WO2011105850A2 - 그래뉼 타입 전극을 이용한 금속 나노 입자 제조장치 및 그 방법 - Google Patents

그래뉼 타입 전극을 이용한 금속 나노 입자 제조장치 및 그 방법 Download PDF

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WO2011105850A2
WO2011105850A2 PCT/KR2011/001332 KR2011001332W WO2011105850A2 WO 2011105850 A2 WO2011105850 A2 WO 2011105850A2 KR 2011001332 W KR2011001332 W KR 2011001332W WO 2011105850 A2 WO2011105850 A2 WO 2011105850A2
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Prior art keywords
electrode
metal
metal nanoparticles
granules
electrolysis
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PCT/KR2011/001332
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English (en)
French (fr)
Korean (ko)
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WO2011105850A3 (ko
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최민영
한병선
강윤재
김태균
송용설
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주식회사 아모그린텍
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Priority to CN201180010573.7A priority Critical patent/CN102770368B/zh
Publication of WO2011105850A2 publication Critical patent/WO2011105850A2/ko
Publication of WO2011105850A3 publication Critical patent/WO2011105850A3/ko
Priority to US13/592,684 priority patent/US20120318678A1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0551—Flake form nanoparticles
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to an apparatus for manufacturing metal nanoparticles using an electrolysis method and a method thereof, and in particular, a pair of electrode housings having a predetermined interval between granules made of the same metal as the metal nanoparticles to be obtained as an electrode material using an alternating voltage.
  • the present invention relates to a metal nanoparticle production apparatus and method using a granule-type electrode capable of producing a large amount of metal nanoparticles having a uniform shape and uniform nano size continuously by filling in an electrolysis.
  • methods for obtaining fine metal powders include chemical methods such as coprecipitation, spraying, sol-gel, electrolysis, and reverse phase microemulsion, and grinding methods such as ball mills and stamp mills. Mechanical methods are used.
  • a chemical method for preparing silver powder is a method of reducing silver oxide nitrate or a silver hydroxide precipitated with a reducing agent such as hydrazine, hydrogen peroxide, or formalin by neutralization of an aqueous solution of silver nitrate with an alkaline solution. It is mainly used to inhale the reduced gas such as hydrogen and carbon monoxide to precipitate the produced silver hydroxide, and to reduce it by adding a reducing agent such as formalin and oxalate to the aqueous solution of alkaline amine complex to reduce it to silver powder. do.
  • a reducing agent such as hydrazine, hydrogen peroxide, or formalin
  • this conventional manufacturing method uses a metal salt as an electrolyte as a starting material, it is not environmentally friendly, takes a lot of cost and time to remove the harmful substances, there is a disadvantage that it is not easy to control the particle size.
  • particles are obtained by metallization on the electrode surface by electrolysis using electrodes and metal salts of metal materials to be synthesized, that is, nitrates, carbonates, sulfates, and the like as electrolytes.
  • the reason why the harmful metal salt is used as an electrolyte for obtaining the metal powder in the electrolysis method is that the metal is not dissolved in water, and when the metal combined with the strong acid salt is dissolved in water, it can be easily dissociated into ions and granulated by a reducing agent or the like.
  • harmful substances are generated as by-products, and harmful gases are generated when the temperature is increased, so that they are not environmentally friendly, and particle sizes are not uniform.
  • the starting material itself is not environmentally friendly, and wastewater treatment problems occur during the neutralization and washing process, and there is a lot of troublesome washing process. During the cleaning process, a lot of metal powder is lost.
  • Korean Patent Publication No. 10-2004-105914 in view of the fact that the starting material itself is not environmentally friendly and wastewater treatment problem occurs in the electrolysis method using the conventional metal salt, only the electrode, a small amount of additives and pure water ( In addition to the use of DI-water, by applying an external force to induce the formation and dispersion of metal particles, it has been proposed a method for producing metal nanoparticles using an electrolysis method that can produce metal nanoparticles in an environmentally friendly manner.
  • a solution (2) in which an environment-friendly metal ion reducing agent or an organic metal ion reducing agent is mixed as a pure water and an additive is introduced into a container (1), and the solution (2)
  • Two electrodes 3 are spaced apart in the chamber.
  • two direct current (DC) power supplies are provided in a state in which the ultrasonic generator 4 for emitting ultrasonic waves to the solution 2 and the agitator 5 for stirring the solution 2 are arranged above and below the vessel. It is applied to the electrode 3.
  • the conventional manufacturing method uses a direct current electrolysis method, in which both the positive electrode electrode and the negative electrode electrode are composed of the same components as the metal particles to be obtained, and thus a metal crystal (crystal) is generated on the electrode due to a potential difference. .
  • a direct current (DC) is applied to the metal cation generated in the anode (Anode) is moved to the cathode and around the cathode (Cathode)
  • a direct current (DC) is applied to the metal cation generated in the anode (Anode) is moved to the cathode and around the cathode (Cathode)
  • the amount is very small in the reaction solution compared to the amount of oxidized Ag 2 O and grown silver particles. It is not suitable for high efficiency mass production method.
  • the method for preparing copper nanoparticles according to the registered patent includes a metal ion reducing agent, which is a substance capable of reducing hydrazine or copper ions, and a metal ion generator, which is a substance capable of ionizing copper on the surface of trisodium citrate or a copper electrode, in water.
