manufacturing method of the spherical composite particles of Conventional Example 2 described above, since the small particles generated by evaporating the surface of the raw material are dispersed and adhered to the surface of the large particles, the materials of the large particles and the small particles are the same. turn into.

  In view of the above-described conventional problems, an object of the present invention is to provide a composite particle manufacturing apparatus and a manufacturing method capable of efficiently synthesizing composite particles by a collective process and capable of synthesizing composite particles even from different materials.

In order to achieve the above object, a composite particle production apparatus according to one aspect of the present invention comprises:
A chamber;
A plasma generating device arranged in the chamber to generate plasma;
A first material supply device connected to the chamber and supplying a first material into the chamber from a first material supply port;
A second material supply device connected to the chamber and supplying a second material into the chamber from a second material supply port;
A recovery device connected to the chamber and recovering the composite particles discharged from the chamber;
With
An apparatus for producing composite particles from the first and second materials supplied from the first and second material supply devices by the plasma generated in the chamber,
The plasma generator generates a plasma high-temperature part having plasma at a higher temperature than the peripheral part in the central part of the chamber,
The first material supply port of the first material supply device is installed so that the first material is supplied to the plasma high temperature part, and the second material supply port of the second material supply device Is installed so that the second material is supplied to a place other than the plasma high temperature part.

In order to achieve the above object, a method for producing composite particles according to another aspect of the present invention is to generate a plasma high temperature part having a plasma at a higher temperature than the peripheral part at the center part of the chamber by a plasma generator installed in the chamber. ,
A first material is charged into the plasma high temperature part, and the first material evaporates or vaporizes into the material gas of the first material when passing through the region of the plasma high temperature part, and At the moment when the material gas of the first material escapes from the region of the plasma high temperature part, the material gas of the first material is rapidly cooled and solidified,
A second material is introduced into a place other than the plasma high temperature part, and the second material is left as it is or is melted, spheroidized and solidified, and the second material is solidified on the solidified surface of the second material. A film of one material is formed, or composite particles having fine particles attached to the surface are synthesized.

  According to the composite particle manufacturing apparatus and the composite particle manufacturing method according to the present invention, the first material is supplied to the plasma high temperature part, and the second material is supplied from a place other than the plasma high temperature part. As a result, the second material remains in the same shape as before the supply or is melted and spheroidized. On the other hand, the first material is evaporated or vaporized by plasma to become a material gas. When the material gas of the first material is rapidly cooled, composite particles in which a film or fine particles made of the first material are attached to the surface of the spherical particles made of the second material can be formed. . Therefore, it is possible to provide a composite particle manufacturing apparatus and a manufacturing method that can synthesize composite particles on which nano-level coatings / fine particles of different materials are formed and adhered by batch processing and can be manufactured at low cost.

It is a schematic longitudinal cross-sectional view of the composite particle manufacturing apparatus which concerns on 1st Embodiment. FIG. 2 is a schematic cross-sectional plan view of the composite particle manufacturing apparatus according to the first embodiment, viewed from the AA direction in FIG. 1. It is a process flowchart of the composite particle manufacturing method which concerns on 1st Embodiment. It is a schematic diagram of the existence probability distribution of the plasma by the arc discharge of 1 period when the frequency of the alternating current power applied to the electrode applied in the composite particle manufacturing apparatus which concerns on 1st Embodiment is changed. It is a schematic sectional drawing of the composite particle manufacturing apparatus of the prior art example 2.

The composite particle manufacturing apparatus according to the first aspect includes a chamber,
A plasma generating device arranged in the chamber to generate plasma;
A first material supply device connected to the chamber and supplying a first material into the chamber from a first material supply port;
A second material supply device connected to the chamber and supplying a second material into the chamber from a second material supply port;
A recovery device connected to the chamber and recovering the composite particles discharged from the chamber;
With
An apparatus for producing composite particles from the first and second materials supplied from the first and second material supply devices by the plasma generated in the chamber,
The plasma generator generates a plasma high-temperature part having plasma at a higher temperature than the peripheral part in the central part of the chamber,
The first material supply port of the first material supply device is installed so that the first material is supplied to the plasma high temperature part, and the second material supply port of the second material supply device Is installed so that the second material is supplied to a place other than the plasma high temperature part.

  In the composite particle manufacturing apparatus according to the second aspect, in the first aspect, the plasma high temperature part may have a plasma existence probability of 0.5 or more.

