WO2005040038A1 - Procede et dispositif pour produire des particules fines - Google Patents

Procede et dispositif pour produire des particules fines Download PDF

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Publication number
WO2005040038A1
WO2005040038A1 PCT/JP2004/015599 JP2004015599W WO2005040038A1 WO 2005040038 A1 WO2005040038 A1 WO 2005040038A1 JP 2004015599 W JP2004015599 W JP 2004015599W WO 2005040038 A1 WO2005040038 A1 WO 2005040038A1
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Prior art keywords
reactor
solution
fine particles
gas
spraying
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PCT/JP2004/015599
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English (en)
Japanese (ja)
Inventor
Zempachi Ogumi
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Zempachi Ogumi
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Publication of WO2005040038A1 publication Critical patent/WO2005040038A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention provides a nanometer-sized (
  • the fine particles of the present invention are included in electrode / electrolyte materials applied to batteries such as lithium ion secondary batteries, nickel metal hydride batteries, and fuel cells, and in image display devices such as plasma display panels and displays using electron-emitting devices. It can be suitably used as a material of a phosphor to be used, an electrode material such as a ceramic multilayer substrate for high-frequency radio, and a photocatalyst material.
  • Patent Literature 1 and Patent Literatures 1 to 3 demand a method for efficiently and easily producing fine particles at low cost. So far, sol, gel method, coprecipitation method, PVD method, hydrothermal method, hydrolysis method, spray thermal decomposition method, etc. are known as methods for producing nanometer-sized fine particles. In the sol-gel method, the starting material alkoxide is expensive, so the raw material cost of fine particles is high. In addition, it is easily affected by manufacturing conditions such as temperature and humidity, so that stable industrial production is difficult.
  • the PVD method is not suitable as a starting material that evaporates at a low temperature, so there is a limitation on the types of fine particles that can be produced, and the production cost is high because a high vacuum device is required for vaporization.
  • the hydrothermal method requires special equipment that can withstand high temperature and pressure, and the Notch method requires expensive fine particles to be produced.
  • the hydrolysis method has a complicated manufacturing process and a wide particle size distribution of the obtained fine particles.
  • the spray pyrolysis method is relatively simple because fine particles are obtained by spraying a raw material solution to generate fine droplets and performing pyrolysis in a high-temperature reaction atmosphere. is there.
  • Various spraying means have been proposed, for example, well-known ultrasonic atomization (Patent Document
  • Patent Document 7 spraying with a two-fluid nozzle
  • Patent Document 8 pressurized spraying
  • vibrational spraying vibrational spraying
  • rotating disk type spraying with a deviation of Patent Document 8
  • electrostatic atomization Patent Document 9
  • Tepuru. V displacement is several tens of micrometer force This is a method that can efficiently produce particles with a size of about submicron meter.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-038150
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-162735
  • Patent Document 3 Japanese Patent No. 2909403
  • Patent Document 4 Japanese Patent Publication No. 63-46002
  • Patent Document 5 JP-A-6-199502
  • Patent Document 6 JP-A-8-170112
  • Patent Document 7 JP-A-11-236607
  • Patent Document 8 JP-A-2003-19427
  • Patent Document 9 JP-A-2002-187729
  • Patent Document 10 JP-A-2003-155504
  • Non-Patent Document 1 JOURNAL of the Electrochemical Society, 2003, 150, A10 00-A1007
  • Non-Patent Document 2 J. Schoonman / Solid State Ionicsl35 (2000) 5-19 Disclosure of Invention
  • an object of the present invention is to provide a method and an apparatus for efficiently producing nanometer-sized fine particles having a uniform particle diameter at low cost.
  • a method for producing fine particles of the present invention comprises:
  • the spraying is preferably performed by using a two-fluid nozzle having a liquid feed pipe for passing a solution and a gas feed pipe for passing gas, for example, a gas feed pipe provided coaxially with the liquid feed pipe. Is applied through the liquid feeding pipe.
  • the gas injected with the solution becomes turbulent near the injection port, and the turbulence of the gas flow causes the solution to become small droplets.
  • the solvent in the droplets gradually evaporates and desorbs during the flight process after spraying, reducing the surface area of the droplets. Since the droplet is charged by applying a voltage, the charge density on the surface of the droplet increases as the surface area decreases, and when it reaches a certain level, it becomes two or more minute droplets due to electrical restrictions. It splits or desorbs ions from the droplet.
  • a manufacturing apparatus suitable for the method for manufacturing fine particles of the present invention includes:
  • a liquid supply pipe having a solution injection port at one end for spraying the solution, and a coaxially provided with the liquid supply pipe over a predetermined length connected to the solution injection port, for injecting gas around the solution injection port.
  • a reactor having one end connected to the solution injection port and the gas injection port, and having a fine particle collection port at the other end;
  • a heating furnace provided around the reactor to heat the reactor
  • the solution passing through the liquid feed pipe is charged.
  • the charged solution is sprayed into the reactor of the two-fluid nozzle capillar, so that the charged solution is formed into droplets and fly in the reactor. Since the gas is also sprayed simultaneously with the spraying of the solution, the spray speed is high and the flight distance is long. Therefore, as described above, the division of the droplet and the desorption of the ions can be repeated in the flight process, and the droplet is miniaturized.