  • a metal ion reducing agent which is a substance capable of reducing hydrazine or copper ions
  • a metal ion generator which is a substance capable of ionizing copper on the surface of trisodium citrate or a copper electrode, in water.
  • Injecting and dissolving Placing a copper electrode in the solution spaced apart, the electrode is composed of the same components as the metal particles to be obtained, the electrical energy generated by the alternating voltage applied to the electrode and ionized in the solution by the metal ion generator Becoming a step; And reducing copper ions by the reducing agent in the solution to precipitate copper particles.
  • the metal electrode for producing copper nanoparticles of the prior art is used that consists of a plate-shaped rod electrode.
  • a plate-shaped bar electrode is disposed before the reaction, and as the electrolysis reaction proceeds, the electrode is gradually consumed, and after a certain time, the end of the bar electrode is deformed to be sharp.
  • the deformed portion in order to maintain a constant interval, the deformed portion must be cut and reset at regular intervals or replaced with a new electrode, so that efficient and effective use of the electrode cannot be achieved, and thus the life of the electrode is not long. Moreover, since the resetting process and the replacement process of these electrodes must be performed by hand periodically during mass production, there is a problem in that productivity is lowered.
  • an object of the present invention is to fill the granules or flakes made of the same metal material as the metal nanoparticles to be obtained in a pair of electrode housings installed at regular intervals in the electrolytic cell, so that the distance between the electrodes even when the electrolysis proceeds. It is to provide a metal nanoparticle manufacturing apparatus and method using a granule-type electrode that can be obtained a metal nanoparticles of a uniform size does not change.
  • Another object of the present invention is to continuously fill the metal granules or flakes as the metal granules or flakes are consumed in the electrolysis process, the metal nanoparticles can be easily produced in a large amount of metal nanoparticles continuously without production interruption due to electrode replacement It is to provide a manufacturing apparatus.
  • the present invention provides a metal nanoparticle manufacturing apparatus that can manufacture a large amount of metal nanoparticles with high efficiency by selecting an optimal frequency from an AC power source and applying it to an electrode.
  • Another object of the present invention is to provide an apparatus for producing metal nanoparticles and a method for producing the metal nanoparticles in an environmentally friendly manner using an alternating current electrolysis method.
  • the present invention is a reaction vessel containing an electrolytic solution; First and second electrodes formed by filling a plurality of granules or flakes made of the same metal as the metal nanoparticles to be obtained in the first and second electrode housings spaced in the reaction vessel, respectively; And a power supply for applying an alternating current power between the first and second electrodes for an electrolysis reaction, wherein the first and second electrode housings are connected from the first and second electrodes in accordance with an electrolysis reaction.
  • an apparatus for producing metal nanoparticles characterized in that it comprises a plurality of holes or slits on at least facing each other to discharge the eluted metal ions.
  • the present invention is a reaction vessel containing an electrolytic solution; A first electrode formed by filling a plurality of granules or flakes made of the same metal as the metal nanoparticles to be obtained in an electrode housing installed inside the reaction vessel; A second electrode disposed in the reaction vessel at intervals from the first electrode; And a power supply device for applying AC power between the first and second electrodes for an electrolysis reaction, wherein the electrode housing includes a plurality of electrode housings to discharge metal ions eluted from the first electrode according to the electrolysis reaction. It provides a metal nanoparticle manufacturing apparatus characterized in that it comprises a hole or a slit.
  • the apparatus for manufacturing metal nanoparticles according to the present invention may further include a support holder for supporting the first electrode housing and the second electrode housing at a predetermined distance from each other in an insulated state.
  • the support holder is granules or flakes filled in the first and second power cables and the first and second electrode housings for supplying AC power applied between the first and second electrodes from the power supply device on both sides. It may further include a first and second electrode terminal for interconnecting the.
  • the first and second electrode housings may each have a cylindrical shape having a rectangular cross section or a polygon.
  • first and second electrode housings each include a plurality of protrusions having a serrated side facing each other and having first and second side plates having a plurality of holes or slits formed on both sides of the protrusions.
  • the first and second side plates may each consist of a mesh made of Ti.
  • first and second electrode housings may have a circular double cylinder structure concentrically arranged with different diameters.
  • the manufacturing apparatus may further include a stirrer having an impeller disposed at the distal end of the rotating shaft extending through the center of the second electrode housing and rotatably supported by a bearing supported by the support holder.
  • the manufacturing apparatus may further include a conductive plate inserted into the inner spaces of the first and second electrode housings to make mutual contact with the granules or the flakes.
  • the granules or flakes are composed of any one or two or more alloys selected from the group consisting of Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni, and Pd, and the size of the granules or flakes Is set in the range of 0.05 to 10 cm, preferably in the range of 0.5 to 5 mm.
  • the first and second electrode housings may be any one selected from the group consisting of polymer polymer, ceramic, glass, and titanium (Ti).
  • the electrode housing has a cross-shaped accommodating space therein, and has a plurality of holes or slits on the lower side thereof, and the second electrode is disposed to face the lower side of the electrode housing and has a plate shape.
  • the electrode housing has a cross-shaped accommodating space therein, a plurality of holes or slits on the side, the second electrode preferably accommodates the electrode housing therein and is made of a cylindrical or cylindrical mesh.
  • the electrode housing is rotationally driven to maintain a constant distance between the first and second electrodes, and the second electrode is made of Ti.