In the composite particle manufacturing apparatus according to the third aspect, in the first or second aspect, the plasma generation apparatus includes:
A plurality of electrodes connected to the chamber and having a tip projecting into the chamber to generate the plasma;
AC power supplies connected to the plurality of electrodes, respectively, and supplying AC power having different phases,
With
The plasma may be generated by supplying AC power having different phases to each of the plurality of electrodes from the AC power source to generate arc discharge between the electrodes.

  The composite particle manufacturing apparatus according to a fourth aspect is the above-described third aspect, wherein the first material supply port is an in-plane defined by the tip portions of the plurality of electrodes when viewed from vertically above. You may arrange | position in the center part or the front-end | tip part of the said electrode.

  In the composite particle production apparatus according to the fifth aspect, in the third or fourth aspect, the second material supply port is disposed at a position between the adjacent electrodes as viewed from vertically above. Also good.

  In the composite particle manufacturing apparatus according to the sixth aspect, in any one of the third to fifth aspects, in the AC power supply that supplies the plurality of electrodes, the frequency of the AC power is greater than 60 Hz and 360 Hz or less. It may be.

In the composite particle manufacturing method according to the seventh aspect, a plasma high temperature part having plasma higher in temperature than the peripheral part is generated in the central part of the chamber by a plasma generator installed in the chamber,
A first material is charged into the plasma high temperature part, and the first material evaporates or vaporizes into the material gas of the first material when passing through the region of the plasma high temperature part, and At the moment when the material gas of the first material escapes from the region of the plasma high temperature part, the material gas of the first material is rapidly cooled and solidified,
A second material is introduced into a place other than the plasma high temperature part, and the second material is left as it is or is melted, spheroidized and solidified, and the second material is solidified on the solidified surface of the second material. A film of one material is formed, or composite particles having fine particles attached to the surface are synthesized.

  In the composite particle manufacturing method according to an eighth aspect, in the seventh aspect, the plasma high temperature part may have a plasma existence probability of 0.5 or more.

In the composite particle manufacturing method according to a ninth aspect, in the seventh or eighth aspect, the plasma generation apparatus comprises:
A plurality of electrodes connected to the chamber and having a tip projecting into the chamber to generate the plasma;
AC power supplies connected to the plurality of electrodes, respectively, and supplying AC power having different phases,
With
The plasma may be generated by supplying AC power having different phases from the AC power source to the plurality of electrodes, and generating arc discharge between the electrodes.

  The composite particle manufacturing method according to a tenth aspect is the above ninth aspect, wherein the first material is viewed from vertically above, and an in-plane central portion defined by tip portions of the plurality of electrodes. Or you may supply from the front-end | tip part of the said electrode.

  In the composite particle manufacturing method according to an eleventh aspect, in the ninth or tenth aspect, the second material may be supplied from a position between the adjacent electrodes as viewed from vertically above.

  In the composite particle manufacturing method according to a twelfth aspect according to any one of the ninth to eleventh aspects, in the AC power supply that supplies AC power to the plurality of electrodes, the frequency of the AC power is higher than 60 Hz. It may be 360 Hz or less.

  In the composite particle manufacturing method according to the thirteenth aspect, in any one of the seventh to twelfth aspects, the supply amount of the first material may be smaller than the supply amount of the second material.

  In the composite particle production method according to a fourteenth aspect, in any one of the seventh to thirteenth aspects, an average particle diameter of the first material before being supplied to the plasma is 0.5 μm or more and 500 μm or less, The average particle diameter of the second material before being supplied to the plasma may be not less than 0.5 μm and not more than 5000 μm.

  In the composite particle manufacturing method according to a fifteenth aspect, in the fourteenth aspect, an average particle diameter of the first material after passing through the plasma is 5 nm or more and 300 nm or less, and the first particle after passing through the plasma is used. The average particle diameter of the second material may be not less than 0.3 μm and not more than 5000 μm.

  In the composite particle manufacturing method according to a sixteenth aspect, in the fourteenth aspect, an average particle diameter of the second material after passing through the plasma is 0.3 μm or more and 5000 μm or less, and after passing through the plasma, The average thickness of the film of the first material formed on the surface of the second material may be 5 nm or more and 1000 nm or less.

  Hereinafter, a composite particle manufacturing apparatus and a composite particle manufacturing method according to an embodiment will be described in detail with reference to the drawings.

