CN107265462A - A kind of method that nano-silicon is prepared by silicon tetrahalogen - Google Patents
A kind of method that nano-silicon is prepared by silicon tetrahalogen Download PDFInfo
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- CN107265462A CN107265462A CN201710313733.4A CN201710313733A CN107265462A CN 107265462 A CN107265462 A CN 107265462A CN 201710313733 A CN201710313733 A CN 201710313733A CN 107265462 A CN107265462 A CN 107265462A
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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
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/033—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by reduction of silicon halides or halosilanes with a metal or a metallic alloy as the only reducing agents
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a kind of method that nano-silicon is prepared by silicon tetrahalogen, strong reducing property of this method based on alkali and alkaline earth metal ions realizes the rapidly and efficiently reduction of silicon tetrahalogen by ball milling at room temperature.This method is extremely simple efficiently, it is not necessary to uses any solvent and other reaction mediums, and can largely synthesize nano-silicon at room temperature, cheap and easy to get with raw material, reacts simple and fast, and yield is high, and cost is low, the advantage such as easy expanding production.Prepared nano-silicon purity is high, and size is small, controllable, and is evenly distributed, available for lithium ion battery negative material, solar cell, sensor, the various aspects, great industrial applications prospect such as optics.
Description
Technical field
The invention belongs to the preparation field of nano silicon particles, it is related to a kind of method that nano-silicon is prepared by silicon tetrahalogen, has
Body relates to the use of the method that alkali and alkaline earth metal ions reduction silicon tetrahalogen prepares nano silicon particles.
Background technology
Nano-silicon is converted in solar energy, and the medium many fields of the lithium ion battery of electronic device and high power capacity have to be weighed very much
The application wanted.But the method for preparing nano-silicon reported at present can only realize that laboratory is prepared on a small quantity, and preparation condition is severe
Carve, it is with high costs, it is difficult to real industrialized production.
SiCl4The higher polysilicon of purity can be prepared by reducing, but traditional SiCl4Restoring method includes 1000 DEG C
Above gaseous state Zn reduces SiCl4(Pan,K.Method for Manufacturing High Purity Crystalline
Silicon with Zinc Reduction.CN102774838A, 2012., He, Z.Method for Preparing
Silicon Nanoparticles by Reducing Silicon Tetrachloride with
Zinc.CN102616785A, 2012.) and 1200 DEG C of H2Reduce SiCl4(Nakagawa,M.,The Dependence of the
Yield of Pure Silicon and the Components of the Exit Gas on the Reduction
Condition ofSilicon Tetrachloride Vapor.Kogyo Kagaku Zasshi 1962,65,466-
470.), but above method reaction temperature is too high, energy consumption is big, and equipment is expensive, and pyroreaction control is complicated.
SiCl in recent years4Reduction prepares the method for nano-silicon and made some progress in organic solvent, this method
Typically that reducing agent is scattered or be dissolved into toluene, in the organic solvent such as tetrahydrofuran, reducing agent includes lithium aluminium hydride reduction, naphthyl
Sodium, (Heath, J.R., A Liquid-Solution-Phase Synthesis of Crystalline such as potassium naphthalide
Silicon.Science 1992,258,1131-1133., Hyejung, K.；Minho,S.；Mi-Hee,P.；Jaephil,C.,
A Critical Size of Silicon Nano-Anodes for Lithium Rechargeable
Batteries.Angewandte Chemie InternationalEdition 2010,49,2146-2149.), but it is this
The reducing agent preparation condition of solution reduction is harsh, and the crystallinity of prepared nano-silicon is poor, while this method yield low yield
It is few, it is impossible to realize extensive prepare.