  • the present invention comprises the steps of preparing an electrolytic solution by dissolving the electrolyte and the dispersant in the pure water in the reaction vessel; First and second granules or flakes made of the same metal as the metal nanoparticles to be obtained in the first and second electrode housings disposed to face the inside of the reaction vessel and having a plurality of holes or slits on opposite surfaces thereof. And forming a second electrode; Generating metal ions by ionizing the metal granules or flakes into the electrolytic solution by applying an AC power source between the first and second electrodes and performing electrolysis; And reducing the metal ion with a reducing agent to form metal nanoparticles.
  • the present invention comprises the steps of preparing an electrolytic solution by dissolving the electrolyte and dispersant in the pure water in the reaction vessel;
  • the first electrode formed by filling a plurality of granules or flakes made of the same metal as the metal nanoparticles to be obtained in the electrode housing, and a second electrode made of a plate or cylindrical shape and facing at least one surface of the first electrode Installing in the reaction vessel;
  • Generating metal ions by ionizing the metal granules or flakes into the electrolytic solution by applying an AC power source between the first and second electrodes and performing electrolysis; And reducing the metal ion with a reducing agent to form metal nanoparticles.
  • the reducing agent may achieve high yield and uniform particle size distribution of the obtained nanoparticles so as to be introduced into the electrolytic solution so that the concentration of the reducing agent is at a constant level corresponding to the concentration of metal ions generated as the electrolysis proceeds.
  • the frequency f of the AC power supply in the range of 0 ⁇ f ⁇ 10Hz in terms of yield and particle size distribution.
  • the present invention preferably further includes the step of periodically detecting the consumption of granules or flakes filled in the first and second electrode housings to fill new granules or flakes.
  • the electrolysis proceeds. It does not change, it is possible to obtain a metal nanoparticles of uniform size.
  • the metal granules or flakes may be continuously filled, thereby easily producing a large amount of metal nanoparticles continuously and without interruption of production due to electrode replacement.
  • mass production of metal nanoparticles can be achieved by reducing metal ions to metal nanoparticles using a reducing agent before metal ions are formed into crystals and converting polarities before metal ions that have not been reduced are grown into nanocrystals.
  • a reducing agent before metal ions are formed into crystals and converting polarities before metal ions that have not been reduced are grown into nanocrystals.
  • the metal nanoparticles may be environmentally friendly while using an alternating current electrolysis method.
  • FIG. 1 is a schematic configuration diagram showing a conventional metal nanoparticle manufacturing apparatus
  • Figure 2 is a photograph showing the state before and after use of the electrode used in the conventional metal nanoparticle manufacturing apparatus
  • FIG. 3 is a schematic view of a metal nanoparticle manufacturing apparatus according to a first embodiment of the present invention
  • FIG. 4 is a perspective view showing a granule type electrode used in the apparatus of FIG. 3;
  • FIG. 5 is a vertical cross-sectional view of the granule type electrode of FIG. 4;
  • FIG. 6 is a perspective view showing a granule-type electrode for a metal nanoparticle manufacturing apparatus according to a second embodiment of the present invention.
  • FIG. 7 is a plan view showing a modification of the granule-type electrode used in the first and second embodiments
  • FIGS. 8 and 9 are schematic cross-sectional view and a bottom view of a metal nanoparticle manufacturing apparatus according to a third embodiment of the present invention.
  • FIGS. 10 and 11 are schematic perspective views of a metal nanoparticle manufacturing apparatus according to a fourth and a fifth embodiment of the present invention, respectively;
  • FIG. 12 is a schematic perspective view of a metal nanoparticle manufacturing apparatus according to a sixth embodiment of the present invention.
  • 13 and 14 are cross-sectional views showing granule-type electrodes of the metal nanoparticle manufacturing apparatus according to the sixth embodiment, respectively.
  • FIG. 3 is a schematic view of the metal nanoparticle manufacturing apparatus according to the first embodiment of the present invention
  • Figure 4 is a perspective view showing a granule-type electrode used in the apparatus of Figure 3
  • Figure 5 is a granule-type electrode of Figure 4 Vertical cross section.
  • an electrolytic solution 11 in which an additive is mixed with pure water is filled in the reaction vessel 10, and the electrolytic solution 11 )
  • the first electrode 30 and the second electrode 40 in which a plurality of metal particles, for example, granules or flakes 30a and 40a made of silver, are placed in the support holder 15. It has a structure arranged opposite to each other by the space
  • a stirrer 20 for stirring the electrolytic solution 11 is selectively disposed under each of the first electrode 30 and the second electrode 40, and an electrolytic solution 11 is disposed below the reaction vessel 10.
  • Heating device 25 is arranged to indirectly heat the heating.
  • the power supply device 50 for applying AC power to the first electrode 30 and the second electrode 40 is connected to the upper portion of the reaction vessel 10.
  • the stirrer 20 may employ a structure in which a magnet piece disposed in the reaction vessel 10 is rotated by a driving device (not shown) disposed outside the reaction vessel 10.
  • a plurality of silver granules or flakes 30a and 40a are used as the first electrode 30 and the second electrode 40, for example, to obtain silver nanoparticles as the metal nanoparticles to be obtained.
  • the present invention may also produce other types of metal nanoparticles in addition to the production of silver nanoparticles using silver granules or flakes 30a and 40a. That is, in the present invention, in addition to granules or flakes of silver (Ag) as the first electrode 30 and the second electrode 40, copper (Cu), nickel (Ni), gold (Au), palladium (Pd), and platinum Any material that can elute metal ions such as (Pt) can be used.