(First embodiment)
FIG. 1 is a schematic longitudinal sectional view of the composite particle manufacturing apparatus according to the first embodiment. FIG. 2 is a schematic cross-sectional plan view of the composite particle manufacturing apparatus according to the first embodiment, as viewed from the direction AA in FIG. FIG. 3 is a process flowchart of the composite particle manufacturing method according to the first embodiment. For convenience, one direction in the horizontal plane is defined as the x direction, and the vertically upward direction is defined as the z direction. As an example, an example of producing composite particles in which nanometer-order solid electrolyte Li ₃ PS ₄ is dispersed and attached to the surface of graphite will be described with reference to FIGS.

<Composite particle production equipment>
The composite particle manufacturing apparatus 40 according to the first embodiment includes at least a reaction chamber 1 as an example of a chamber, a first material supply apparatus 10, a second material supply apparatus 11, and an arc discharge to generate plasma. For example, a plurality of electrodes 4, a gas supply pipe 14 connected to the electrodes 4, and a composite particle recovery unit 3 as an example of a recovery device for recovering the generated composite particles. It is composed. The first material supply device 10 and the second material supply device 11 are disposed below the bottom of the reaction chamber 1 and supply the first material and the second material into the reaction chamber 1, respectively. The composite particle recovery unit 3 is connected to the upper end of the reaction chamber 1 and is exhausted by the pump 22 through the pipe 20 to recover the composite particles generated in the reaction chamber 1. By this composite particle manufacturing apparatus, arc discharge is generated in the reaction chamber 1, and composite particles are manufactured from the first material particles and the second material particles supplied from the first and second material supply apparatuses.

  According to this composite particle manufacturing apparatus, the first material is supplied to the plasma high temperature part, and the second material is supplied from a place other than the plasma high temperature part. As a result, the second material remains in the same shape as before the supply or is melted and spheroidized. On the other hand, the first material is evaporated or vaporized by plasma to become a material gas. When the material gas of the first material is rapidly cooled, composite particles in which a film or fine particles made of the first material are attached to the surface of the spherical particles made of the second material can be formed. .

  Hereinafter, the configuration of the composite particle manufacturing apparatus 40 will be described in detail.

<Reaction chamber>
The reaction chamber 1 is an example of a chamber and extends along the upper side from the lower side in the vertical direction.

<Plasma generator>
The plasma generator generates a plasma high temperature portion having plasma at a temperature higher than that of the peripheral portion in the central portion of the chamber in the reaction chamber 1. The plasma high-temperature portion is a region having high-temperature plasma and having a plasma existence probability of 0.5 or more. As this plasma generator, for example, there are a plurality of electrodes 4, and AC power is applied between the electrodes 4 to generate arc discharge to generate plasma. The plurality of electrodes 4 are arranged at predetermined intervals on the side part of the central part of the reaction chamber 1 so that the tips protrude inside. The plurality of electrodes 4 may be two or more electrodes 4. For example, a pair of electrodes 4 arranged opposite to each other via the central portion of the reaction chamber 1 may be included. Further, by applying AC power between two or three or more electrodes 4, arc discharge can be generated in the central portion of the reaction chamber 1 between the electrodes 4 to generate plasma. In the case of FIG. 2, six electrodes 4 are arranged radially so that adjacent electrodes 4 form an angle of 60 ° when viewed from the center in the xy plane. In addition, it is not restricted to the example of FIG. 2, What is necessary is just at least 2 electrode 4. FIG. Plasma is generated in the reaction chamber 1 by the plurality of electrodes 4, and the first material particles 30 supplied from the first material supply device 10 can be evaporated and vaporized by the generated plasma.
In addition, in the plane defined by the tip portions of a plurality of electrodes as viewed from above vertically, plasma at a higher temperature than that between adjacent electrodes that are peripheral portions at the center portion between the opposing electrodes or the tip portion of the electrodes. It is considered that a “plasma high temperature portion” is generated in which the phenomenon occurs. As shown in FIG. 4, this “plasma high temperature portion” is a region having plasma having a temperature higher than that of the peripheral portion in the central portion of the chamber as described above. Specifically, the “plasma high temperature part” has a plasma existence probability of 0.5 or more and has high temperature plasma. On the other hand, it can be considered that plasma is not generated at a position between adjacent electrodes as viewed from above, or only plasma having a temperature lower than that of the central portion is present.