In addition, reducing SiCl in fuse salt4The method for preparing nano-silicon was also once reported, but this method needs 200-
500 DEG C of high temperature, and it is necessarily required to use substantial amounts of fuse salt as reaction medium, so that the nano-silicon system of significantly increasing
Standby cost (Ning Lin, Ying Han, Liangbiao Wang, Jianbin Zhou, Jie Zhou, Yongchun Zhu,
Yitai Qian, Preparation ofNanocrystalline Silicon from SiCl4at 2008C in Molten
Salt for High-PerformanceAnodes for Lithium Ion Batteries,
Angew.Chem.Int.Ed.2015,54,3822–3825)。
If it is possible to further reduce SiCl4Reduction temperature, and without using any organic solvent and reaction
In the case of medium, SiCl is directly realized by4Reduction prepares nano-silicon and undoubtedly simplifies the preparation method of nano-silicon by great, and drops
Low its prepares cost.
The content of the invention
The invention provides a kind of method that nano-silicon is prepared by silicon tetrahalogen, alkali metal or alkali are realized by room-temperature ball-milling
Earth metal direct-reduction silicon tetrahalogen prepares nano-silicon.This method is extremely simple efficiently, it is not necessary to use any solvent and other
Reaction medium, and nano-silicon can be largely synthesized at room temperature, prepared nano-silicon purity is high, and size is small, controllable, and
It is evenly distributed, can be with expanding production.
To achieve these goals, the present invention uses following technical scheme：
A kind of method that nano-silicon is prepared by silicon tetrahalogen, is comprised the following steps that：
(1) silicon tetrahalogen and alkali metal/alkaline-earth metal is taken to carry out ball milling.
(2) toward sequentially adding second alcohol and water in the mixture after ball milling, then wash, separate, drying, obtaining nano-silicon.
Silicon tetrahalogen can be silicon tetrachloride or silicon bromide described in above method step (1).
Alkali metal can be sodium, lithium, potassium, rubidium or caesium described in above method step (1).
The mol ratio of silicon tetrahalogen and alkali metal described in above method step (1) is 1:0.5-1:20, preferably 1:2-1:
8。
Alkaline-earth metal can be magnesium, calcium, strontium or barium described in above method step (1).
The mol ratio of silicon tetrahalogen and alkaline-earth metal described in above method step (1) is 1:0.5-1:10, preferably 1:2-
1:8。
Ball milling is carried out using vibrator or planetary ball mill in above method step (1), ratio of grinding media to material is 1:1-
400:1, preferably 5:1-100:1, Ball-milling Time 1-5000min, preferably 10-240min.
Washing refers to that being washed with water to inorganic salts all washes away described in above method step (2).
The method that separation is used in above method step (2) is centrifugation or is separated by filtration.
Centrifuged in above method step (2) and refer to centrifuge under 500-30000rpm rotating speeds.
In order to prevent the surface of nano-silicon from further aoxidizing in above method step (2), drying can be carried out under vacuo.It is excellent
It is selected under normal pressure or vacuum, 25-150 DEG C of heat drying 1-36h.
The above method also includes：Step (2) is obtained after nano-silicon, in order to remove the oxide layer on surface, used weight percentage
Specific concentration is 0.1%wt-40%wt (preferably 2%wt-40%wt) HF solution etches, removes surface oxide layer, and washing (uses second
Alcohol is washed, general washing twice), under normal pressure or vacuum, 25-150 DEG C of heat drying 1-100h (preferred vacuum drying oven 70
DEG C heating 3h), obtain the pure nano-silicon of surface non-oxidation layer.
The reagent (such as second alcohol and water) and step (being such as separated by filtration) used in the above method, unless otherwise specified, is used
Conventional reagent and step are that can be achieved in laboratory.
The technique effect of the present invention
Ball milling is generally used for grinding hard solid matter, but SiCl4It is liquid, it is impossible to grind, is generally used for liquid phase conjunction
Into realizing SiCl currently without using ball milling4The report of reaction is participated in, and metallic sodium is a kind of metal of dead-soft, ductility pole
It is good, it can not also be ground using ball milling, so also not utilizing ball milling to realize that metallic sodium participates in the report of reaction at present.The present invention is beaten
Broken conventional thought, the liquid Si Cl that ordinary person can not apparently be ground4Room-temperature ball-milling is carried out together with metal Na blocks, has been obtained extremely
Astonishing effect, metal Na blocks reduction liquid SiCl4Powder product is fully converted to, silicon nanometer has extremely been efficiently obtained
Particle.