  • the first electrode 30 and the second electrode 40 may include a plurality of granules or flakes (hereinafter, simply abbreviated as “granules”) 30a and 40a, respectively.
  • granules granules or flakes
  • the second electrode housings 32 and 42 are filled in an example, the shape of the electrode housing may accommodate granules therein, and an electrolyte solution between the first electrode 30 and the second electrode 40. If the contact area with (11) is large, the shape of the first and second electrode housings 32 and 42 is not limited.
  • the granules 30a and 40a used for the second electrode 40 and the first electrode 30 may be made of the same material as the metal nanoparticles (or particles) to be manufactured, and the granules 30a and 40a of the granules 30a and 40a may be used.
  • the size is preferably 0.05 to 10 cm, more preferably 0.5 to 5 mm, if the first and second electrode housings 32 and 42 have a plurality of slits, holes or nets.
  • the first and second electrode housings 32 and 42 filled with the granules 30a and 40a used as the first electrode 30 and the second electrode 40, respectively, are spaced at regular intervals by the support holder 15.
  • the support holder 15 has a pair of rectangular through holes corresponding to the cross-sectional shapes of the first and second electrode housings 32 and 42, and supports the first and second electrode housings 32 and 42.
  • the support holder 15 maintains a constant distance while supporting the upper side of each electrode housing (32, 42) in an insulating state.
  • the remaining portions of the first and second electrode housings 32 and 42 are exposed to the lower side of the support holder 15 to face each other at regular intervals.
  • a plurality of slits or holes are formed on opposite surfaces and side surfaces of the first and second electrode housings 32 and 42, respectively.
  • 33 and 43 may be any shape as long as the electrolyte solution 11 is accommodated in the first and second electrode housings 32 and 42 and the electrolytic metal nanoparticles can be eluted. .
  • the first and second electrode housings 32 and 42 can be continuously filled, so there is no need to replace the electrodes.
  • the slits 33 and 43 on the outer surfaces of the housings 32 and 42 may be formed to be inclined upward toward the outside of the electrode housings 32 and 42 in a structure in which the granules 30a and 40a cannot escape.
  • the widths of the slits 33 and 43 are set smaller than the sizes of the granules 30a and 40a, and preferably 0.1-1 mm.
  • the materials used for the first and second electrode housings 32 and 42 are materials insoluble in the electrolytic solution 11, preferably insulating materials such as MC nylon, nylon, polyester, Polymer family such as polystyrene, polyvinyl chloride, carbon, ceramic or glass, for example, Pyrex glass, or insoluble in the electrolyte solution 11, the current flowing titanium ( Ti) can be used.
  • insulating materials such as MC nylon, nylon, polyester, Polymer family such as polystyrene, polyvinyl chloride, carbon, ceramic or glass, for example, Pyrex glass, or insoluble in the electrolyte solution 11, the current flowing titanium ( Ti) can be used.
  • first and second electrode housings 32 and 42 may have any number of slits, holes, gratings or nets through which metal, for example, silver (Ag) ions, can pass on opposite surfaces or sides. Forms or materials are also possible.
  • first and second electrode housings 32 and 42 may face each other, and the opposite surfaces may be formed of titanium (Ti), and separately form side plates having a plurality of slits, holes, gratings or meshes, and the remaining portions may be formed. It is also possible to fabricate one polymer family, ceramic or glass and then assemble it.
  • a bag made of a woven or nonwoven fabric made of a material insoluble in the electrolytic solution it is also possible to use a powder having a particle size of 0.5 ⁇ m to 1 cm for the first electrode 30 and the second electrode 40 instead of granules.
  • bolt-shaped first and second electrode terminals 34 and 44 are fixed to both side surfaces of the support holder 15, and are formed through the bolt-shaped first and second electrode terminals 34 and 44.
  • An alternating current (AC) voltage is applied to the granules 30a and 40a inside the first and second electrode housings 32 and 42.
  • the first and second electrode terminals 34 and 44 are connected to the power supply device 50 through a pair of power cables 55 connected by the first and second lugs 35 and 45 for protecting the terminal. (AC) voltage is applied.
  • the support holder 15, the first and second electrode terminals 34 and 44, and the pair of power cables 55 are exposed to the outside of the reaction vessel 10 so as not to contact the electrolyte solution 11. It is desirable to be.
  • a pair of power cables 55 exposed to the outside is connected to a power supply device 50 for supplying AC power required for electrolysis from the outside of the reaction vessel 10.
  • the power supply device 50 includes, for example, a function generator capable of selecting the waveform and frequency of the AC power required for electrolysis, and an amplifier for amplifying the current or voltage of the AC power generated from the function generator. The output of the amplifier is connected to the first electrode 30 and the second electrode 40.
  • the power supply device 50 has a predetermined waveform and frequency at the first and second electrodes 30 and 40, and can set a current or voltage having a desired size in advance. Any type of power supply can be used, including a dedicated power supply that can supply power.
  • a constant current source may be provided in the power supply device to supply a constant current intensity set between the first and second electrodes 30 and 40 during electrolysis.
  • the waveform of the AC power supply may be any waveform such as, for example, a sine wave, square wave, triangular wave, sawtooth wave, etc., and the waveform change of the AC power supply is merely There is only a slight difference in the yield of the resulting metal nanoparticles and the shape of the particles.