  The plurality of electrodes 4 are connected to AC power supplies 5 for supplying electric powers having different phases, and 60 Hz AC voltages whose phases are shifted by 60 °, for example, can be respectively applied. Each electrode 4 is independently movable back and forth in the radiation direction with respect to the center of the reaction chamber 1 by an electrode driving device 4a composed of a motor or the like.

<First material supply device and second material supply device>
The first material supply device 10 and the second material supply device 11 are connected to the reaction chamber 1 by the first material supply tube 10a and the second material supply tube 11a. First material particles 30 and second material particles 31 from the first material supply device 10 and second material supply device 11, and first material supply pipe 10 a and second material from the bottom side of the reaction chamber 1. It supplies in the reaction chamber 1 through the supply pipe | tube 11a. The first material supply pipe 10a and the second material supply pipe 11a are erected so as to extend vertically upward from below from the bottom of the reaction chamber 1 to the vicinity of the center. As shown in FIG. 2, the first material supply port 12 of the first material supply pipe 10 a has a central portion or an electrode in the plane defined by the tip of the electrode 4 when viewed from vertically above (z direction). 4 is arranged at a position opposite to the tip of 4. In addition, the first material supply port 12 is disposed at a position corresponding to a vertically lower portion with respect to a position facing the center portion in the plane or the tip portion of the electrode 4 when viewed from the direction perpendicular to the vertical direction. Further, the second material supply port 13 of the second material supply pipe 11a is disposed between the adjacent electrodes 4 when viewed from vertically above (z direction). In other words, the second material supply port 13 of the second material supply pipe 11 a is disposed between two adjacent first material supply ports 12. Further, the second material supply port 13 is disposed at a corresponding position vertically below the position between the adjacent electrodes 4 when viewed from the direction perpendicular to the vertical direction.

<Composite particle production method>
Hereinafter, a method for producing composite particles by the composite particle production apparatus will be described with reference to the process flowchart of FIG.

(Step S1) The material is placed and vacuumed.
First, the first material particles 30 and the second material particles 31 are installed in the first material supply device 10 and the second material supply device 11. Next, the inside of the reaction chamber 1, the composite particle recovery unit 3, and the first material supply device 10 and the second material supply device 11 are exhausted to, for example, several tens of Pa by the pump 22. Reduce the effect of oxygen. In the case of a material that deteriorates in the air, the material may be installed in an inert atmosphere.

(Step S2) Gas introduction and pressure adjustment are performed.
Next, from each of the plurality of gas supply devices 27 to the first material supply device 10 and the second material supply device 11 and the gas supply pipe 14 connected to the electrode 4 through the flow rate regulator 26, respectively. Supply gas while adjusting the flow rate. The supplied gas is adjusted to a predetermined pressure by a pressure adjusting valve 21 attached to the front stage of the pump 22.

In the first example of the first embodiment, as an example, composite particles having nanometer-order Li ₃ PS ₄ dispersed on the surface of graphite are produced. Therefore, argon is supplied into the reaction chamber 1 through the gas supply pipe 14 from the gas supply device 27, and the inside of the reaction chamber 1 is maintained at a pressure near the atmospheric pressure of an inert gas atmosphere of argon. The following fine particle manufacturing process is performed. Further, in order to control the flow of the plasma and the generated composite particles and the particle diameter, a gas may be supplied from the lower part of the reaction chamber 1 or the upper part of the electrode 4. Further, in order to promote the reduction of the material, hydrogen gas and a small amount of carbonized gas may be mixed and introduced into the reaction chamber 1 from the gas supply device 27 via the gas supply pipe.

(Step S3) Discharge is started.
The electrode 4 that generates the arc discharge is, for example, a carbon material. As shown in FIG. 2, six tips are provided on the circumferential wall of the reaction chamber 1 at intervals of 60 ° with the tip protruding in the reaction chamber 1 in the lateral direction (for example, upward from 5 ° to 30 ° with respect to the horizontal direction). The electrodes 4 are arranged radially. In order to reduce the evaporation of the electrode material, the electrode 4 is cooled as a water-cooled type in which the gas from the gas supply pipe 14 and specifically, although not shown, water is flown inside.

  In the first embodiment, six electrodes 4 are arranged radially, but if the number of electrodes is a multiple of 6, not only the number of electrodes is increased or they are arranged on the same plane, Alternatively, the electrode arrangement may be multi-stage such as three stages. By arranging the electrodes 4 in multiple stages, the arc discharge, which is a heat source for evaporating the material, can be further expanded in the vertical direction, which is advantageous for producing a large amount of fine particles. Moreover, although the carbon material is used as an example of the material of the electrode 4, an electrode made of a refractory metal such as tungsten or tantalum may be used.