  • the droplets are thermally decomposed into nanometer-sized particles.
  • a solution containing a metal element is charged and sprayed to form fine droplets, and these particles are made uniform by a simple manufacturing process of thermally decomposing the droplets. Nanometer-sized fine particles can be continuously and efficiently produced. Since the fine particles obtained by the present invention have high crystallinity and uniform particle size, the materials for electronic devices such as batteries, displays, and ceramic multilayer substrates, magnetic materials, ferroelectrics, superconductors, photocatalysts It shows excellent performance.
  • FIG. 1 is a schematic diagram showing a two-fluid nozzle.
  • FIG. 2 is a configuration diagram of a manufacturing apparatus used in Examples 17 and 18 and Comparative Example 1.
  • FIG. 3 is a configuration diagram of a manufacturing apparatus used in Examples 8-10 and Comparative Example 2.
  • FIG. 4 is a configuration diagram of a manufacturing apparatus used in Examples 11 to 14.
  • FIG. 5 is a configuration diagram of a manufacturing apparatus used in Example 15.
  • FIG. 6 is a configuration diagram of a manufacturing apparatus used in Example 16.
  • FIG. 1 shows an example of the two-fluid nozzle used in the present invention.
  • the two-fluid nozzle has a solution jetting port 3 at one end, and a liquid sending pipe 1 through which the solution 4 flows with the other end connected to the solution supply container, and a gas introducing pipe 2 through which gas passes.
  • the liquid feed pipe 1 is linear at least over a certain length connected to the solution injection port 3, and a gas introduction pipe 2 is provided so as to coaxially surround the outside of the linear part.
  • the tip of the gas inlet pipe 2 is a ring-shaped gas jet concentric with the solution jet port 3. Make a mouth.
  • the gas introduction pipe 2 is preferably tapered. It is also preferable that the liquid sending pipe 1 is tapered. When both pipes are tapered, the gradient of the taper of the gas inlet pipe 2 is made larger. By forming the taper in this manner, the gap between the liquid feed pipe and the gas inlet pipe at the tip, that is, the difference between the inner and outer diameters of the gas injection port is reduced, so that the gas flow rate increases to about the speed of sound, and the solution is further reduced. It can be sprayed vigorously.
  • the inner diameter of the liquid sending pipe 1 in the solution injection port 3 is 10 to 1000 m and the thickness is 10 to 500 ⁇ m. If the inner diameter is less than 10 ⁇ m, the liquid sending pipe 1 may be clogged by impurities, and if the inner diameter exceeds 1000 m, it tends to become fine particles. In addition, if the thickness of the liquid sending pipe at the tip is less than 10 m, the liquid sending pipe tends to be damaged and handling is difficult, and if it is more than 500 m, coarse liquid droplets tend to be generated.
  • the conductive material may be any material that is conductive to the inner surface that comes in contact with the solution and is not easily corroded by the solution, and that has conductivity over a predetermined length. And metals such as copper, gold, and platinum. It is not necessary that all of the pipes be made of the same material.
  • V you can.
  • the tip of the liquid sending pipe made of metal or alloy, but if processing is difficult, the tip of the liquid sending pipe should be insulated with glass or the like.
  • Use materials ⁇ .
  • an insulating material such as glass and a conductive material, it is preferable to use, for example, Kovar as the conductive material.
  • the insulating material may be subjected to metal plating using an electroless plating method or the like.
  • the two-fluid nozzle is a nozzle in which part or all of the liquid feed pipe or Z and the gas inlet pipe are made non-linear, and the liquid feed pipe or / and gas inlet Nozzle with multiple pipes, Nozzles that generate ultrasonic waves, and the like can be given.
  • the gas flow injected from the gas introduction pipe swirl the gas-liquid mixing is promoted and finer particles are achieved. Also, clogging of the nozzle can be prevented by the swirling gas flow.
  • a nozzle provided with a plurality of liquid feeding pipes and / or gas introduction pipes is used, different solution gases can flow in each path.
  • the type of the carrier gas flowing through the gas introduction pipe 2 is one that does not react with the solution at normal temperature and normal pressure, but is preferably selected according to the type of the fine particles to be produced.
  • the gas pressure is controlled by using a pressure regulator such as a regulator, etc., in consideration of the shape of the two-fluid nozzle and the pressure in the reactor, which are preferably controlled to be higher than the pressure in the reactor.
  • the pressure is approximately 0.8 atm or more and 20 atm or less. Above 20 atmospheres, the two-fluid nozzle is easily broken.
  • the gas flow velocity depends on the gap between the liquid sending pipe and the gas introduction pipe at the tip of the two-fluid nozzle, and is approximately 0.1-50 liters Z. If it is less than 0.1 liter Z, the spray speed is low and it is not practical. If it exceeds 50 liter Z, the flow of the sprayed droplets tends to become turbulent.
  • the spraying rate of the solution has a direct effect on the rate of fine particle formation, and is preferably 0.5-10 4 mlZ min, more preferably 10-5 x 10 3 mlZ min.
  • the two-fluid nozzle is connected to a rotary atomizer whose liquid sending pipe 1 and gas introducing pipe 2 rotate at high speed around the axis. Is preferred.
