WO2005111272A1 - Procédé de production de microparticules par électrolyse plasma-induite - Google Patents

Procédé de production de microparticules par électrolyse plasma-induite Download PDF

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Publication number
WO2005111272A1
WO2005111272A1 PCT/JP2005/006792 JP2005006792W WO2005111272A1 WO 2005111272 A1 WO2005111272 A1 WO 2005111272A1 JP 2005006792 W JP2005006792 W JP 2005006792W WO 2005111272 A1 WO2005111272 A1 WO 2005111272A1
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Prior art keywords
metal
molten salt
group
fine particles
electrolytic bath
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PCT/JP2005/006792
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English (en)
Japanese (ja)
Inventor
Yasuhiko Ito
Takuya Goto
Hiroyuki Kawamura
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Iox Co., Ltd.
The Doshisha
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Application filed by Iox Co., Ltd., The Doshisha filed Critical Iox Co., Ltd.
Priority to JP2006513507A priority Critical patent/JP4688796B2/ja
Publication of WO2005111272A1 publication Critical patent/WO2005111272A1/fr

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    • 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
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts

Definitions

  • the present invention relates to a method for producing metal fine particles by molten salt electrolysis and a recycling method.
  • Metal fine particles are widely used in the field of industrial materials such as magnetic recording media, photocatalysts, pigments, battery electrodes, and catalysts because they have higher functionality than bulk materials and have better processability of products. I have.
  • Patent Documents 1 and 2 As a conventional method for producing metal fine particles, a method using plasma induced by arc discharge or the like in a gas has recently attracted attention (for example, Patent Documents 1 and 2).
  • a voltage is applied between a discharge electrode arranged in close proximity and a base material as a raw material to generate plasma, and the base material is evaporated and solidified to form fine particles.
  • a voltage is applied between a plurality of discharge electrodes arranged close to each other to generate plasma, a raw material is supplied in the plasma, and the raw material is evaporated and solidified to form fine particles.
  • Patent Document 1 JP 2002-241811
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-045684
  • a main object of the present invention is to provide a method for producing fine metal fine particles and a method for recycling.
  • the present invention relates to a method for producing the following metal fine particles.
  • At least one metal selected from the group consisting of metals belonging to Group 3, 4, 5, 6, 7, 8, 9, 9, 10, 11, 12, 13, and 14 A method for producing fine metal particles, comprising: melting a metal raw material containing an oxide of the above in an electrolytic bath; and performing a molten salt electrolysis by placing a cathode near the electrolytic bath.
  • the metal raw material includes an oxide of at least one metal selected from the group consisting of titanium, zirconium, vanadium, niobium, tantalum, molybdenum, tungsten, chromium, platinum, cobalt, nickel and silicon.
  • Group consisting of metals belonging to groups 3, 4, 5, 6, 7, 8, 9, 9, 10, 11, 12, 13, and 14 at least one metal selected from the group consisting of
  • the anode containing at least one selected from the group consisting of the metal and a compound of the metal is placed in a molten salt, and the cathode is placed near the electrolytic bath to form the molten salt.
  • a method for producing metal fine particles comprising performing electrolysis.
  • the molten salt is selected from the group consisting of a metal and a metal compound as a raw material of the metal fine particles.
  • Item 4 The method according to Item 3, containing at least one of the following.
  • Item 5 The method according to any one of Items 1 to 4, wherein the molten salt electrolysis is performed by setting an electric resistance between the power supply and the anode.
  • a metal recycling method characterized by melting used metal in an electrolytic bath, installing a cathode near the electrolytic bath and performing molten salt electrolysis to obtain fine metal particles.
  • a metal recycling method comprising using used metal as an anode material, and installing a cathode near an electrolytic bath and performing molten salt electrolysis to obtain fine metal particles.
  • a metal raw material (a material serving as a raw material of metal fine particles) in a molten salt is produced as metal fine particles by installing a cathode in the vicinity of the electrolytic bath without in contact with the electrolytic bath and inducing plasma. On how to do it. That is, a metal power belonging to 3, 4, 5, 6, 7, 8, 9, 9, 10, 11, 12, 13, and 14 groups.
  • a method for producing fine metal particles comprising dissolving a metal raw material containing a metal oxide in an electrolytic bath, and performing electrolysis by inducing a plasma by setting a cathode near the electrolytic bath (hereinafter, referred to as a method of producing fine metal particles).