The invention provides a kind of alkali metal or alkaline-earth metal room temperature, directly efficiently reduction silicon tetrahalogen prepares nano-silicon
New method, strong reducing property of this method based on alkali and alkaline earth metal ions, the fast of silicon tetrahalogen is realized by ball milling at room temperature
Fast efficiently reduction.It is cheap and easy to get with raw material, simple and fast is reacted, yield is high, and cost is low, the advantage such as easy expanding production, system
It is small for the silicon nanoparticle size gone out, it is evenly distributed, available for lithium ion battery negative material, solar cell, sensor, light
Learn the various aspects such as device.The present invention is just because of have the advantages that above highly significant, therefore great industrial applications prospect.
Brief description of the drawings
The high-purity nm Si powder X-ray diffractogram prepared in Fig. 1 embodiments 1.
The high-purity nm silicon scanning electron microscope diagram prepared in Fig. 2 embodiments 1.
Embodiment
The present invention is explained below by embodiment.But present invention is not limited to these embodiments.
Wherein, planetary ball mill model FRITSCH, pulveriszttz 5 used, vibrator model QM-
3B。
The mol ratio 1 of the silicon tetrachloride of embodiment 1 and sodium:4 ball millings prepare nano-silicon
(1) take raw material 3.6g silicon tetrachlorides and 1.95g sodium blocks to be placed in ball grinder, add the zirconium oxide that 20 quality are 4g
Ball, using vibrating ball mill ball milling 30min.
(2) ethanol is sequentially added in the mixture toward after after ball milling, water, 15000rpm centrifuges nano-silicon, then spends
Ion water washing is all removed to NaCl, 70 DEG C of vacuum drying 3h, obtains nano-silicon.
(3) nano-silicon for obtaining upper step 5%wt HF solution etches, remove surface oxide layer, and ethanol is washed one time,
70 DEG C of baking 3h of vacuum drying oven, collect dried nano-silicon.
The high-purity nm Si powder X-ray diffractogram obtained after above-mentioned three step, SEM respectively such as Fig. 1 and
Shown in 2, it can be seen that nano-silicon crystallinity is preferably, particle diameter is 20nm.Isothermal nitrogen adsorption draws the ratio table of the sample
Area is 173m2/g。
The mol ratio 1 of the silicon bromide of embodiment 2 and potassium block:8 ball millings prepare nano-silicon
(1) take raw material 10g silicon bromides and 6.7g potassium blocks to be placed in ball grinder, add the zirconium oxide that 20 quality are 4g
Ball, using vibrating ball mill ball milling 10min.
(2) ethanol is sequentially added in the mixture toward after after ball milling, water is separated by filtration nano-silicon, then be washed with deionized water
Wash to KBr and all remove, 40 DEG C of vacuum drying 20h obtain nano-silicon.
The nano-silicon crystallinity obtained after above-mentioned two step is preferable, particle diameter about 30nm, aperture about 4nm.Isothermal nitrogen adsorption
The specific surface area for drawing the sample is 600m2/g。
The mol ratio 1 of the silicon tetrachloride of embodiment 3 and lithium:2 ball millings prepare nano-silicon
(1) take raw material 20g silicon tetrachlorides and 1.65g lithiums to be placed in ball grinder, add the zirconia ball that 30 quality are 4g,
Utilize planetary ball mill ball milling 50min.
(2) ethanol, water are sequentially added in the mixture toward after after ball milling, 500rpm centrifuges nano-silicon, then spend from
Sub- water washing is all removed to LiCl, and 25 DEG C of dry 36h obtain nano-silicon.