  • the pipe axis direction of the two-fluid nozzle is set at —90 (spray direction is directly above)-+ 90 ° (spray direction) in consideration of the installation space of the device and the like. Can be selected in the range below).
  • the tube axis direction of the two-fluid nozzle is preferably 9030 °.
  • the solution flowing through the liquid sending pipe 1 is lithium (Li), sodium (Na), potassium), magnesium. (Mg), Ca (calcium), strontium (Sr), barium (Ba), carbon (C), aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), molybdenum (Mo), palladium (Pd ), Silver (Ag), tin (Sn), tungsten (W), lanthanum (La), platinum (Pt), and gold (Au).
  • a solution can be prepared by dissolving the compound containing these metal elements in a solvent.
  • the types of metal compounds include alkoxides, sulfates, chlorides, nitrates, phosphates, carbonates, acetates, perchlorates, ammonium salts, cyanide compounds, and the like. However, it is not limited to these.
  • the conductivity of the solution to be sprayed and the dielectric constant of the solvent constituting the solution be as high as possible.
  • the former has a metal element concentration closely related, 10-6 - 2 moles Z liter properly at it is preferred to preferred instrument range of 10 4 - 1 mole Z liter. If it exceeds 2 mol Z liters, the content of the solvent is small and the droplets are not easily formed into fine particles, so that coarse particles are easily generated. On the other hand, the rate of formation of fine particles becomes difficult to say that very slow because practically is less than 10-6 mole Z rates Torr.
  • the solvent constituting the solution is desired to be selected in consideration of the solubility of a solute such as a compound containing a metal element, and the like. It is preferable that the point force of the droplet to be easily charged has a high dielectric constant. . Further, from the viewpoint of the ease with which the droplets are broken, the surface tension of the solution is preferably 80 mNZm 2 or less, more preferably 50 mN / m 2 or less.
  • solvent contained in such a solution examples include methanol, ethanol, 2-propanol, n-propanol, butanol, pentanole, hexanol, ethylene glycol, propylene glycol, 3-methyl-3-methoxybutanol, Alcohols such as benzyl alcohol, 3-methyl-3-methoxybutanol, ⁇ -butyrolataton, ⁇ -methyl-2-pyrrolidone, dimethylacetamide, propylene glycol monomethyl ethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl Polar solvents such as ketone, dimethylacetamide, ⁇ , ⁇ -dimethylformamide, tetrahydrofuran, acetone and water Can be used alone or as a mixture.
  • the solution preferably contains a surfactant. Further, it is preferable that a solvent having a boiling point of 100 ° C. or less be used as a main solvent in view of the ease of desolvation. In addition, it is desirable to keep the viscosity of the solution below 100 cP from the viewpoint of the smoothness of liquid sending.
  • the two-fluid nozzle is connected to one end of a long tubular reactor 11 for performing a thermal decomposition reaction at the tip as shown in FIG.
  • the pressure in the reactor 11 should be kept at a pressure of usually at most 1 atm, preferably at most 0.5 atm, more preferably at most 0.05 atm.
  • the pressure is reduced by a vacuum pump 9 connected to the other end of the reactor 11 via the trap 8.
  • a low pressure promotes desolvation, but if the pressure is too low, it becomes difficult to spray droplets due to the characteristics of the two-fluid nozzle.
  • the pressure in the reactor near the two-fluid nozzle should be increased so that good spraying can be obtained.
  • an evacuation device such as an aspirator can be used more simply besides a vacuum evacuation pump.
  • the pumping speed VI (liter Z minute) of these pumping devices can be appropriately selected according to the volume V2 (liter) of the reactor 11 and the spraying speed of the solution, but is in a range of about 0.055 ⁇ V2 ⁇ V1 ⁇ 5. Is preferred.
  • the pressure in the solution supply container is 0.01 to 0.9 atm, preferably 0 to 0.9 atm, higher than the pressure in the reactor. It is preferable to control so that the pressure becomes higher by 1 to 0.5 atm.
  • a portion of the liquid supply pipe 11 made of a conductive material is connected to the high-voltage DC power supply 7.
  • the voltage E1 applied from the power supply 7 to the liquid sending pipe 11 can be appropriately selected according to the shape of the liquid sending pipe, the pressure and temperature in the heating furnace, the presence or absence of a counter electrode described later, and the voltage of the counter electrode.
  • a heating furnace 12 is arranged around the reactor 11.
  • the temperature inside the reactor 11 is controlled by the heating furnace 12 at room temperature or higher, preferably in the range of 40 to 1200 ° C. Temperature is measured by thermocouple 13. Therefore, the droplets sprayed into the two-fluid nozzle capillar reactor 11 receive heat from the caro heating furnace 12 and are decomposed.
  • the heating furnace 12 at least one selected from the group consisting of an infrared heating furnace, a microwave induction heating furnace, and a resistance heating furnace can be used in consideration of the physical properties of the solvent and the temperature at which fine particles are generated.
  • a heat source such as a heater may be provided in the reactor to promote heat transfer to the droplets. Also, in order to promote thermal decomposition of droplets, connect a gas burner to the reactor and burn combustible gas such as oxygen in the reactor.
  • the shape of the reactor 11 is not limited to the tubular shape as described above, and may be a spherical shape or a radial shape centered on a two-fluid nozzle for the purpose of keeping the flight distance of droplets constant.