  • metal particles are produced by performing a plasma discharge on a metal raw material in a molten salt.
  • the present invention provides (1) a group consisting of metals belonging to groups 3, 4, 5, 6, 7, 7, 8, 9, 10, 11, 12, 13, and 14.
  • the present invention relates to a method for producing metal particles, which is characterized by performing salt electrolysis (hereinafter, may be referred to as production method 2).
  • the metal or metal compound contained in the anode is ionized and eluted into the molten salt by the molten salt electrolysis.
  • a metal and Z or a metal compound serving as a raw material of the fine particles are added to the molten salt.
  • the raw material is supplied from the anode, and the metal fine particles can be continuously produced.
  • a metal and a metal compound as raw materials of fine particles are contained in a molten salt.
  • the metal or metal compound which also eluted the anodic force is subjected to plasma discharge near the cathode to produce metal fine particles.
  • metal oxides for example, used metal oxides
  • An apparatus generally used for performing molten salt electrolysis can be used.
  • an electrolytic bath generally used in molten salt electrolysis can be used as the electrolytic bath.
  • alkali metal halide, alkaline earth metal halide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal sulfate, alkaline earth metal sulfate, alkali metal nitrate, alkaline earth metal It is preferable to use a molten salt obtained alone or in combination of two or more of nitrates as a solvent for the electrolytic bath.
  • Examples of the alkali metal halide include LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KC1, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, Lil, Nal, KI, Rbl, Csl. And the like.
  • Examples of the alkaline earth metal halide include MgF, CaF, SrF, BaF, MgCl, CaCl,
  • SrCl, BaCl, MgBr, CaBr, SrBr, BaBr, Mgl, Cal, Sri, Bal etc. S can be used.
  • the above compounds can be used alone or in combination of two or more.
  • the combination of these compounds, the number of compounds to be combined, the mixing ratio, and the like are not limited, and can be appropriately selected according to the type of metal to be electrolyzed.
  • metal raw material a metal compound (hereinafter, referred to as "metal raw material” or By dissolving an “ion source” and performing molten salt electrolysis, metal fine particles can be obtained.
  • metal raw material a metal compound
  • the anode contains a metal or a metal compound as a raw material of the metal fine particles
  • the addition of the metal raw material to the molten salt is optional.
  • the electrolytic bath in the present invention may contain other impurities, a solubilizing agent, an electrolytic assisting agent, and the like as long as the properties of the obtained metal fine particles are not impaired.
  • the metal fine particles obtained by the method of the present invention are selected from metals belonging to groups 3, 4, 5, 6, 6, 7, 8, 9, 10, 11, 12, 13, and 14. At least one kind of metal fine particles selected from the group consisting of: Among the above metals, titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), chromium (Cr), platinum (Pt ), Cobalt (Co), nickel (Ni), and silicon (Si).
  • the production method 1 at least one of the above-mentioned metal oxides is contained in the electrolytic bath as a metal raw material as a raw material of these metal fine particles.
  • the metal raw material may be a mixture of a metal oxide or a metal or a metal compound, or a metal or metal compound. Further, other components may be included.
  • Titanium oxides include TiO, TiO, and TiO; zirconium oxides include ZrO
  • Vanadium oxides include VO, VO, V 0, V 0, V 0 etc .
  • Oxides such as MoO and MoO; tungsten oxides such as WO and WO;
  • the oxides of 232 rom include CrO, CrO, Cr 0 and the like; the oxides of platinum include PtO, PtO,
  • silicon oxide examples include SiO and SiO 2.
  • the metal oxide may be a naturally oxidized metal or a used metal used for various purposes.
  • the used metal include metals used in magnetic recording media, photocatalysts, pigments, fuel cells, catalysts, and the like. By performing molten salt electrolysis using such a metal oxide, it is possible to recycle used metal.
  • fine metal particles composed of a single metal atom can be obtained.
  • alloy fine particles can be obtained.
  • Fine metal particles (comprising a plurality of metals) can also be obtained. Therefore, metal fine particles include alloy fine particles.
  • metal compound sulfates, nitrates, phosphates, halides (such as chlorides, fluorides, bromides, and iodides) of the above metals can be used.
  • sulfates, nitrates, phosphates, halides such as chlorides, fluorides, bromides, and iodides
  • K TaF, NiCl, K TiF K TaF, NiCl, K TiF
  • the metal compounds can be used alone or in combination of two or more.
