WO2014178455A1 - Procédé de fabrication de microsphères creuses de métaux de transition-silicone - Google Patents

Procédé de fabrication de microsphères creuses de métaux de transition-silicone Download PDF

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Publication number
WO2014178455A1
WO2014178455A1 PCT/KR2013/003737 KR2013003737W WO2014178455A1 WO 2014178455 A1 WO2014178455 A1 WO 2014178455A1 KR 2013003737 W KR2013003737 W KR 2013003737W WO 2014178455 A1 WO2014178455 A1 WO 2014178455A1
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WO
WIPO (PCT)
Prior art keywords
transition metal
silicon
producing
microspheres
solution containing
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PCT/KR2013/003737
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English (en)
Korean (ko)
Inventor
김해진
이진배
홍원기
Original Assignee
한국기초과학지원연구원
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Publication of WO2014178455A1 publication Critical patent/WO2014178455A1/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
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B22F1/0655—Hollow particles

Definitions

  • the present invention relates to a method for producing a transition metal-silicon microspheres, and more particularly, to a method for producing a transition metal-silicon microspheres, in which a simple and bulky transition metal-silicon hollow sphere can be produced in large quantities. It is about.
  • the fine hollow spheres have a low density and a large specific surface area, and are capable of exchanging materials through micropores, and have a strong characteristic against physical impact or pressure due to their spherical shape.
  • micro hollow spheres of metal materials are known, and due to the characteristics of the materials and the characteristics of the micro hollow spheres, hydrogen storage media, building materials, heat radiation materials, sound insulation and electromagnetic shielding materials, beauty materials , Coating materials, filling materials, catalyst carriers, drug delivery materials, adsorbents for removing harmful substances, fuel cell electrode materials, etc. are being used.
  • hydrogen storage media building materials
  • heat radiation materials heat radiation materials
  • sound insulation and electromagnetic shielding materials beauty materials
  • Coating materials filling materials
  • catalyst carriers drug delivery materials
  • micro hollow spheres are mostly to manufacture micro hollow spheres with a single series of materials such as metal materials, organic materials, and inorganic materials, and thus are applicable to the manufacture of fine hollow spheres of composite materials such as metal-inorganic materials. There is a limit to doing so.
  • an object of the present invention is to provide a method for producing a transition metal-silicon micro-hollow sphere that can easily produce a large amount of hollow spheres having a fine size.
  • Another object of the present invention is to provide a method for producing fine hollow spheres made of a composite material of a transition metal and silicon.
  • the present invention provides a method for producing a transition metal-silicon microspheres, the method for producing a transition metal-silicon microspheres,
  • the reaction made in the second step is preferably performed for 5 to 50 hours in a temperature range of 100 to 300 °C.
  • the heat treatment performed in the third step is preferably performed for 1 to 10 hours in a temperature range of 300 to 500 °C under a vacuum atmosphere.
  • the fine hollow spheres produced by the present invention have the characteristics that the size of the microspheres is uniform and small, and the wall thickness is thin, compared to the hollow spheres produced by the conventional method.
  • the fine hollow sphere prepared by the present invention can express the properties of the material having a transition metal and silicon in addition to the properties of the fine hollow sphere itself can be effectively applied to a variety of industries.
  • 1 is a TEM image of manganese-silicon microspheres prepared according to an embodiment of the present invention.
  • Figure 2 shows the XRD data of the manganese-silicon microspheres prepared by the embodiment of the present invention.
  • FIG. 3 is a TEM image of the manganese-silicon microspheres prepared by Comparative Example 1.
  • FIG. 4 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 2.
  • FIG. 5 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 3.
  • FIG. 5 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 3.
  • the hollow spheres are relatively large, the wall thickness is relatively thick, the process conditions are complicated, and the control is not easy, so it is not suitable for mass production, and is a single series such as metal or inorganic materials.
  • the hollow spheres of the material there has been a limit in expressing a variety of functions.
  • the inventors of the present invention have studied a method for producing a micro hollow sphere made of a composite material of a transition metal and silicon, which is applied to various industrial fields due to its characteristics, and in the following process, a transition metal-silicon The present invention was completed by confirming that fine hollow spheres can be efficiently produced.
  • the transition metal precursor may be variously selected according to the characteristics of the transition metal to be imparted to the micro hollow spheres, as long as it is known as a transition metal precursor may be used.
  • a transition metal precursor in particular, manganese (Mn) is more environmentally friendly than other transition metals, and is relatively inexpensive and has a high energy density so that it can be efficiently applied to various fields. Therefore, it is preferable to use a manganese precursor as the transition metal precursor. Can be.
  • the manganese precursor may be used as long as it is known as a manganese precursor.
  • the compound containing silicon may be used as long as the compound containing silicon.
  • the compound containing silicon may include Na 2 SiO 3 , SiCl 4 , Si (OCOCH 3 ) 4 , SiI 4 , SiF 4 , SiC 32 H 8 O 2 , SiC 48 H 26 N 8 O 2 , SiC 32 H 18 N 2 O 2 and mixtures thereof, but is not limited thereto.
  • the solvent used in the first step may be used as long as it dissolves the compound including the transition metal precursor and silicon.
  • Various organic solvents, water and the like can be used.
  • the solvent for dissolving the transition metal precursor is preferably alcohol, more preferably ethanol.
  • alcohol more preferably ethanol.
  • the solvent for dissolving the transition metal precursor is not limited to alcohol, in particular ethanol.