  • the inner diameter of the tube is preferably 30 to 1000 mm. If the diameter is less than 30 mm, the production speed of the fine particles is remarkably reduced, which is not practical.If the diameter exceeds 1000 mm, the heat from the heating furnace 12 is not sufficiently transmitted to the droplets, and the crystallinity of the obtained fine particles is remarkably high. Tends to decrease.
  • the length of the tube is preferably 100-10000 mm, more preferably 300-7000 mm.
  • the diameter is less than 100 mm, the flight distance of the sprayed droplet is short, so that the size is insufficiently reduced and coarse particles are easily generated. If it exceeds 10,000 mm, the generated fine particles stay and remain in the reactor because the reactor is long, and it becomes difficult to collect the fine particles.
  • the solution 4 containing the metal element is charged by the voltage applied from the power supply 7 to the liquid sending pipe 1 while passing through the liquid sending pipe 1. Then, the charged solution 4 is applied to the two-fluid nozzle
  • the droplets are sprayed into the reactor 11 in a charged state.
  • the droplets fly in the reactor 11, are miniaturized due to electrical restrictions during the flight, and are decomposed by receiving heat from the heating furnace 12 to become nanometer-sized fine particles.
  • a known collection method can be used, and examples thereof include a filter set using a cyclone and a bag filter, and an electrostatic collection type. In the illustrated example, the fine particles are deposited on the collecting substrate 14 placed at the other end in the reactor 11, so that the fine particles can be easily collected.
  • a heater may be provided in the reactor to increase the amount of heat supplied to the droplets to promote thermal decomposition. Further, by fixing the collecting substrate on the heater, a film containing nanometer-sized fine particles can be formed on the collecting substrate.
  • the average particle diameter of the fine particles produced by the production method of the present invention is generally in the range of 11 100 nm. Therefore, the production method of the present invention is, for example, LiCoO, LiNiO, LiMnO (provided that 0.8 ⁇ a ⁇ l. 3) used as a positive electrode active material of a lithium ion secondary battery,
  • Li FePO (provided that 0.8 ⁇ a ⁇ l. 3)
  • Li Ni Co O (provided that 0.8 ⁇ a ⁇ l. 3, b + c a 3 a b c 2
  • Me represents at least one element selected from the group consisting of B, Al, Mg, Si, Cu, Ti, V, Mn, Ni, Sn, Zr and Cr. ) And the like. Also, the production of carbon fine particles such as graphite, non-graphitizable carbon, and graphitizable carbon, which are preferably used as a negative electrode active material of a lithium ion secondary battery, silicon, tin, and LiTiO.
  • the production method of the present invention is also preferably used when producing an electrolyte for a lithium ion secondary battery, for example, LiPF, LiBF, LiCF SO, LiN (CF S),
  • the present invention can be preferably applied not only to lithium ion secondary batteries, but also to batteries such as nickel-metal hydride batteries, fuel cells, and solar cells.
  • batteries such as nickel-metal hydride batteries, fuel cells, and solar cells.
  • a negative electrode material such as LiTiO is deposited on a metal substrate such as copper by using a known appropriate method. Then, on top of this,
  • An electrolyte such as Li La TiO and a positive electrode such as LiMn O
  • the fine particles of the present invention are also suitable as an electrode catalyst material for a fuel cell, for example, Pt, Au, Ni, Rh, Zr, Ag, Ir, Ru, Fe, Co, Ni, Cr, Metal fine particles containing at least one metal element selected from W, Mn, V and Pd can be used. These metals may be alloyed alloy fine particles. In addition, these metal fine particles or alloy fine particles may be fine particles containing acid oxide fine particles. Further, it is also suitable as an electrolyte material for a fuel cell, for example, ZrO, CeO, SnO, WO, SrO, LaO, and these.
  • Solid solution oxide fine particles or these oxide fine particles contain at least one metal element selected from Sc, Ga, Y, Yb, La, Ce, Pr, Nd, Sm, Gd and Dy in an amount of 110 to 30 mol%.
  • the fine particles of the present invention are also preferably used as an electrode material for a fuel cell.
  • the fine particles of ZrO, CeO and Zr CeO are used.
  • Silver ion conductor such as O, Ag I WO, j8-alumina, ,,-alumina, Rb Cu CI I
  • Fine particles of a magnesium ion conductor such as y ⁇ 6.5, 0 ⁇ z ⁇ 0.5).
  • the fine particles of the present invention can also be preferably used for ferroelectric materials, for example, barium titanate BaTiO, and Mg, Ca, Nb, Co, Mn, Ni, Si, B, Bi, Zn , Cu,
  • Group strength of Ho, Zr, Hf and Sr Examples include barium titanate containing at least one selected element.
  • Neodymium rare earth magnets such as l ⁇ a ⁇ 6, 10 ⁇ b ⁇ 35) containing at least one selected metal element, SmCo and Sm Co
  • the fine particles of the present invention are also preferably used as a superconducting material, for example, BiSrCaCuO, YBaCuO, MgB, Tl
  • Fine particles such as Ba Ca Cu O may be used.
  • the fine particles of the present invention are also suitable as phosphor particles used in a plasma display.
  • red particles such as YEuTaO (but 0.005 ⁇ x ⁇ 0.1) and YO: Eu can be used.