  • the shape of the metal raw material used is not limited.
  • various shapes such as a scrap shape, a lump shape, or a powder shape may be used.
  • the amount of the metal compound and the oxide of Z or metal added to the electrolytic bath is not limited, and can be appropriately selected according to the electrolysis time, the amount and size of the fine particles.
  • the metal raw material should be dissolved in an amount of about 0.0001 to 10 mol / L, preferably about 0.1 to 5.0 mol / L per solvent of the electrolytic bath.
  • the metal raw material since the metal raw material is supplied with an anodic force by electrolysis, the addition of the metal raw material to the electrolytic bath can be arbitrarily selected.
  • the metal raw material may be any one selected from the group consisting of a metal and a metal compound which are raw materials for fine particles. Therefore, in Production Method 1, a metal oxidant is indispensable as a metal raw material, but in Production Method 2, the metal raw material added to the molten salt is not limited to a metal oxidant, but may be a metal or metal. The compounds can be used widely.
  • the concentration of the metal raw material to be added to the molten salt can be reduced as compared with the case of the production method 1. .
  • fine particles of an alloy are obtained. Included in particles.
  • an electrode generally used as an anode in molten salt electrolysis can be used, and is not particularly limited.
  • carbon materials such as glass, graphite, conductive diamond and the like, tantalum, tungsten, molybdenum, platinum and the like can be used as electrodes.
  • a thin film formed of a metal such as tantalum, tungsten, molybdenum, or platinum on a dissimilar material can be used as the anode.
  • used metals can be used as anode materials.
  • it is required to suppress the generation of chlorine gas it can be suppressed by allowing the anode to contain a fine particle source metal or a compound of the metal.
  • the anode may be (1) a group of 3, 4, 5, 6, 7, 8, 8, 9, 11, 12, 13, At least one metal selected from the group consisting of metals belonging to Group 14 and Group 14; and (2) a compound of the metal; Preferred metal species are the same as the preferred metal species of the metal fine particles.
  • the compound of the metal is the same as the metal compound in the metal raw material.
  • generation of chlorine gas is suppressed because the anode contains a raw material of fine particles.
  • the combination of metal species contained in the anode is appropriately selected according to the metal species of the target fine particles.
  • the shape, size, and the like of the electrode used in the present invention are not limited.
  • As the shape of the electrode for example, a plate shape, a rod shape, a lump shape, a spring shape, a prism shape, or the like can be used.
  • the anode when performing electrolysis, is preferably immersed in an electrolytic bath so as to generally perform the electrolysis.
  • the mode in which the entire anode is immersed or a part thereof is immersed is not particularly limited.
  • an anode generally used for molten salt electrolysis and capable of generating plasma can be used, and is not particularly limited.
  • various metals such as iron, nickel, molybdenum, tantalum, and tungsten, alloys thereof, carbon materials such as glassy carbon and conductive diamond, conductive ceramics, and semiconductor ceramics can be used.
  • those formed as thin films on different materials can also be used as cathodes.
  • a high melting point metal such as tungsten or tantalum which is not easily consumed when plasma is induced.
  • the present invention it is installed near the electrolytic bath so that it is not in contact with or immersed in the electrolytic bath.
  • the installation place is not particularly limited as long as the metal fine particles are generated in the molten salt by the plasma generated by the cathode, but it is preferable that the installation place is above the liquid level of the molten salt. By doing so, cathodic plasma is induced, and fine metal particles are generated in the electrolytic bath.
  • the distance from the surface of the electrolytic bath to the lowermost part of the cathode is not limited, as long as the plasma is stably induced.
  • the electrolysis conditions in the present invention can be generally performed under the conditions for performing molten salt electrolysis, and can be appropriately selected according to the composition of the solvent, the type of target metal fine particles, and the like.
  • the voltage to be applied is preferably about 200 to 400 V in order to reduce the load on the electric circuit, for example, about 200 to 800 V.
  • the voltage can be reduced to 10 to 200 V, preferably 30 to 150 V, at a stage where the generation of plasma-induced discharge is stable.
  • the type of generated current is preferably a direct current, and the current per discharge electrode is preferably about 0.05 to 50 A, and more preferably about 0.1 to 20 A.
  • an electric resistor in order to stably induce plasma, it is preferable to secure electric discharge stability by inserting an electric resistor between the power supply and the electrode.
  • the electrical resistance can be inserted on the cathode side, the anode side or both.