  As shown in FIGS. 1 and 2, when the arc discharge is ignited, any two electrodes 4 are moved to the center side of the reaction chamber 1 by the electrode driving device 4a. After the arc discharge is ignited, the electrodes 4 are driven in the radiation direction (the direction from the center position of the radially arranged electrodes 4 to the outside) while adjusting the current applied to the electrodes 4 to be constant. It is moved by the device 4 a and is moved away from the center position of the electrode 4. Thereby, for example, the area of arc discharge, which is thermal plasma of about 10,000 ° C., can be increased, and the processing amount can be increased. As each electrode drive device 4a, as an example, a ball screw can be rotated forward and backward by a motor, and the electrode 4 connected to a nut member screwed to the ball screw can be advanced and retracted in the axial direction.

(Step S4) Material supply is started.
Next, the supply of the first material particles 30 and the second material particles 31 together with the gas is started.
As an example, the first material particles 30 are supplied to the plasma high-temperature part and evaporated to become a raw material for the nanometer-order fine particles 32. The first material particles 30 are installed in the first material supply apparatus 10 using Li ₃ PS ₄ having an average particle diameter of about 20 μm. The plasma high temperature part can evaporate the material if it is 500 ° C. or more and 12000 ° C. or less although it depends on the material.
The second material particles 31 are supplied to locations other than the plasma high temperature portion and are not evaporated. The second material particles 31 are made of graphite having an average particle diameter of about 5 microns and installed in the second material supply apparatus 11. The location where the second material 31 is supplied depends on the material when it is desired to maintain the shape as it is or when it is desired to make it spherical. For example, since the sublimation point of carbon is 3642 ° C., the temperature at which carbon is supplied may be 3500 ° C. or lower. In the first embodiment, particles having an average particle size of 20 microns and a maximum particle size of about 50 microns are used as the first material particles 30, but it also depends on plasma conditions and materials. For example, if the particle diameter is larger than 0.5 microns and not larger than 500 microns, it is possible to produce fine particles 32 of nanometer order by evaporating with thermal plasma. When the material particles 30 having a particle diameter larger than 500 μm are used, the material particles 30 cannot be completely evaporated, and the generated fine particles 32 may become large.
As the first material supply device 10 and the second material supply device 11, as an example, a local fluid powder supply device can be used. In this local flow type powder supply apparatus, the supply amount of the material particles is controlled by the flow rate of the carrier gas and the rotation speed of the container for introducing the material particles, so that the material particles as the powder material are supplied to the material supply pipe at a constant rate. Can send. Other examples of the material supply device include a surface scanning powder feeder and a quantitative powder feeder. In the surface copying type powder feeder, the distance between the surface of the powder material and the nozzle is controlled using a laser or the like. In the quantitative powder feeder, a fixed amount of powder material is supplied to the groove from a hopper or the like and sucked. Any type of powder material supply apparatus may be used, but it is preferable to use them properly depending on the amount of powder material to be supplied. In the first embodiment, particles of about 5 microns are used as the second material particles 31, but this also depends on the shape of the particles, the gas flow rate, and the like. For example, if the particle diameter is larger than 0.5 microns and smaller than 5000 microns, it can be supplied stably. When using the above-mentioned local flow type powder supply device, if it is smaller than 0.5 micron, the fluidity is deteriorated, the supply becomes unstable, and if it is larger than 5000 micron, fine adjustment of the supply amount becomes difficult. The ratio with the material particles 30 cannot be controlled.

  Further, by adding a material supply device and a material supply pipe, it is possible to form two or more types of composite particles or composite particles while synthesizing.

  In the first embodiment, the fine particles are formed. However, it is also possible to form a film of the first material particles on the surface of the second material particles depending on the material, the material supply conditions, and the plasma conditions.

  Also, the thermal energy applied to the second material particles can be reduced by making the gas flow rate or gas flow rate of the second material particles not desired to be evaporated larger than the gas flow rate or gas flow rate of the first material particles. A material having a lower melting point / boiling point can be used.

  The supply amounts of the first material particles 30 and the second material particles 31 are supplied so as to have a predetermined ratio.

