CN108147414A - A kind of preparation method of nanoscalar silicon particles - Google Patents

A kind of preparation method of nanoscalar silicon particles Download PDF

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Publication number
CN108147414A
CN108147414A CN201711428161.0A CN201711428161A CN108147414A CN 108147414 A CN108147414 A CN 108147414A CN 201711428161 A CN201711428161 A CN 201711428161A CN 108147414 A CN108147414 A CN 108147414A
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vitreum
sio
degree
vertically hung
hung scroll
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CN108147414B (en
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王海龙
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Ningxia University
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Ningxia University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention discloses a kind of preparation method of nanoscalar silicon particles, this method includes the following steps：With cheap silica and other oxide materials such as B2O3For raw material, using simple sinter bonded heat-treating methods, induce the spontaneous vertically hung scroll of Si base oxide materials and decompose, realize minimum nanoscale SiO first2The separation of particle and other element oxides, recycles the difference of different oxide sublimation temperatures, and quick heating sublimation point processed removes other oxides, finally obtains nanoscalar silicon particles using the methods of reduction technique such as magnesiothermic reduction.

Description

A kind of preparation method of nanoscalar silicon particles
Technical field
The invention belongs to technical field of chemistry, are related to a kind of preparation method of nanoscalar silicon particles.
Background technology
Nano silicon material technology of preparing has CVD, PVD, PLD, electrolysis etc. at present, and energy consumption is big, and equipment is expensive, and preparation condition is severe It carves, efficiency is low.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of nanoscalar silicon particles.With cheap silica and other Oxide material such as B2O3For raw material, using simple sinter bonded heat-treating methods, it is spontaneous to induce Si base oxide materials Vertically hung scroll decomposes, and realizes minimum nanoscale SiO first2The separation of particle and other element oxides, recycles different oxide liters The difference of magnificent temperature, quickly heats up to sublimation point, removes other oxides, finally using reduction technique such as magnesiothermic reduction the methods of Obtain nanoscalar silicon particles.
Its specific technical solution is：
A kind of preparation method of nanoscalar silicon particles, includes the following steps：
Step 1, by SiO2Powder (particle size is unlimited) and other oxide M Ox that vertically hung scroll decomposition reaction can occur with it Powder according to the corresponding molar ratio of vertically hung scroll decomposition reaction, uniformly mixes after weighing, and the two fusing is heated in air and forms glass Glass body, is cooled to room temperature.
More than vitreum is heated to vertically hung scroll stable reaction (Ts) 0.1- is kept the temperature between 0.85Ts by step 2 in air 24 hours, vertically hung scroll decomposition reaction, the superfine small SiO to be distributed alternately occurs2With MOx two-phase substances.
Vitreum after above heat treatment is rapidly heated to the sublimation temperature point of MOx by step 3, and 400 degree of heating rate/ - 2000 degrees/min of minute, making MOx, the vitreum being detached from after vertically hung scroll decomposition leaves superfine small SiO in sublimation point direct gasification2 Particle.
Step 4, by superfine small SiO2 particles achieved above and metal magnesium powder according to molar ratio 1：2 to 1：100 lazy Property gas or vacuum in uniformly mix, be then heated in closed container 650-1050 degree keep the temperature 0.1-24 hours, restore To silicon nanoparticle.
Step 5, pickling remove MgO, and then deionized water rinses to obtain pure silicon nanoparticle.
The best most fast temperature that vertically hung scroll decomposes is in below Ts 10%, and optimum temperature is 360 degree for 1.
B2O3After distillation, residue of salt acid rinse can be advanced with, removes B to greatest extent2O3。
Compared with prior art, beneficial effects of the present invention：
The method of the present invention requires low, low raw-material cost, production equipment letter for granularity, pattern to initial feed etc. It is single cheap, it can be carried out in air in addition to step 4, simple for process, production efficiency is high.
Description of the drawings
Fig. 1 is SiO2With B2O3After mixed melting forms vitreum, superfine small Nano-meter SiO_2 is formed under vertically hung scroll decomposition temperature2 The images of transmissive electron microscope of particle.
Fig. 2 is product X RD figures after spinodal decomposition, it is seen that SiO2Phase and B2O3Phase；
Fig. 3 is to remove B by distillation2O3Afterwards, using obtaining the transmission electron microscope of nano Si particle after 650 degree of magnesiothermic reductions Image.
Fig. 4 is product X RD figures after magnesiothermic reduction, it is seen that has obtained pure silicon.
Specific embodiment
Technical scheme of the present invention is described in more detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method of nanoscalar silicon particles, includes the following steps：
Step 1, by SiO2Powder (particle size is unlimited) and other oxide M Ox that vertically hung scroll decomposition reaction can occur with it Powder according to the corresponding molar ratio of vertically hung scroll decomposition reaction, uniformly mixes after weighing, and the two fusing is heated in air and forms glass Glass body, is cooled to room temperature.
Step 2, more than vitreum is heated to vertically hung scroll stable reaction (Ts) in air, and that 0.1 is kept the temperature between 0.85Ts is small When, vertically hung scroll decomposition reaction, the superfine small SiO to be distributed alternately occurs2With MOx two-phase substances.
Vitreum after above heat treatment is rapidly heated to the sublimation temperature point of MOx by step 3, and 400 degree of heating rate/ Minute, making MOx, the vitreum being detached from after vertically hung scroll decomposition leaves superfine small SiO in sublimation point direct gasification2Particle.
Step 4, by superfine small SiO achieved above2Particle is with metal magnesium powder according to molar ratio 1：2 in inert gas or It is uniformly mixed in vacuum, 650 degree is then heated in closed container and keeps the temperature 24 hours, reduction obtains silicon nanoparticle.
Step 5, pickling remove MgO, and then deionized water rinses to obtain pure silicon nanoparticle.
Embodiment 2
A kind of preparation method of nanoscalar silicon particles, includes the following steps：
Step 1, by SiO2Powder (particle size is unlimited) and other oxide M Ox that vertically hung scroll decomposition reaction can occur with it Powder according to the corresponding molar ratio of vertically hung scroll decomposition reaction, uniformly mixes after weighing, and the two fusing is heated in air and forms glass Glass body, is cooled to room temperature.
Step 2, more than vitreum is heated to vertically hung scroll stable reaction (Ts) in air, and that 12 are kept the temperature between 0.85Ts is small When, vertically hung scroll decomposition reaction, the superfine small SiO to be distributed alternately occurs2With MOx two-phase substances.
Vitreum after above heat treatment is rapidly heated to the sublimation temperature point of MOx by step 3, and 1200 degree of heating rate/ Minute, making MOx, the vitreum being detached from after vertically hung scroll decomposition leaves superfine small SiO in sublimation point direct gasification2Particle.
Step 4, by superfine small SiO achieved above2Particle is with metal magnesium powder according to molar ratio 1：50 in inert gas Or uniformly mixed in vacuum, 800 degree are then heated in closed container and keeps the temperature 12 hours, reduction obtains silicon nanoparticle.
Step 5, pickling remove MgO, and then deionized water rinses to obtain pure silicon nanoparticle.
Embodiment 3
A kind of preparation method of nanoscalar silicon particles, includes the following steps：
Step 1, by SiO2Powder (particle size is unlimited) and other oxide M Ox that vertically hung scroll decomposition reaction can occur with it Powder according to the corresponding molar ratio of vertically hung scroll decomposition reaction, uniformly mixes after weighing, and the two fusing is heated in air and forms glass Glass body, is cooled to room temperature.
Step 2, more than vitreum is heated to vertically hung scroll stable reaction (Ts) in air, and that 24 are kept the temperature between 0.85Ts is small When, vertically hung scroll decomposition reaction, the superfine small SiO to be distributed alternately occurs2With MOx two-phase substances.
Vitreum after above heat treatment is rapidly heated to the sublimation temperature point of MOx by step 3, and 2000 degree of heating rate/ Minute, making MOx, the vitreum being detached from after vertically hung scroll decomposition leaves superfine small SiO in sublimation point direct gasification2Particle.
Step 4, by superfine small SiO achieved above2Particle is with metal magnesium powder according to molar ratio 1：100 in inert gas Or uniformly mixed in vacuum, 1050 degree are then heated in closed container and keeps the temperature 0.1 hour, reduction obtains silicon nanoparticle.
Step 5, pickling remove MgO, and then deionized water rinses to obtain pure silicon nanoparticle.
The foregoing is only a preferred embodiment of the present invention, protection scope of the present invention is without being limited thereto, it is any ripe Those skilled in the art are known in the technical scope of present disclosure, the letter for the technical solution that can be become apparent to Altered or equivalence replacement are each fallen in protection scope of the present invention.