  • the type of the electric resistance is not limited as long as it is a resistor having a capacity to withstand the current during electrolysis.
  • a cement resistor, an enamel resistor, a non-combustible fixed wire resistor, or the like can be used. Fixed resistors are more preferred.
  • the value of the resistance is usually about 1 ⁇ to 51 ⁇ , preferably 3 ⁇ to 31 ⁇ .
  • the temperature of the electrolytic bath is also not limited, and can be appropriately selected according to the melting point of the solvent, the melting point of the ion source, and the like. For example, it is about 250 to 700 ° C, preferably about 400 to 500 ° C.
  • the electrolysis is generally performed under atmospheric pressure, but may be performed under increased or reduced pressure.
  • examples of the inert gas which is preferably performed in an inert gas atmosphere include nitrogen, argon, and neon, and argon is preferable.
  • the electrolysis time is also not limited, and is appropriately selected according to the type, particle size, and the like of the target metal particles. Can. For example, it is about 0.1 to 10 hours, preferably about 1 to 5 hours.
  • metal fine particles having an arbitrary particle size of about 100 ⁇ m or less, preferably in the range of about lnm to 100 ⁇ m are obtained. be able to.
  • very small metal particles of nano size can be obtained.
  • the size of the metal fine particles can be reduced by shortening the electrolysis time or the time until the recovery of the electrolytic power, reducing the concentration of the ion source in the electrolytic bath, or keeping the temperature of the electrolytic bath low during the electrolysis. Can be smaller.
  • the following mechanism is considered as a mechanism for obtaining metal fine particles by the method of the present invention.
  • the present invention is not limited to this mechanism.
  • a cation M n + serving as a raw material of fine particles in a solvent is generated according to the following equation (1), and a reduction reaction of an alkali metal ion L + present in the solvent (formula (1)) According to (2)), it is reduced to an atomic substance as represented by equation (3).
  • atomic-level clusters are formed by collisions between atomic substances in a solvent, and furthermore, collisions between atomic-level clusters are sequentially repeated, so that fine particles of several nm or several / zm are thought to grow. .
  • M represents a metal contained in an oxide or the like
  • MA represents an oxide or the like.
  • the obtained metal particles can be recovered in the following manner.
  • the present invention is not limited to these.
  • electrolytic bath power A molten salt containing metal particles can be taken out, cooled and solidified, preferably in an inert gas atmosphere.
  • the type of the inert gas is as described above.
  • the solidified electrolytic solution may be crushed and immersed in the cleaning solution! ⁇ .
  • the means for pulverization is not limited, and may be, for example, a hammer, a mixer, or the like.
  • the device for performing the ultrasonic treatment is not limited, and a commercially available device can be used.
  • the condition of the ultrasonic wave is not limited.For example, the ultrasonic treatment may be performed at a frequency of about 10 to 100 kHz, about 20 to 60 kHz, for about 100 to 300 minutes per 100 g of the solidified electrolyte, preferably about 150 to 200 minutes. ⁇ .
  • the metal particles of the present invention can be obtained by washing and centrifuging.
  • the condition of the centrifugation is not limited as long as the metal fine particles obtained in the present invention and the solidified electrolyte are separated, and can be appropriately selected.
  • the speed can be about 1000 to 5000 rpm, preferably about 1500 to 3000 rpm, and about 10 minutes to 2 hours, preferably about 30 minutes to 1.5 hours.
  • the washing method is not limited as long as the metal fine particles obtained in the present invention can be subjected to ultrasonic wave, centrifugal separation, and the like.
  • water an aqueous solution in which a reducing agent generally used for electroless plating is dissolved, or the like can be used.
  • a reducing agent such as dimethylamine borane and trimethylamine borane
  • borohydride compounds such as potassium borohydride and sodium borohydride
  • formaldehyde and the like can be used. These concentrations are not limited.
  • ultrasonic treatment and centrifugation of the precipitate may be repeated. By repeating the process, metal fine particles can be obtained with high efficiency from the solidified electrolytic solution.
  • the particle size of the obtained metal particles can be determined by a conventional method such as observation with an electron microscope.
  • the particle size distribution can also be determined by a conventional method such as dynamic light scattering measurement.
  • the oxygen content in the metal fine particles can also be determined by a conventional method such as, for example, an electroinert gas melting infrared absorption method.