(Step S5) Composite particles are formed.
Next, as shown in FIG. 1, the first material particles 30 and the second material particles 31 together with the gas from the first material supply device 10 and the second material supply device 11 are supplied to the first material supply pipe 10a and It is sent to the second material supply pipe 11a. Then, the first material particles 30 and the second material particles 31 are provided from the first material supply port 12 and the second material supply port 13 at the upper ends of the first material supply tube 10a and the second material supply tube 11a. Each is introduced into the reaction chamber 1 together with the gas. The material supply ports 12 and 13 at the upper ends of the first material supply pipe 10a and the second material supply pipe 11a are installed below the center position of the plurality of electrodes 4 in the vertical direction. In particular, the material supply ports 12 and 13 at the upper ends of the first material supply pipe 10 a and the second material supply pipe 11 a are arranged so as to be positioned below the region of the arc discharge 35.
Further, the material supply ports 12 and 13 can be arranged in various other modes in the plane and in the height direction depending on the arrangement of the electrodes, the state of plasma due to the application of AC power to the electrodes, and the like. For example, by installing the second material supply port 13 of the second material supply pipe 11 a that does not want to evaporate the material, in the vertical direction above the center position of the plurality of electrodes 4, the second material particles 31. It is possible to reduce the heat energy applied to the substrate and to use a lower melting point / boiling point.

  Further, as shown in FIG. 2, the first material particles 30 to be evaporated by thermal plasma are arranged at the lower side in the vertical direction between the centers of the plurality of electrodes 4 that are plasma high-temperature parts and the opposed electrodes. It supplies from the 1st material supply port 12 of the one material supply pipe | tube 10a. The second material particles 31 that are not evaporated are supplied from the second material supply port 13 of the second material supply pipe 11a that is disposed on the lower side in the vertical direction between the adjacent electrodes that are not the plasma high temperature part.

  FIG. 4 is a schematic diagram of the existence probability distribution of plasma due to arc discharge of one cycle when the frequency of AC power applied to the electrode applied in the composite particle manufacturing apparatus according to the first embodiment is changed. In FIG. 4, the electrodes and the plasma are shown, and the existence probability of the plasma is shown by shading in the region where the plasma spreads. As shown in FIG. 4, it can be seen that the fluctuation of the plasma, that is, the spread, is suppressed by increasing the frequency of the AC power applied to the electrodes from 60 Hz to 120 Hz and 180 Hz. In addition, it can be seen that the high temperature region, which is a high probability of plasma existing between the tips of the electrodes 4 facing each other, becomes narrower as the frequency increases, and gathers at the center between the tips of the electrodes 4. Therefore, by increasing the frequency, the temperature between the adjacent electrodes 4 becomes lower, and the thermal energy applied to the second material particles 31 supplied from between the adjacent electrodes 4 can be reduced. That is, a material having a lower melting point / boiling point can be used, the material supply port can be made closer to the center, and the dispersibility with the fine particles 32 generated from the first material particles can be increased. Further, the heat energy applied to the first material particles 30 can be increased, and a large amount of material can be made into fine particles. When the frequency is higher than 360 Hz, the high temperature region of the plasma high temperature portion between the tips of the opposing electrodes 4 becomes too narrow, and the first material particles 30 that do not pass through the high temperature region of the plasma high temperature portion are generated. Processing efficiency will deteriorate.

  The first material particles 30 introduced together with the gas into the reaction chamber 1 evaporate or vaporize (hereinafter, typically referred to as “evaporation”) when passing through the high temperature region of the plasma high temperature portion by the arc discharge 35. The first material particles 30 are gasified. The material gas produced by evaporating the first material particles 30 ascends in the reaction chamber 1 due to an upward air flow caused by the heat of the arc discharge 35 or a gas flow from the gas supply pipe 14 of the electrode 4. Thereafter, the moment the gas escapes from the area of the arc discharge 35, the material gas is rapidly cooled, and spherical fine particles 32 are generated. On the other hand, since the second material particle 31 passes through a portion other than the high temperature region of the plasma high temperature portion caused by the arc discharge 35 or a portion where the arc discharge 35 is not generated, the second material particle 31 is not evaporated but is ascended in the shape before melting or treatment Ascending in the reaction chamber 1 by the flow of gas. Thereafter, the particles are mixed with the spherical fine particles 32 at the top of the arc discharge 35 or after exiting from the arc discharge 35, thereby forming composite particles in which the spherical fine particles 32 adhere to the surface of the second material particles 31.

  Further, the dispersibility can be improved by introducing gas from the lower part or the upper part of the arc discharge 35 to control the flow, for example, causing a swirling flow.