  • a transition metal-silicon hollow sphere is formed by reacting the solution containing the transition metal prepared in the first step with a solution containing silicon. That is, in the second step, when the solution containing the transition metal and the solution containing silicon are reacted at a specific temperature range and reaction time, the two solutions react to form a transition metal-silicon composite, and as the reaction proceeds, The transition metal-silicon composite is dried into a hollow sphere shape to form a transition metal-silicon micro hollow sphere. In other words, after the transition metal-silicon composite is formed, if the reaction proceeds continuously, the transition metal-silicon composite formed due to the difference in the material properties of the transition metal and silicon is dried, and the reaction proceeds to form a hollow sphere. do.
  • the transition metal-silicon micro hollow spheres formed in this step are in the shape of hollow spheres, but are not perfectly stabilized, and are perfectly stabilized through heat treatment to be described later.
  • the reaction is preferably carried out for 5 to 50 hours in the temperature range of 100 to 300 °C, when the reaction temperature and the reaction time is less than the lower limit, the transition metal-silicon composite may not be sufficiently formed with a spherical shape If the reaction temperature and the reaction time exceeds the upper limit, the transition metal-silicon hollow sphere formed as the transition metal-silicon composite is cracked or crushed is spherical. It is not preferable because it may have a shape other than a phase.
  • the transition metal-silicon hollow sphere formed through the second step may be subjected to a process of washing and drying, wherein the washing and drying are for minimizing unwanted side reactions in the heat treatment process to be described later, As such, detailed description thereof will be omitted.
  • transition metal-silicon hollow sphere is heat-treated through the process of the third step, and the shape of the hollow sphere perfectly stabilized through the heat treatment.
  • the heat treatment is preferably carried out in a vacuum atmosphere, but not performed in a vacuum atmosphere, for example, when the heat treatment is performed in an air atmosphere, a part of the manufactured micro hollow spheres may be changed into transition metal oxide micro hollow spheres. Not. That is, when the heat treatment is performed in an air atmosphere, a part of the transition metal-silicon hollow spheres is changed to transition metal oxide hollow spheres, so that the transition metal-silicon micro hollow spheres and the transition metal oxide micro hollow spheres are simultaneously prepared to obtain the transition metal-silicon micro hollow spheres. Yield may be lowered, which is not preferred.
  • transition metal-silicon hollow spheres do not change into transition metal oxide hollow spheres, and thus, a stabilized transition metal-silicon microspheres can be obtained, thereby increasing the yield.
  • the heat treatment is preferably performed for 1 to 10 hours in the temperature range of 300 to 500 °C, when the heat treatment temperature and time is less than the lower limit, the transition metal-silicon micro hollow spheres are not sufficiently stable, This is not preferable because there is a fear of lowering, and when the heat treatment temperature and time exceeds the upper limit, there is a possibility that the transition metal-silicon micro hollow spheres may be broken or the structure may be deformed.
  • the manganese-containing solution and the silicon-containing solution were reacted at 185 ° C. for 30 hours to prepare manganese-silicon micro hollow spheres.
  • the prepared manganese-silicon microspheres were washed three times with distilled water, and then dried at 50 ° C. in a vacuum atmosphere for 5 hours.
  • the dried manganese-silicon microspheres were heat-treated at 400 ° C. for 2 hours in a vacuum atmosphere to prepare stabilized manganese-silicon microspheres.
  • the manganese-silicon microspheres prepared according to an embodiment of the present invention may have a uniform hollow sphere shape while having a size of about 6 to 7 nm or less.
  • Figure 2 shows the XRD data of the manganese-silicon microspheres prepared by the embodiment of the present invention. As shown in FIG. 2, in the case of the manganese-silicon micro hollow spheres prepared according to the embodiment of the present invention, it was confirmed that the micro hollow spheres were made of manganese-silicon composite (MnSiO 3 ).
  • FIG. 3 is a TEM image of the manganese-silicon microspheres prepared by Comparative Example 1.
  • FIG. 3 As shown in FIG. 3, in the case of Comparative Example 1, it could be confirmed that there was a portion that could not be rolled into a hollow sphere shape.
  • FIG. 4 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 2.
  • FIG. 4 As shown in FIG. 4, in the case of Comparative Example 2, it could be confirmed that the hollow sphere shape was partially broken due to excessive reaction.
  • FIG. 5 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 3.
  • FIG. 5 As shown in FIG. 5, in the case of Comparative Example 3, the hollow sphere shape was broken or collapsed due to excessive heat treatment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de fabrication de microsphères creuses de métaux de transition-silicone. Le procédé de fabrication des microsphères creuses de métaux de transition-silicone, selon la présente invention, comporte : (1) une première étape consistant à préparer une solution contenant des métaux de transition par l'ajout d'un solvant à un précurseur de métaux de transition, et à préparer une solution contenant de la silicone par l'ajout d'un solvant à un composé contenant de la silicone ; (2) une deuxième étape consistant à former des microsphères creuses de métaux de transition-silicone par réaction de la solution contenant les métaux de transition avec la solution contenant la silicone, lesquelles sont préparées à la première étape ; et (3) une troisième étape consistant à stabiliser les microsphères creuses de métaux de transition-silicone par la réalisation d'un traitement thermique sur les microsphères creuses de métaux-silicone formées lors de la deuxième étape. Le procédé de fabrication des microsphères creuses de métaux de transition-silicone, selon la présente invention, peut faciliter la production à grande échelle des microsphères creuses qui présentent une petite taille uniforme et sont constituées d'un matériau composite de métaux de transition et de silicone.
PCT/KR2013/003737 2013-04-29 2013-04-30 Procédé de fabrication de microsphères creuses de métaux de transition-silicone WO2014178455A1 (fr)