  • the recycling method of the present invention utilizes the above-described method for producing fine metal particles, and uses a used metal or metal compound as a metal raw material. That is, the used metal or metal compound is added to the molten salt as a metal raw material, or is held at the anode. As a result, fine metal particles corresponding to the metal species of the used metal or metal compound are generated, so that the used metal or metal compound can be reused.
  • a holder (3) for installing a high-purity aluminum crucible (2) as an electrolytic cell in an electric furnace (1) capable of heating at about 500 ° C is provided.
  • the inert gas is circulated at atmospheric pressure through the inlet pipe (4) and the exhaust pipe (5).
  • the alkali metal halide is melted and used as a solvent (6) for the electrolytic bath.
  • the temperature of the solvent is measured with a thermocouple (7) and set to a predetermined temperature.
  • an ion source serving as a raw material of the metal fine particles is added to the solvent.
  • a power supply device (10) is installed between the discharge electrode (8) placed on the solvent and the electrode (9) placed in the solvent, and a voltage is applied to connect the solvent and the discharge electrode. Plasma is induced in between.
  • the electrode (9) in the solvent may have a portion capable of holding the substance (11) containing the raw material of the metal fine particles. By doing so, it is possible to stably or continuously supply an ion source serving as a raw material of metal fine particles during electrolysis.
  • the ion source may be held in a solvent other than the electrode.
  • the method for producing metal fine particles of the present invention is particularly excellent in that not only the metal but also an oxide of the metal can be used as a raw material of the metal fine particles. Further, by controlling parameters such as electrolyte composition, electrolyte temperature, and electrolysis time in molten salt electrolysis, the particle size, particle size distribution, and the like of the fine particles can be easily controlled.
  • the present invention does not require expensive equipment and equipment, and does not require advanced knowledge or advanced technology, and can produce desired fine metal particles. Therefore, the production cost of metal particles is greatly reduced. You. Also, the electrolytic bath does not contain harmful substances and can be reused.
  • the form of the metal raw material used as the raw material of the metal fine particles it is possible to produce the metal fine particles by using a scrap or lump-shaped raw material.
  • an ion source is supplied by anodic dissolution or chemical dissolution of the substance by holding the substance containing the raw material of the microparticles to be produced in the electrode part disposed in the solvent in the electrolytic bath or in the solvent. it can.
  • the state force such as scrap can again produce a material necessary for the device, the method of the present invention is very excellent as a metal recycling method.
  • FIG. 1 is a conceptual diagram of an apparatus for performing molten salt electrolysis.
  • FIG. 2 (a) shows a scanning electron micrograph of the tantalum fine particles obtained in Example 1, and FIG. 2 (b) shows the analysis result of the white rectangular portion of (a) by an X-ray microanalyzer.
  • FIG. 3 (a) shows a scanning electron micrograph of the tantalum fine particles obtained in Example 3, and (b) shows the result of X-ray diffraction of the tantalum fine particles.
  • LiCl—KCl (58.5: 41.5mol%; 100g in total) mixed in a eutectic composition was vacuum-dried at 180 ° C for several days in the solvent (electrolytic bath) and then melted at 450 ° C in an argon atmosphere. I used something.
  • Heptafluorotantalum potassium (K TaF) was used as the tantalum source.
  • a tungsten wire was placed on a solvent as a discharge electrode (cathode), and tantalum condenser scrap (pin scrap) was placed in the solvent as an anode.
  • a cylindrical tantalum metal electrode holding the garnish was 0.5% by weight of the entire scrap was disposed.
  • Under an argon atmosphere maintain the solvent temperature at 450 ° C, apply 250 V between the discharge electrode and the electrode in the solvent, induce a plus and minus between the discharge electrode and the solvent, and Electrolysis was performed.
  • the solvent containing the fine particles is cooled and solidified to room temperature under an argon atmosphere, subjected to ultrasonic treatment for several hours in a 2M aqueous hydrazine solution until the solidified solvent is dissolved, and then left for about 10 minutes.
  • the sonication and the centrifugation operation were repeated.
  • the centrifugation operation was performed at 2000 rpm, and the first time was about 10 minutes, the second time was about 30 minutes, and the third time was about 60 minutes.
  • the K TaF force equivalent to 0.1 mol% added in a solvent is also the theoretical value of fine particles obtained by electrolysis.