  In addition, when the average particle size of the second material particles 31 that are not evaporated is melted with respect to the minimum size of 0.5 μm before supply and becomes an spherical shape from an indefinite shape, the average particle size is slightly reduced to 0.3 μm. become. For this reason, the average particle diameter of the second material particles 31 is from 0.5 μm to 5000 μm before the treatment and from 0.3 μm to 5000 μm after the treatment. On the other hand, the average particle diameter and the average film of the first material particles 30 to be evaporated depend on the material, plasma conditions, conditions for introducing a cooling gas from the top of the arc discharge 35, and the like. In the cooling rate in the present embodiment, when the particles are made fine, for example, the average particle diameter is 5 nm or more and 300 nm or less, and when a film is formed, the average thickness of the film is 5 nm or more and 1000 nm or less.

(Step S6) The discharge is stopped and the composite particles are collected.
Next, as shown in FIG. 1, the generated composite particles 34 are recovered by the composite particle recovery unit 3 by the gas flow. Although not shown, the composite particle recovery unit 3 is provided with a bag filter that can recover desired composite particles. Since the bag filter for recovering the composite particles flows a high-temperature gas, a filter using silica fibers having high heat resistance can be used as an example. Moreover, when taking out the collect | recovered composite particle | grains to air | atmosphere, since there exists a possibility of deterioration, it takes out in inert atmosphere. By these processes, composite particles in which Li ₃ PS ₄ fine particles of 10 nm or more and 300 nm or less adhere to the surface of, for example, about 5 μm of graphite can be recovered from the bag filter. In this embodiment, a carbon material may be used for the electrode 4 and an internal member such as an inner chamber (not shown). This prevents high temperature plasma from coming into contact with the reaction chamber wall 15 and the electrode, which are generally made of metal, and can suppress an increase in impurities such as metal in the process, and the metal material in the generated composite particles The content of can be made 0.5% or less. Furthermore, _Li 3 PS _4, since reacts with metal such as Cu, by using a carbon material or SUS material on the electrode 4 and the inner member in contact with the _Li 3 PS _4, the degradation by the reaction of _Li 3 PS ₄ Can be suppressed. When the produced composite particles are used in a lithium battery, the solid electrolyte can be efficiently dispersed around the active material, so that battery characteristics such as battery capacity and charge / discharge speed can be improved.

  Further, according to the first embodiment, since the AC power source 5 is connected to each of the plurality of electrodes 4 to generate the arc discharge 35, the first material particles 30 are evaporated as compared with the conventional method. The area of the thermal plasma by the arc discharge 35 can be increased, and a large amount of material can be processed.

  In addition, it can be made to show the effect which each has by combining arbitrary embodiment or modification of the said various embodiment or modification suitably. In addition, combinations of the embodiments, combinations of the examples, or combinations of the embodiments and examples are possible, and combinations of features in different embodiments or examples are also possible.

  In the composite particle manufacturing apparatus and manufacturing method according to the present invention, the first material to be evaporated is charged into the high temperature region of the plasma high temperature portion, and the second material not to be evaporated is a portion where plasma is not generated other than the plasma high temperature portion or It is thrown into the low temperature part. As a result, the gas / vapor of the generated first material and the second material are mixed to form a film of the first material on the surface of the second material or to collect composite particles of different materials with fine particles attached together. A large amount can be processed efficiently. Therefore, the production amount of the composite particles can be increased and the production can be performed at low cost. Therefore, the composite particle manufacturing apparatus and manufacturing method according to the present invention are useful as a composite particle manufacturing apparatus and manufacturing method used for devices that require mass production such as lithium ion secondary batteries or ceramic capacitors.

DESCRIPTION OF SYMBOLS 1 Reaction chamber 3 Composite particle | grain collection | recovery part 4 Electrode 5 AC power supply 10 1st material supply apparatus 10a 1st material supply pipe 11 2nd material supply apparatus 11a 2nd material supply pipe 12 1st material supply port 13 1st Second material supply port 14 Gas supply pipe 15 Reaction chamber wall 20 Pipe 21 Pressure adjustment valve 22 Pump 26 Flow rate regulator 27 Gas supply device 30 First material particle 31 Second material particle 32 First material fine particle 34 Composite Particle 35 Arc discharge

Claims (16)