  • Phosphor, Zn SiO Green such as Mn and Y Tb TaO (however, 0.001 ⁇ x ⁇ 0.2)
  • Fine particles of a blue phosphor may be used.
  • the fine particles of the present invention are also suitable for circuit materials such as ceramic multilayer substrates for high-frequency wireless. It is. Typical examples of inorganic powders constituting the matrix of the multilayer circuit include alumina, zircon-a, magnesia, beryllia, mullite, spinel, forsterite, anosite, cellian and glass ceramics including aluminum nitride. . Furthermore, it can be preferably applied to fine particles of Cu, Cr, Ag, Ni, Al and Au used as wiring conductors.
  • the fine particles of the present invention are also suitable as titanium oxide fine particles used as a photocatalyst and titanium oxide fine particles containing Al, Si, Fe and the like.
  • the titanium oxide referred to here is a titanium oxide such as titanium monoxide, dititanium trioxide, or titanium dioxide, and particularly in the case of titanium dioxide, the crystal form is either rutile or anatase. Good.
  • an electrostatic collector 10 is provided outside a reactor 11, and a collecting substrate 14 is placed therein.
  • Other configurations are the same as those of the first embodiment. By providing the collector 10 outside in this way, it is possible to avoid collecting relatively coarse particles.
  • a plurality of heating furnaces 12 are arranged on the outer periphery of the reactor 11 in the axial direction.
  • a temperature gradient can be provided in parallel with the direction of the tube axis of the two-fluid nozzle, and the temperature can be set according to the [Solute Z solvent] ratio of the droplet in flight.
  • a single heating furnace may be used as long as a plurality of heating temperature ranges can be provided.
  • the opposite electrode 15 applied with a voltage having a different polarity from the voltage applied to the liquid sending pipe from the power supply 18 different from the power supply 7 is applied to the two-fluid nozzle side end in the reactor 11. It is arranged in non-contact with the two-fluid nozzle.
  • the opposite electrode 15 may be applied with a voltage E2 having a polarity different from that of E1, or may be grounded.
  • the droplet 5 is accelerated, and the flight distance and the flight time of the droplet are extended, so that the atomization is promoted. As a result, fine particles with a uniform particle size tend to be obtained.
  • the shape of the counter electrode 15 has a mesh or an orifice, a partition that stands upright with respect to the axis of the two-fluid nozzle, or a cone that has a concentric orifice with the two-fluid nozzle. It is preferable to use a trapezoidal or conical schema.
  • the number of meshes in the case of a mesh is preferably 5 to 800 mesh. When the mesh size is less than 5 meshes, the eyes are too large, so that the droplets are hardly charged.
  • Diaphragm with orifice ⁇ The diameter of the orifice when using the scheme 1 is preferably 30 to 5000 ⁇ m
  • the electrification of the droplets is promoted and the coarse droplets can be removed as soon as possible, thereby suppressing the generation of coarse particles.
  • two or more orifices exist in one partition / schema in order to increase the amount of droplets introduced into the heating furnace.
  • two magnets 16 are fixed on the outer periphery of the reactor 11 near the connection with the two-fluid nozzle.
  • Other configurations are the same as those of the first embodiment.
  • the two magnets are provided to face each other with the reactor 11 therebetween, and have different polarities.
  • a magnetic field is formed in the radial direction of the reactor 11, and coarse droplets of the sprayed droplets are directed in the radial direction by the action of the magnetic field, and collide with and adhere to the inner surface of the reactor 11. Therefore, large particles derived from coarse droplets are not placed on the collecting substrate 14, and fine particles having a uniform particle diameter can be obtained.
  • the magnetic flux density by the magnet 16 is preferably 50 to 250 mT.
  • the magnet 16 is preferably rotated about the axis of the two-fluid nozzle. This is to prevent coarse particles from adhering to the same location on the inner surface of the reactor 11.
  • Embodiment 5 In this embodiment, as shown in FIG. 6, a laser light source 17 is arranged on one side near the connection with the two-fluid nozzle on the outer periphery of the reactor 11. This laser beam contains a wavelength that can be absorbed by the droplet 5, and by irradiating the laser beam onto the droplet 5 immediately after spraying, the desorption of the solvent is promoted.
  • Other configurations are the same as those of the second embodiment.
  • TEM transmission electron microscope
  • Particles obtained by dispersing the obtained fine particles in three kinds of solvents of ethanol, acetone and water at a concentration of 3 wt% each were measured using a particle size distribution analyzer NICOMP3 80ZDLS of Particle sizing systems. The smallest! /, The average particle diameter was defined as the average particle diameter B, and D was determined for the sample showing the average particle diameter B.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and a quartz tube having an inner diameter of 30 mm and a length of 100 mm was used as the reactor 11.
  • a thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 500 ° C. in the resistance heating furnace 12.
  • X-ray diffraction measurement was performed on the prepared fine particles. It was found to be zeolite titanium oxide.
  • the average particle diameter A of the fine particles was 35 nm
  • the average particle diameter B was 25 nm
  • D was 185 nm.
  • a platinum salt solution having a sulfur concentration of 1 mol / liter was prepared.