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KR10-2013-0047461 2013-04-29
KR1020130047461A KR101526476B1 (ko) 2013-04-29 2013-04-29 전이금속-실리콘 미세 중공구의 제조방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104439273A (zh) * 2014-11-06 2015-03-25 南京航空航天大学 一种FeCo/ZnO复合吸波材料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060055722A (ko) * 2004-11-19 2006-05-24 주식회사 사임당화장품 고분자 중공구의 물리적 제조 방법
KR20080006402A (ko) * 2006-07-12 2008-01-16 한국화학연구원 금속촉매가 함유된 고분자를 이용한 중공형 그라파이트나노카본 및 이의 제조방법
KR20080071856A (ko) * 2007-01-31 2008-08-05 부산대학교 산학협력단 반도체 중공 입자 및 이의 제조 방법
KR20100090551A (ko) * 2009-02-06 2010-08-16 에이비씨상사 주식회사 그라펜 중공 나노구 제조방법
KR20120076043A (ko) * 2010-12-29 2012-07-09 한국세라믹기술원 분무 건조법을 이용한 실리카 중공입자 및 그 제조방법과 실리카-티타니아 복합 중공입자 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060055722A (ko) * 2004-11-19 2006-05-24 주식회사 사임당화장품 고분자 중공구의 물리적 제조 방법
KR20080006402A (ko) * 2006-07-12 2008-01-16 한국화학연구원 금속촉매가 함유된 고분자를 이용한 중공형 그라파이트나노카본 및 이의 제조방법
KR20080071856A (ko) * 2007-01-31 2008-08-05 부산대학교 산학협력단 반도체 중공 입자 및 이의 제조 방법
KR20100090551A (ko) * 2009-02-06 2010-08-16 에이비씨상사 주식회사 그라펜 중공 나노구 제조방법
KR20120076043A (ko) * 2010-12-29 2012-07-09 한국세라믹기술원 분무 건조법을 이용한 실리카 중공입자 및 그 제조방법과 실리카-티타니아 복합 중공입자 및 그 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104439273A (zh) * 2014-11-06 2015-03-25 南京航空航天大学 一种FeCo/ZnO复合吸波材料的制备方法
CN104439273B (zh) * 2014-11-06 2017-01-11 南京航空航天大学 一种FeCo/ZnO复合吸波材料的制备方法

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KR20140129447A (ko) 2014-11-07
KR101526476B1 (ko) 2015-06-10

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