A chamber;
A plasma generating device arranged in the chamber to generate plasma;
A first material supply device connected to the chamber and supplying a first material into the chamber from a first material supply port;
A second material supply device connected to the chamber and supplying a second material into the chamber from a second material supply port;
A recovery device connected to the chamber and recovering the composite particles discharged from the chamber;
With
An apparatus for producing composite particles from the first and second materials supplied from the first and second material supply devices by the plasma generated in the chamber,
The plasma generator generates a plasma high-temperature part having plasma at a higher temperature than the peripheral part in the central part of the chamber,
The first material supply port of the first material supply device is installed so that the first material is supplied to the plasma high temperature part, and the second material supply port of the second material supply device Is installed such that the second material is supplied to a place other than the plasma high temperature part.   2. The composite particle manufacturing apparatus according to claim 1, wherein the plasma high temperature part has a plasma existence probability of 0.5 or more. The plasma generator comprises:
A plurality of electrodes connected to the chamber and having a tip projecting into the chamber to generate the plasma;
AC power supplies connected to the plurality of electrodes, respectively, and supplying AC power having different phases,
With
3. The composite particle according to claim 1, wherein AC power having different phases is supplied to each of the plurality of electrodes from the AC power source to generate arc discharge between the electrodes to generate the plasma. 4. manufacturing device.   The said 1st material supply port is arrange | positioned at the center part in the surface defined by the front-end | tip part of these electrodes, or the front-end | tip part of the said electrode seeing from perpendicular | vertical upper direction. Composite particle production equipment.   5. The composite particle manufacturing apparatus according to claim 3, wherein the second material supply port is disposed at a position between the adjacent electrodes as viewed from vertically above.   6. The composite particle manufacturing apparatus according to claim 3, wherein in the AC power source supplied to the plurality of electrodes, the frequency of the AC power is greater than 60 Hz and equal to or less than 360 Hz. A plasma high temperature part having a plasma higher than the peripheral part is generated in the central part of the chamber by a plasma generator installed in the chamber,
A first material is charged into the plasma high-temperature part plasma, and when the first material passes through the region of the plasma high-temperature part, it evaporates or vaporizes to become a material gas of the first material, Furthermore, at the moment when the material gas of the first material escapes from the region of the plasma high temperature portion, the material gas of the first material is rapidly cooled and solidified,
A second material is introduced into a place other than the plasma high temperature part, and the second material is left as it is or is melted, spheroidized and solidified, and the second material is solidified on the solidified surface of the second material. Forming a film of one material or synthesizing composite particles having fine particles attached to the surface;
Composite particle manufacturing method.   The said plasma high temperature part is a composite particle manufacturing method of Claim 7 whose plasma existence probability is 0.5 or more. The plasma generator comprises:
A plurality of electrodes connected to the chamber and having a tip projecting into the chamber to generate the plasma;
AC power supplies connected to the plurality of electrodes, respectively, and supplying AC power having different phases,
With
The composite particle production according to claim 7 or 8, wherein AC power having different phases is supplied from the AC power source to the plurality of electrodes, respectively, and arc discharge is generated between the electrodes to generate the plasma. Method.   10. The first material is supplied from a center portion in a plane defined by tip portions of the plurality of electrodes or a position facing the tip portions of the electrodes as viewed from above in the vertical direction. The composite particle manufacturing method.   The method for producing composite particles according to claim 9 or 10, wherein the second material is supplied from a position between adjacent electrodes as viewed from above.   12. The method for producing composite particles according to claim 9, wherein in the AC power source that supplies AC power to the plurality of electrodes, the frequency of the AC power is greater than 60 Hz and 360 Hz or less.   The method for producing composite particles according to any one of claims 7 to 12, wherein a supply amount of the first material is smaller than a supply amount of the second material.   The average particle diameter of the first material before being supplied to the plasma is 0.5 μm or more and 500 μm or less, and the average particle diameter of the second material before being supplied to the plasma is 0.5 μm or more and 5000 μm or less, The method for producing composite particles according to any one of claims 7 to 13.   The average particle diameter of the first material after passing through the plasma is 5 nm or more and 300 nm or less, and the average particle diameter of the second material after passing through the plasma is 0.3 μm or more and 5000 μm or less. 14. The method for producing composite particles according to 14.   The average particle diameter of the second material after passing through the plasma is 0.3 μm or more and 5000 μm or less, and the film of the first material formed on the surface of the second material after passing through the plasma The composite particle manufacturing method according to claim 14, wherein the average thickness is 5 nm or more and 1000 nm or less.

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