  • the carrier gas is a mixed gas of argon and hydrogen (1: 1 by volume)
  • the carrier gas pressure is 2 atm
  • the pressure in the reactor 11 is 0.06 atm
  • Fine particles were produced under the conditions that the voltage applied to the liquid tube 1 was 135 kV DC and the spraying rate of the solution was 100,000 mlZ, and the fine particles were collected on the same collecting substrate 14 as that in Example 1.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and an alumina tube having an inner diameter of 950 mm and a length of 9200 mm was used as the reactor 11.
  • thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 600 ° C. in the resistance heating furnace 12. X-ray diffraction measurement of the prepared fine particles revealed that the particles were platinum. Average particle size A of fine particles is 30 nm, average particle size B is 35 nm, D is 180 nm
  • the carrier gas is argon
  • the carrier gas pressure is 4 atm
  • the pressure in the reactor 11 is 0.79 atm
  • the voltage applied to the liquid sending pipe 1 is 48 kV
  • the solution spray speed Prepared fine particles under the conditions of 4700 mlZ and collected them on the same collecting substrate 14 as in Example 1.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and a quartz tube having an inner diameter of 30 mm and a length of 300 mm was used as the reactor 11.
  • thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 450 ° C. in the resistance heating furnace 12. X-ray diffraction measurement of the produced fine particles showed that they were spinel-type LiMn O.
  • Average particle size A of fine particles is 25nm, average particle size B is 28nm, D is 165 ⁇
  • a solution having a total elemental concentration of lead, manganese and silicon of 0.9 mol Z liter was prepared.
  • the carrier gas is air
  • the carrier gas pressure is 5 atm
  • the pressure in the reactor is 0.1 atm
  • the voltage applied to the liquid sending pipe 1 is 2 kV DC
  • the spraying speed of the solution is Fine particles were produced under the condition of lOmlZ, and were collected on the same collecting substrate 14 as in Example 1.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and an alumina tube having an inner diameter of S950 mm and a length of 7000 mm was used as the reactor 11.
  • thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 750 ° C. in the resistance heating furnace 12. X-ray diffraction measurement of the produced microparticles showed that it was spinel-type ZnSiO: Mn.
  • Average particle size A of fine particles is 21 nm
  • average particle size B is 25 nm
  • D is 160 nm
  • a solution having a total elemental concentration of lanthanum and lithium of 0.15 mol Z liter was prepared.
  • the carrier gas is a mixed gas of nitrogen and argon (volume ratio: 5:95)
  • the carrier gas pressure is 3 atm
  • the pressure in the reactor 11 is 0.15 atm
  • the liquid supply pipe 1 Microparticles were produced under the conditions of a voltage of 4 kV DC applied and a spraying rate of 30 mlZ for the solution, and the fine particles were collected on the same collecting substrate 14 as in Example 1.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and a quartz tube having an inner diameter of 100 mm and a length of 900 mm was used as the reactor 11.
  • thermocouple 13 for measuring the temperature of the reactor 11 was attached at the center of the tube, and was maintained at 850 ° C. in a resistance heating furnace 12 having an axial length of 900 mm.
  • the particles were perovskite type Li La TiO.
  • Average particle diameter A of fine particles is 5 nm, average particle diameter B is 6 nm, D is 45 ⁇
  • Lithium perchlorate LiCIO, water and getyl ether were used to determine the elemental concentration of lithium.
  • Particle size B was 19 nm and D was 52 nm.
  • a solution having a total elemental concentration of titanium, lanthanum and lithium of 0.1 mol Z liter was prepared using 3 7 4 3 7 and 2-propanol.
  • the carrier gas was argon
  • the carrier gas pressure was 2.5 atm
  • the pressure inside the reactor 11 was 0.75 atm
  • the voltage applied to the liquid sending pipe 1 was 25 kV DC
  • the solution Fine particles were prepared under the condition of a spraying rate of 70 mlZ, and were collected on the same collecting substrate 14 as in Example 1.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and a quartz tube having an inner diameter of 150 mm and a length of 1000 mm was used as the reactor 11.
  • thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 400 ° C. in the resistance heating furnace 12.
  • X-ray diffraction measurement of the prepared fine particles revealed that the particles were spinel-type LiTiO.
  • Average particle size A of fine particles is 15 ⁇
  • the average particle diameter was 13 nm, and D was 62 nm.
  • a solution having a total elemental concentration of 0.003 mol Zl of titanium was prepared.
  • the carrier gas was air
  • the carrier gas pressure was 2.5 atm
  • the pressure inside the reactor 11 was 0.5 atm
  • the voltage applied to the liquid sending pipe 1 was 30 kV DC
  • the solution Fine particles were prepared at a spraying rate of 950 mlZ, and were collected on a 20 mm square collecting substrate 14 made of quartz using an electrostatic collector 10.
  • the axial direction of the two-fluid nozzle is parallel (0 °) to the ground
  • As the reactor 11, a quartz tube having an inner diameter of 50 mm and a length of 1000 mm was used.
  • thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 750 ° C. in a resistance heating furnace 12 having an axial length of 1000 mm.
  • a thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 750 ° C. in a resistance heating furnace 12 having an axial length of 1000 mm.
  • the average particle diameter A of the fine particles was 20 nm
  • the average particle diameter B was 25 nm
  • D was 85 nm.
  • a 4 molar Z liter solution was prepared.