  • the yield and particle size distribution of the nanoparticles obtained by changing the frequency of the AC power source from 100Hz to 0.1Hz to see the effect of the frequency as a factor affecting the yield in the production of metal nanoparticles by the electrolysis method The growth of the particles was investigated.
  • the yield of the nanoparticles is preferably a frequency f of 0 ⁇ f ⁇ 10Hz as the frequency f of the AC power supply, more preferably 0.1 ⁇ f ⁇ 5Hz.
  • the most preferable interval is 0.1 ⁇ f ⁇ 1Hz considering both the yield, particle size distribution and growth of particles.
  • the frequency of the power supply is 0 Hz, that is, direct current (DC)
  • metal ions are oxidized at the anode, and electrons provided from the cathode are moved to the cathode by an electric field before the unoxidized metal ions are reduced by the reducing agent.
  • the metal nanoparticles are reduced to metal on the surface of the negative electrode and grow up to a micrometer size, the desired metal nanoparticles have a problem of low yield.
  • the distribution and particle size of the metal nanoparticles decreased as the frequency decreased from 100Hz to 10Hz.
  • the distribution and particle size of the metal nanoparticles decreased when the frequency decreased from 10Hz to 0.1Hz. The size is further reduced.
  • the amount of metal particles to be obtained is determined as in the chemical method, and the amount of metal ions suitable for the initial reaction conditions is not put in the reaction vessel and the reaction is continuously performed. Accordingly, the metal ions are generated in the metal electrode and the ions are reduced by the reducing agent. As a result, the metal nanoparticles generated due to the polarity of the electrode and the interaction of the nanoparticles in this reaction process may exhibit the characteristics of returning to the electrode. However, this phenomenon is the biggest problem in yield, that is, mass productivity.
  • the amount of generated metal ions is determined by the strength of the current of the alternating current power applied between the two electrodes, and the strength of the current can be controlled by the concentration of the electrolyte and the voltage applied to the electrode. According to the research results of the present inventors, it was found that the yield of the metal nanoparticles is high when the concentration of the reducing agent is maintained at a constant level in consideration of the concentration of the metal ions generated by the constant current intensity (current value). .
  • the amount of the reducing agent is relatively insufficient, so that the rate of reduction of the metal ions is relatively reduced, but it does not cause significant problems in yield.
  • the amount of the reducing agent is relatively insufficient, the side effect of increasing the size of the particle occurs.
  • the concentration of the reducing agent is too large than the concentration of the metal ions produced, the reduction rate is too fast to produce particles of several nanometers or less, and the yield is drastically reduced by returning back to the electrode even before capping with the dispersant.
  • the type and concentration of the electrolyte is directly related to the strength of the pH and current.
  • electrolytes are usually divided into acidic electrolytes, basic electrolytes and neutral electrolytes.
  • the pH is less than 7, for example, when a weak alkaline hydrazine is added as a reducing agent, hydrazines are acidic electrolytes and acids. It is a base reaction. Therefore, a sufficient amount of weak alkaline hydrazine should be put in order to control the size of the particles by controlling the reduction reaction rate.
  • the pH of the reaction solution becomes 7 or more, which increases the chance of electrons moving in the reaction solution, and the reaction rate of the hydrazine, a weak alkali used as a reducing agent, increases, thereby increasing the reaction rate of several nano-sized particles. Is generated and returned to the electrode before being protected by the dispersant.
  • an acid and basic electrolyte are mixed and used, and the pH is set to 7-9.
  • Method for producing metal nanoparticles using the electrolysis method according to the present invention can be implemented using the above metal nanoparticle manufacturing apparatus, the dispersant and the electrolyte in the reaction vessel 10 by dissolving in ultrapure water (DI-water) electrolysis Preparing a solution 11, disposing the first and second electrodes 30, 40 made of the same metal material as the nanoparticles to be synthesized in the electrolytic solution 11 at a distance, the first electrode Ionizing metals of the first and second electrodes 30 and 40 into the electrolytic solution according to an electrolysis method in which an AC power source having a predetermined frequency f is applied between the 30 and second electrodes 40. And reducing the metal ions with a reducing agent to form metal nanoparticles.
  • DI-water ultrapure water
  • the electrolytic solution 11 contains an electrolyte, a reducing agent and a dispersant as an additive in pure water, particularly preferably ultrapure water.
  • the electrolyte solution is used by mixing an acidic electrolyte and a basic electrolyte, it is preferably set to pH 7 to pH 9.
  • the electrolyte may be used by mixing citric acid (citric acid) and hydrazine (Hydrazine).
  • the electrolyte is nitric acid, formic acid (acetic acid), acetic acid (acetic acid), citric acid (citric acid), tartaric acid (tataric acid), glutaric acid (glutaric acid), acid consisting of hexanoic acid (hexanoic acid), the Any one or two or more selected from the group consisting of an alkali metal salt of an acid, ammonia (NH 3 ), triethyl amine (TEA), and an amine of pyridine can be used.
  • the electrolyte used in the present invention may use citric acid as an environmentally friendly electrolyte, and may use amino acids such as glycine as necessary.
  • hydrazine hydrazine: N 2 H 4
  • sodium hypophosphite NaH 2 PO 2
  • sodium borohydride NaBH 4
  • dimethylamine borane dimethylamine borane: ( Any one or two or more selected from the group consisting of CH 3 ) 2 NHBH 3 ), formaldehyde (HCHO), and ascorbic acid can be used.