Claims (1)

1. a kind of preparation method of nanoscalar silicon particles, which is characterized in that include the following steps：
Step 1, by SiO2And B2O3According to molar ratio 1：1 uniformly mixes very much, and 900 degree are heated in air and keeps the temperature 4 hours, is obtained Vitreum；
More than vitreum is kept the temperature 2 hours for 400 degree by step 2 in air, is decomposed vitreum generation vertically hung scroll and is distributed alternately SiO2And B2O3；
Step 3, the vitreum for decomposing above generation vertically hung scroll, are heated rapidly in rapid heating furnace with 500 degrees/min of rates 1500 degree, reach B2O3Sublimation point is vaporized disengaging, is left Nano-meter SiO_22Particle；
Step 4, by residual powder and metal magnesium powder according to 1：6 molar ratios uniformly mix in ar gas environment, in closed vacuum Under the conditions of be heated to 650 degree occur magnesiothermic reductions reaction, obtain nano-silicon and magnesia mixture；
Step 5 adds in more than mixture in hydrochloric acid so that magnesia dissolves, and is then rinsed and removed with deionized water, after dry Obtain pure silicon nanoparticle.
CN201711428161.0A 2017-12-26 2017-12-26 Preparation method of nano-scale silicon particles Active CN108147414B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4460556A (en) * 1982-04-29 1984-07-17 Siemens Aktiengesellschaft Method for producing high purity Si for solar cells
US5976478A (en) * 1997-06-09 1999-11-02 E. I. Du Pont De Nemours And Company Low density silica particles and method for their preparation
CN101688068A (en) * 2007-07-06 2010-03-31 赢创德固赛有限责任公司 Process for preparing high-purity silicon dioxide granule

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4460556A (en) * 1982-04-29 1984-07-17 Siemens Aktiengesellschaft Method for producing high purity Si for solar cells
US5976478A (en) * 1997-06-09 1999-11-02 E. I. Du Pont De Nemours And Company Low density silica particles and method for their preparation
CN101688068A (en) * 2007-07-06 2010-03-31 赢创德固赛有限责任公司 Process for preparing high-purity silicon dioxide granule

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