  • the mass is 0.32 g, and the fine particles collected for force analysis alone exceed 0.4 g, and it can be said that tantalum fine particles were formed from pin scraps or a tantalum ion source obtained by melting from a tantalum metal electrode. It was confirmed that the present invention can be used as a resource recycling type process using scrap as a raw material.
  • Metal compounds other than tantalum include nickel (using NiCl as an ion source), titanium (using
  • K TiF as an ion source silver (AgCl as an ion source), zirconium (ion
  • a cylindrical graphite electrode holding 1.502 g of tantalum condenser scrap (pin scraps) in a solvent was placed as the anode, and the current value was set to 0.80 A.
  • the experiment was performed in the same manner as in Example 1 except that the electrolysis was performed for 1.7 hours. X-ray diffraction of the obtained fine particles confirmed that they were tantalum fine particles with a lattice constant of about 3% wider.
  • NiCl nickel ion source
  • K TiF titanium ion source
  • AgCl silver
  • K ZrF zirconium ion source
  • VC1 vanadium ion source
  • NbF niobium ion source
  • K MoO molecular oxygen species
  • K WO tungsten
  • the metal fine particles are formed only by the electrode that holds the scrap without previously including the ion source in the solvent, and the present invention is further described as a resource recycling process using scrap as a raw material. Confirmed to be valid.
  • the present invention is useful in the field of producing fine metal particles and the field of recycling metal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Sont fournis : un procédé de production de microparticules métalliques, caractérisé en ce qu'un oxyde d'espèce métallique (métal appartenant aux Groupe 3, Groupe 4, Groupe 5, Groupe 6, Groupe 7, Groupe 8, Groupe 9, Groupe 10, Groupe 11, Groupe 12, Groupe 13 ou Groupe 14) de microparticules de métal est fondu dans un bain électrolytique et qu'une électrolyse du sel fondu est exécutée avec une électrode négative disposée à proximité du bain électrolytique ; un procédé de production de microparticules, caractérisé en ce qu'une électrolyse de sel fondu est effectuée avec une électrode positive contenant l'espèce métallique disposée dans un sel fondu et avec l'électrode négative disposée à proximité du bain électrolytique, ou un procédé de recyclage du métal utilisé par l'utilisation de ces procédés de production ; un procédé de recyclage d'un métal, caractérisé en ce qu'une électrolyse d'un sel fondu est menée avec le métal utilisé fondu dans un bain électrolytique et avec une électrode négative disposée à proximité du bain électrolytique pour obtenir de cette façon des microparticules de métal ; et un procédé de recyclage d'un métal, caractérisé en ce qu'une électrolyse de sel fondu est menée avec le métal usagé utilisé comme électrode positive et avec une électrode négative disposée à proximité d'un bain électrolytique pour obtenir de cette façon des microparticules métalliques.
PCT/JP2005/006792 2004-04-06 2005-04-06 Procédé de production de microparticules par électrolyse plasma-induite WO2005111272A1 (fr)

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JP2007084890A (ja) * 2005-09-22 2007-04-05 Kyoto Univ 溶融塩中における酸素発生装置および酸素発生方法
JP2008106309A (ja) * 2006-10-26 2008-05-08 Doshisha プラズマ誘起電解による微粒子の製造方法およびその装置
JP2009215569A (ja) * 2008-03-07 2009-09-24 Doshisha 溶融塩反応浴を利用した合金粉末製造法
WO2013065511A1 (fr) * 2011-11-04 2013-05-10 住友電気工業株式会社 Procédé de fabrication de métal par électrolyse en sel fondu et appareil destiné à être utilisé dans celui-ci
JP2013117063A (ja) * 2011-11-04 2013-06-13 Sumitomo Electric Ind Ltd 溶融塩電解による金属の製造方法
JP2013147731A (ja) * 2011-12-22 2013-08-01 Sumitomo Electric Ind Ltd 溶融塩電解による金属の製造方法
JP2016191153A (ja) * 2010-11-02 2016-11-10 学校法人同志社 シリコンナノ粒子の製造方法
US10309022B2 (en) 2011-08-10 2019-06-04 Sumitomo Electric Industries, Ltd. Element recovery method and element recovery apparatus

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JP2016191153A (ja) * 2010-11-02 2016-11-10 学校法人同志社 シリコンナノ粒子の製造方法
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WO2013065511A1 (fr) * 2011-11-04 2013-05-10 住友電気工業株式会社 Procédé de fabrication de métal par électrolyse en sel fondu et appareil destiné à être utilisé dans celui-ci
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