  • the reducing agent is an environmentally friendly reducing agent, for example, it is preferable to use an organic ion reducing agent such as hydrazine (Hydrazine).
  • the organic ion reducing agent is not harmful after the completion of the reaction because it is consumed by generating both nitrogen gas and water during the reaction.
  • the reducing agent is introduced into the electrolytic solution so that the concentration of the reducing agent becomes a constant level corresponding to the concentration of the metal ions generated when the electrolysis reaction proceeds according to the application of an AC power supply through a reducing agent supply device (not shown).
  • metal nanoparticles can be obtained through an environmentally simple method by using an environmentally friendly electrolyte and an environmentally friendly organic ion reducing agent without using an electrolyte harmful to the environment based on pure water (DI-water). .
  • the dispersant is dissociated from the first and second electrodes 30 and 40 by electrolysis, and ionized metal ions are reduced by the reducing agent, and then the reduced metal nanoparticles are returned to the electrode and attached or the metal nanoparticles. It serves to cap the surface of the metal nanoparticles to prevent the phenomenon of precipitation by cohesion of the liver, it may be used a water-soluble polymer dispersant or a water dispersion polymer dispersant.
  • the water-soluble polymer dispersant may be a polyacryl, polyurethane, or polysiloxane-based aqueous polymer dispersant
  • the water-dispersible polymer dispersant may be a polyacryl, polyurethane, or polysiloxane-based aqueous polymer dispersant.
  • the ultra-pure water refers to tertiary distilled water having almost no anions and cations existing in tap water or bottled water, which is impurity in the desired metal nanoparticles when anions and cations are added in addition to the electrolyte and the reducing agent when preparing the metal nanoparticles. This may occur, and complex compounds may not be formed to obtain metal nanoparticles.
  • the silver metal nanoparticles to be synthesized in the reaction vessel 10 of the metal nanoparticle manufacturing apparatus as the same metal material each of the plurality of silver granules
  • the first electrode 30 and the second electrode 40 made of the 30a and 40a are disposed in the support holder 15 so that the first electrode 30 and the second electrode 40 are spaced apart from each other.
  • Heat was added to the aqueous solution in which all the additives were dissolved to raise the temperature of the aqueous solution to 90 ° C, and then coolant was flowed to the reaction vessel to maintain the set temperature.
  • the electrolysis was performed by setting the current value to 4.3 A while applying between the first and second electrodes. Further, the reaction was carried out while injecting 18.0 mmol of hydrazine as a reducing agent by constant speed injection using a pump while performing electrolysis for 1 hour and 30 minutes.
  • the preparation of the metal nanoparticles using the electrolysis method according to the first embodiment of the present invention was able to obtain silver nanoparticles having a small, uniform size and a uniform shape on the order of tens of nanometers.
  • a metal plate or a rod instead of a metal plate or a rod, it is changed into a granule to fill a pair of electrode housings so as to maintain a constant interval, and a pair of electrodes is formed. Since the distance does not occur in the liver, metal nanoparticles of uniform shape and uniform nano size can be manufactured in large quantities.
  • the new granules may be filled according to the consumption of the granules filled in the pair of electrode housings to continuously manufacture a large amount of metal nanoparticles without stopping the electrolysis process.
  • the present invention it is possible to prevent interruption of the electrolysis process by replenishing granule-shaped metal grains in the internal space of the electrode housing without having to replace the electrode consumed in the electrolysis process, thereby increasing productivity.
  • Figure 6 is a perspective view showing a granule type electrode for a metal nanoparticle manufacturing apparatus according to a second embodiment of the present invention.
  • the granule-type electrode for the metal nanoparticle manufacturing apparatus according to the second embodiment of the present invention is compared with the granule-type electrode of the first embodiment shown in FIG. 3, and the first and second electrode housings 32 There is a difference in that a plurality of holes 33a and 43a are formed instead of slits on opposite sides of 42, and the rest of the configuration is the same.
  • the holes 33a and 43a may be formed to be inclined upward toward the outside of the electrode housings 32 and 42 in a structure in which the granules 30a and 40a cannot escape.
  • FIG. 7 is a plan view showing a modification of the granule type electrode used in the first and second embodiments.
  • the granule-type first and second electrodes 30 and 40 have a first and second electrode housing 32 filled with a plurality of granules 30a and 40a to further improve electrical conductivity.
  • the conductive plate 37 is inserted into the inner space of 42 in the longitudinal direction, respectively.
  • the conductive plate 37 is made of the same material as the granules 30a and 40a.
  • the electrical conductivity can be further improved, and the electrolysis efficiency can be increased.
  • FIGS. 8 and 9 are schematic cross-sectional view and a bottom view of a metal nanoparticle manufacturing apparatus according to a third embodiment of the present invention.
  • the same components as those of the metal nanoparticle manufacturing apparatus of the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.
  • the metal nanoparticle manufacturing apparatus has a cylindrical shape of a double cylinder structure in order to maximize the opposing area between the first electrode 60 and the second electrode 70.
  • An example employing an electrode housing is proposed.
  • the cylindrical first and second electrode housings 62 and 72 according to the third embodiment of the present invention have a double-cylinder structure whose bottom is closed so as to have an annular accommodating space for filling a plurality of granules 60a and 70a, respectively. Consists of
  • the first electrode 60 and the second electrode 70 filled with a plurality of granules 60a and 70a made of the same material are used.