  • the carrier gas is argon
  • the carrier gas pressure is 1.5 atm
  • the pressure inside the reactor 11 is 0.35 atm
  • the voltage applied to the liquid supply pipe is 15 kV DC
  • the solution is sprayed. Fine particles were produced at a speed of 3 mlZ and collected on the collecting substrate 14 in the same manner as in Example 8.
  • the axial direction of the two-fluid nozzle was 45 ° above the ground.
  • a quartz tube having an inner diameter of 150 mm and a length of 700 mm was used as the reactor 11, a quartz tube having an inner diameter of 150 mm and a length of 700 mm was used.
  • a thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 900 ° C. in the resistance heating furnace 12.
  • the carbon material was a non-graphitizable carbon material.
  • the average particle diameter A of the fine particles was 8 nm
  • the average particle diameter B was 9 nm
  • D was 72 nm.
  • a 4 molar Z liter solution was prepared.
  • the carrier gas is argon
  • the carrier gas pressure is 2 atm
  • the pressure in the reactor 11 is 0.35 atm
  • the voltage applied to the liquid supply pipe 1 is 20 kV
  • the spraying speed of the solution Prepared fine particles under the condition of 5 mlZ and collected them on a quartz substrate of 20 mm square.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and a quartz tube having an inner diameter of 150 mm and a length of 700 mm was used as the reactor 11.
  • a thermocouple 13 for measuring the temperature of the reactor 11 was attached to the center of the tube, and was maintained at 900 ° C. in the resistance heating furnace 12.
  • the average particle diameter A of the fine particles was 10 ⁇ m
  • the average particle diameter B was 13 nm
  • D was 100 nm.
  • Example 11 A stainless steel mesh electrode (5 mesh) arranged in the reactor 11 at a distance of 20 mm from the tip of the two-fluid nozzle was used as the counter electrode 15, and a heating furnace 12 having three heating zones was used. Example 7 was repeated except for ( Figure 4). A DC voltage of 10 kV was applied to the counter electrode. The length of each zone was 330 mm, and the thermocouple 13 located at the center of each zone showed 200, 300, and 400 ° C from the side near the two-fluid nozzle. X-ray diffraction measurement of the prepared fine particles showed that it was spinel-type LiTiO. Particulate
  • the average particle diameter A was 13 nm, the average particle diameter B was 10 nm, and D was 42 nm, which was smaller than that of Example 7.
  • the particle size distribution has become narrower.
  • a stainless steel mesh electrode (800 mesh) arranged in the reactor 11 at a distance of 35 mm from the tip of the two-fluid nozzle was used as the counter electrode 15, and a heating furnace 12 having three heating zones was used.
  • Example 7 was repeated except for ( Figure 4).
  • a DC voltage of 25 kV was applied to the counter electrode.
  • the length of each zone was 330 mm, and the thermocouple 13 arranged in the center of each zone showed 180, 350, and 400 ° C from the side near the two-fluid nozzle.
  • X-ray diffraction measurement of the produced fine particles revealed that the particles were spinel-type LiTiO. Fine grain
  • the average particle size A of the particles was 16 nm, the average particle size B was 15 nm, and D was 30 nm.
  • the particle size distribution became narrower than that of.
  • Example 7 (FIG. 4). A single 30 m diameter orifice was placed at the top of a regular pentagon with a side length of lmm surrounding the axial center of the two-fluid nozzle viewed from the tube axis direction of the two-fluid nozzle.
  • One electrode of the schema was connected to the ground, and was set to substantially 0V.
  • each zone was 330 mm, and the thermocouple 13 located at the center of each zone showed 180, 350, and 400 ° C from the side near the two-fluid nozzle.
  • X-ray diffraction measurement of the produced fine particles showed that the particles were spinel-type Li Ti O.
  • the average particle diameter A of the fine particles is 13 nm
  • the average particle diameter B is 10 nm
  • D is 42 nm.
  • the average particle size B is 14 nm and D is 39 nm, and the particle size distribution is narrower than that of Example 7.
  • a pair of magnets 16 having an axial length of 150mm and a magnetic flux density of 250mT are arranged at a position 100mm away from the tip of the two-fluid nozzle on the outer periphery of the reactor 11, and the length of the heating furnace 12 Example 5 was repeated except that was changed to 650 mm (FIG. 5).
  • the magnets 16 were opposed to each other with the reactor 11 interposed therebetween, and were rotated around the reactor 11 at a speed of 10 rotations Z.
  • the fine particles were perovskite-type Li La TiO.
  • the average particle diameter A of the fine particles is 5 nm
  • the average particle size B was 7 nm, and D was 30 nm. Compared with Example 5, coarse particles were reduced.
  • a neodymium YAG laser light source 17 having a wavelength of 1 ⁇ m is disposed on the outer periphery of the reactor 11 at a distance of 100 mm from the tip of the two-fluid nozzle over an axial length of 150 mm.
  • Example 8 was repeated except that the length of the reactor was 750 mm and the temperature of the reactor 11 was 500 ° C. (FIG. 6). The laser was irradiated continuously at the atomized droplets.
  • the perovskite Li As a result of composition analysis and X-ray diffraction measurement of the prepared fine particles, the perovskite Li
  • the average particle size A was 18 nm, the average particle size B was 23 nm, and D was 80 nm, which was smaller than that of Example 8.