  • the first electrode 60 and the second electrode 70 are spaced apart from each other as they are connected to each other by the plurality of connection parts 12 having the same length between the first electrode housing 62 and the second electrode housing 72. do.
  • the interval between the first electrode housing 62 and the second electrode housing 72 is set constant for all of the outer peripheral surfaces facing each other, so that the interval between the first electrode 60 and the second electrode 70 is also determined. It is set constant.
  • a plurality of slits or holes 63 are formed on the inner circumferential surface of the first electrode housing 62, and a plurality of slits or holes 73 are formed on the outer circumferential surface of the second electrode housing 73 facing the first electrode housing 62. have.
  • an impeller that is, an agitator 20
  • the rotating shaft 22 of the stirrer 20 is disposed to penetrate the center of the second electrode housing 72, and a bearing 14 supported by a plurality of connection parts 13 inside the lower side of the second electrode housing 72.
  • One end of the rotation shaft 20 is rotatably supported.
  • an electrolytic solution 11 containing an electrolyte, a dispersant, and a reducing agent as an additive is contained in ultrapure water, and a heating apparatus for indirectly heating the electrolytic solution 11 at the lower side of the reaction vessel 10. (Not shown), and a pair of power supplies are provided on top of the reaction vessel 10 for supplying AC power to the first electrode 60 and the second electrode 70. It is connected via a cable 55.
  • the metal nanoparticle manufacturing apparatus configured as described above has a cylindrical first and second cylindrical structure having a double cylinder structure in order to maximize the opposing area between the first electrode 60 and the second electrode 70. As the electrode housings 62 and 72 are employed, the opposing area increases, whereby the yield of the metal nanoparticles can be increased.
  • the first and second electrode housings 62 and 72 are filled to form the first and second electrodes 60 and 70 so as to maintain a predetermined interval by replacing the metal plate or rod with granules.
  • the electrolysis is performed using an AC power source, even though the electrolysis proceeds, the distance does not change between the first and second electrodes 60 and 70, so that a large amount of metal nano particles having a uniform shape and a uniform nano size can be obtained. It can manufacture.
  • the present invention does not stop the electrolysis process by filling the new granules 60a and 70a according to the consumption of the granules 60a and 70a filled in the first and second electrode housings 62 and 72 as the electrolysis proceeds. It is possible to produce a large amount of metal nanoparticles continuously without. As a result, in the present invention, it is possible to prevent the interruption of the electrolysis process by replenishing granule-shaped metal grains in the internal space of the electrode housing without having to replace the electrodes consumed in the electrolysis process and to increase productivity by the continuous process. have.
  • FIGS 10 and 11 are schematic perspective views of the metal nanoparticle manufacturing apparatus according to the fourth and fifth embodiments of the present invention, respectively.
  • the metal nanoparticle manufacturing apparatus may include the electrode housings 82 and 82a respectively accommodating granules (not shown). Unlike the first to third embodiments, there is a difference in that only one electrode housing is used.
  • the second electrodes 90 and 90a facing the first electrode 80 formed by granules accommodated in the electrode housings 82 and 82a may be a disk or a cylinder which may be energized only when an AC power source for electrolysis is applied. Consists of, the electrode housing (82, 82a) for accommodating the granule is made by the rotation drive (not shown).
  • the second electrodes 90 and 90a of the fourth and fifth embodiments are selected as metal materials which are not eluted from the electrolytic solution, such as Ti.
  • the electrode housing 82 accommodating the granules may have, for example, a cross-sectional accommodating space.
  • the shape of the electrode housing 82 may be any shape in addition to the cross shape described above as long as it is a tubular structure capable of accommodating granules, for example, a star-shaped cylinder, a cylinder, a polygonal cylinder, and the like. Therefore, the first electrode 80 is composed of a plurality of granules accommodated in the electrode housing 82.
  • the slit 83 of the electrode housing 82 through which the metal ions eluted during electrolysis are discharged has a lower side ( 84).
  • the electrode housing 82 As the electrode housing 82 is rotated, a constant interval is maintained between the first and second electrodes 80 and 90 during the electrolysis reaction, and at the same time, an effective reaction environment of the generated metal ions and the reducing agent is created. The efficiency of mixing can be maximized.
  • reference numeral 91 denotes a conduit 91 in which a power cable for applying AC power to the second electrode 90 disposed at the bottom of the reaction vessel 10 is accommodated.
  • the metal nanoparticle manufacturing apparatus according to the fifth embodiment of the present invention shown in FIG. 11 uses an electrode housing 82a accommodating granules having the same structure as the electrode housing 82 according to the fourth embodiment.
  • the difference between the fifth embodiment and the fourth embodiment of the present invention is that the second electrode 90a facing the first electrode 80a surrounds the electrode housing 82 of the first electrode 80a and has a cylindrical thickness. Or there is a difference in that it is made of a cylindrical net (net) structure.
  • the cylindrical second electrode 90a is disposed on the side of the first electrode 80a, the slit 83a of the electrode housing 82a through which the metal ions eluted at the time of electrolysis is discharged is formed in the electrode housing ( 82a).
  • the electrode housing 82a has a cross shape
  • the four side surfaces 84a and the cylindrical second electrodes 90a are disposed at regular intervals, so that a constant interval is also provided between the first and second electrodes 80a and 90a. Stays on.
  • the fourth and fifth embodiments described above use only one electrode housing 82, 82a, which makes it easy to manage the replenishment of the spent granules.