  • Example 7 was repeated, except that the entire apparatus was rotated 90 ° so that the spray direction of the two-fluid nozzle was perpendicular (directly above) the ground.
  • the average particle diameter A of the fine particles was 14 nm
  • the average particle diameter B was 11 nm
  • D was 50 nm.
  • the coarse particles were smaller than those in Example 7.
  • Example 7 By repeating Example 7 except that a copper substrate was used in place of the quartz substrate as the collecting substrate 14, Lithium oxide having a thickness of 100 m and a group force of fine particles deposited on the copper substrate was also obtained.
  • a TiO film is formed, and the LiMn O film having a thickness of 80 m is further formed thereon by repeating Example 3.
  • the fine particles were prepared under the conditions of minute and collected on the collecting substrate 14.
  • the axial direction of the two-fluid nozzle was parallel (0 °) to the ground, and a quartz tube having an inner diameter of 900 mm and a length of 1000 mm was used as the reactor 11.
  • the reaction tube 11 was heated using a resistance heating furnace 12 having three heating zones.
  • the length of each zone was 330 mm, and a thermocouple 13 for measuring the temperature of the reactor 11 was placed at the center of each zone.
  • the thermocouple is close to a 13-powder two-fluid nozzle. Norihara et al. Showed 200, 600, and 300 ° C.
  • Average particle size A of fine particles is 5 nm, average particle size B is 9 nm, D is 28 nm
  • Example 19 was repeated except that the spray solution was a solution having a total elemental concentration of chloroauric acid, water and ethanol of 0.0005 mol Zl, and argon was used as a carrier gas.
  • X-ray diffraction measurement of the prepared fine particles showed that the particles were gold.
  • the average particle diameter A of the fine particles is 3 nm
  • the average particle diameter B is 5 nm
  • D is 15 nm.
  • Example 19 was repeated except that a solution having a total elemental concentration of nickel acetate and nickel of ethanol of 0.0005 mol Z liter was used as the spraying solution, and argon was used as the carrier gas.
  • X-ray diffraction measurement, Raman measurement and TEM observation of the produced fine particles revealed that they were single-walled carbon nanotubes. Using TEM, we observed and photographed 10 times at 10 non-overlapping locations, and obtained the diameter of 100 arbitrary carbon nanotubes from the photograph. Their average diameter was 3 nm.
  • Example 1 was repeated except that no voltage was applied to the liquid sending tube 1.
  • the obtained particles were subjected to X-ray diffraction measurement, and it was found that the particles were anatase-type titanium oxide.
  • the average particle size A of the particles is 515 nm
  • the average particle size B is 485 nm
  • D is 780 nm.
  • the nanometer-sized fine particles aimed at by the invention were not obtained.
  • Example 8 was repeated except that no voltage was applied to the liquid sending tube 1.
  • the average particle diameter A of the particles is 630 nm, the average particle diameter B is 645 nm, and D is 980 nm.

Abstract

La présente invention concerne un procédé pour produire des particules nanométriques qui présentent des diamètres uniformes, ainsi qu'un dispositif pour produire ces particules. Le procédé pour produire des particules fines consiste à pulvériser et à décomposer thermiquement une solution comprenant un élément métallique qui est soumise à une certaine tension avant d'être pulvérisée avec un gaz. Le dispositif de production est caractérisé en ce qu'il comprend une buse à deux liquides, un réacteur (11), un four de chauffage (12), ainsi qu'une source d'alimentation (7). La buse à deux liquides présente un tube d'alimentation en liquide (1) qui comprend à une extrémité une ouverture à jets de solution (3) conçue pour pulvériser la solution et un tube d'introduction de gaz (2) qui est coaxial au tube d'alimentation en liquide (1) sur une longueur prédéfinie sur l'ouverture à jets de solution (3) et comprend une ouverture à jets de gaz située autour de l'ouverture à jets de solution. Le réacteur (11) est relié à une extrémité à l'ouverture à jets de solution et à l'ouverture à jets de gaz et à l'autre extrémité à une ouverture de récupération de particules. Le four de chauffage (12) se trouve autour du réacteur (11) et chauffe le réacteur (11). La source d'alimentation (7) applique une tension sur le tube d'alimentation en liquide (1).
PCT/JP2004/015599 2003-10-23 2004-10-21 Procede et dispositif pour produire des particules fines WO2005040038A1 (fr)

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JPWO2020080400A1 (ja) * 2018-10-19 2021-09-16 日本化学産業株式会社 担持金属触媒及びその製造方法
JP7309154B2 (ja) 2018-10-19 2023-07-18 日本化学産業株式会社 担持金属触媒
US11752490B2 (en) 2018-10-19 2023-09-12 Nihon Kagaku Sangyo, Co, Ltd. Supported metal catalyst and method for producing same
JP2021039872A (ja) * 2019-09-02 2021-03-11 太平洋セメント株式会社 リチウムイオン二次電池の固体電解質用チタン酸ランタンリチウム結晶粒子の製造方法
JP7299110B2 (ja) 2019-09-02 2023-06-27 太平洋セメント株式会社 リチウムイオン二次電池の固体電解質用チタン酸ランタンリチウム結晶粒子の製造方法

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