  • FIGS. 13 and 14 are cross-sectional views illustrating granule-type electrodes of the metal nanoparticle manufacturing apparatus according to the sixth embodiment, respectively.
  • the first electrode 300a and the second electrode 400a face each other (particularly, the first and second side plates 34a and 44a) are set at the same distance, but the structure of the opposite side is different. It is shown in a state opened at a constant angle for convenience of explanation.
  • the metal nanoparticle manufacturing apparatus maximizes the so-called "edge effect" in which the ion elution from the electrode is greater at the corners of the electrode than at other corners at the time of electrolysis.
  • An electrode structure can be proposed.
  • the apparatus for manufacturing metal nanoparticles includes, for example, first and second electrode housings 32a and 42a having a rectangular cylindrical shape to accommodate granules (not shown).
  • Each side has a structure consisting of first and second side plates 34a and 44a, each of which is made of an insoluble electrode material such as Ti, and a plurality of serrated protrusions (corresponding to threaded threads) 35a and 45a protrude to a constant height. .
  • the first and second electrode housings 32a and 42a are insulative materials insoluble in the electrolytic solution, for example, MC nylon, nylon, and polyester, as in the electrode housings of the first to third embodiments.
  • Polymer family such as polystyrene, polyvinyl chloride, ceramic or glass, for example Pyrex glass, may be used, and the first and second side plates 34a and 44a may be current carrying.
  • Insoluble material titanium (Ti) may be used.
  • the first and second side plates 34a and 44a may be formed of the first and second side plates 34a and 44a. And contact with a plurality of granules filled in the second electrode housings 32a and 42a, so that when the AC power is applied to the granules, the first and second side plates 34a and 44a are energized with the plurality of granules. .
  • the first and second side plates 34a and 44a have a plurality of jagged protrusions (corresponding to the threaded threads) 35a and 45a protruding at a constant height so as to face the opposite protrusions (corresponding to the threaded threads) (
  • the spacing between 35a and 45a is set equal, and a number of holes or slits 33a and 43a are formed on the side surfaces of each of the projections 35a and 45a.
  • the first and second side plates 34a and 44a may be used by bending a Ti sheet having a net structure so that a plurality of holes or slits 33a and 43a are regularly arranged.
  • first and second side plates 34a and 44a have a plurality of jagged protrusions (corresponding to threaded threads) 35a and 45a, so that the surface areas facing each other increase as compared with the flat plate structure. As a result, the efficiency of the metal nanoparticles obtained can be increased.
  • the first and second granules are energized according to the edge effect. And a plurality of granules filled on one side between the second electrode housings 32a and 42a to form the first electrode 300a and eluted with an electrolytic solution while giving electrons to the plurality of granules of the second electrode 400a on the other side.
  • the elution amount of the metal ions to be increased.
  • the metal nanoparticle manufacturing apparatus is a projection of the first and second side plates 34a and 44a in the first and second electrode housings 32a and 42a as shown in FIG. 14.
  • (35a, 45a) is set to the structure arrange
  • the projections 35a and 45a of the first and second side plates 34a and 44a are arranged in parallel to each other in the vertical direction.
  • the protrusions 35a and 45a of the first and second side plates 34a and 44a are arranged in parallel to each other in the horizontal direction.
  • the granules or flakes made of the same material as the metal nanoparticles to be obtained are filled in a pair of electrode housings installed at predetermined intervals in the electrolytic cell, so that the electrolysis proceeds between the two electrodes. Since the distance does not change, metal nanoparticles of uniform shape and uniform size can be obtained.
  • the present invention as the metal granules or flakes are consumed in the electrolysis process, new metal granules or flakes are continuously filled, thereby allowing a large amount of metal nanoparticles to be produced continuously and conveniently without interruption of production due to electrode replacement.
  • it is possible to prevent the interruption of the electrolysis process by replenishing the granules with the electrode housing without having to replace the electrodes consumed in the electrolysis process, thereby increasing productivity.
  • mass production of metal nanoparticles can be achieved by reducing metal ions to metal nanoparticles using a reducing agent before metal ions are formed into crystals and converting polarities before metal ions that have not been reduced are grown into nanocrystals.
  • a reducing agent before metal ions are formed into crystals and converting polarities before metal ions that have not been reduced are grown into nanocrystals.
  • silver (Ag) which is a metal having a low ionization tendency
  • a metal having a high ionization tendency for example, Mg, Al, Zn, Fe, Cu
  • Pt, Au, etc. Similar results can be obtained by applying Pt, Au, etc., which have a small tendency to ionize.
  • pure silver (Ag) is used as a material of granule or flake, but is selected from the group consisting of Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni, and Pd.
  • Two or more alloys for example, Ag-Cu, Ag-Mg, Ag-Al, Ag-Ni, Ag-Fe, Cu-Mg, Cu-Fe, Cu-Al, Cu-Zn, Cu-Ni, etc. When using the alloy nanoparticles can be obtained.
  • the alloy nanoparticles have a melting point lower than the melting point of each metal before the pure alloy, low sintering temperature can be expected in preparing the ink using the alloy nanoparticles.
  • the present invention manufactures metal nanoparticles that can mass-produce eco-friendly and uniformly the metal nanoparticles, especially silver nanoparticles used in applications such as metal ink, medical, clothing, cosmetics, catalysts, electrode materials, electronic materials, etc. in a simple process. Can be used extensively.

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