(3) nano-silicon for obtaining upper step 1%wt HF solution etches, remove surface oxide layer, and ethanol is washed one time,
50 DEG C of baking 24h of vacuum drying oven, collect dried nano-silicon.
Preferably, particle diameter is between 2-5nm for the high-purity nm silicon crystallinity obtained after above-mentioned three step.Isothermal nitrogen adsorption is obtained
The specific surface area for going out the sample is 170m2/g。
The mol ratio 1 of the silicon tetrachloride of embodiment 4 and magnesium:8 ball millings prepare nano-silicon
(1) take raw material 5g silicon tetrachlorides and 5.64g magnesium to be placed in ball grinder, add the zirconia ball that 10 quality are 4g,
Using vibrating ball mill ball milling 120min.
(2) ethanol, water are sequentially added in the mixture toward after after ball milling, 5000rpm centrifuges nano-silicon, then spend from
Sub- water washing is to MgF2All remove, 150 DEG C of dry 1h obtain nano-silicon.
(3) nano-silicon for obtaining upper step 1%wt HF solution etches, remove surface oxide layer, and ethanol is washed one time,
50 DEG C of baking 24h of vacuum drying oven, collect dried nano-silicon.
Preferably, particle diameter is about 500nm to the high-purity nm silicon crystallinity obtained after above-mentioned three step.Isothermal nitrogen adsorption is drawn
The specific surface area of the sample is 40m2/g。
The mol ratio 1 of the silicon bromide of embodiment 5 and calcium:0.5 ball milling prepares nano-silicon
(1) take raw material 1g silicon bromides and 0.058g calcium to be placed in ball grinder, add the zirconia ball that 26 quality are 4g,
Utilize planetary ball mill ball milling 240min.
(2) ethanol is sequentially added in the mixture toward after after ball milling, water is separated by filtration nano-silicon, then be washed with deionized water
Wash to CaBr2All remove, 40 DEG C of dry 12h obtain nano-silicon.
(3) nano-silicon for obtaining upper step 5%wt HF solution etches, remove surface oxide layer, and ethanol is washed one time,
30 DEG C of baking 24h of vacuum drying oven, collect dried nano-silicon.
Preferably, particle diameter is about 10nm to the high-purity nm silicon crystallinity obtained after above-mentioned three step.Isothermal nitrogen adsorption is drawn
The specific surface area of the sample is 100m2/g。
The mol ratio 1 of the silicon tetrachloride of embodiment 6 and barium:2 ball millings prepare nano-silicon
(1) take raw material 10g silicon tetrachlorides and 16.2 barium to be placed in ball grinder, add the zirconia ball that 5 quality are 4g, profit
With vibration ball mill ball milling 5min.
(2) ethanol is sequentially added in the mixture toward after after ball milling, water, 30000rpm centrifuges nano-silicon, then spends
Ion water washing is to BaCl2All remove, 120 DEG C of dry 3h obtain nano-silicon.
Preferably, particle diameter is about 150nm to the nano-silicon crystallinity obtained after above-mentioned two step.Isothermal nitrogen adsorption draws the sample
The specific surface area of product is 120m2/g。
Claims (10)
1. a kind of method that nano-silicon is prepared by silicon tetrahalogen, is comprised the following steps that：
(1) silicon tetrahalogen and alkali metal/alkaline-earth metal is taken to carry out ball milling；
(2) second alcohol and water is sequentially added in the mixture toward after after ball milling, then washs, separate, drying, nano-silicon is obtained.
2. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that the silicon tetrahalogen
It is silicon tetrachloride or silicon bromide.
3. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that the alkali metal is
Sodium, lithium, potassium, rubidium or caesium, the mol ratio of the silicon tetrahalogen and alkali metal is 1:0.5-1:20.
4. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that the alkaline-earth metal
It is magnesium, calcium, strontium or barium, the mol ratio of the silicon tetrahalogen and alkaline-earth metal is 1:0.5-1:10.
5. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that use vibratory milling
Machine or planetary ball mill carry out ball milling, and ratio of grinding media to material is 1:1-400:1, Ball-milling Time 1-5000min.
6. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that the washing refers to
Inorganic salts are washed with water to all to wash away.
7. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that the separation is used
Method for centrifuge or be separated by filtration.
8. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 7, it is characterised in that the centrifugation
Refer to centrifuge under 500-30000rpm rotating speeds.
9. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that in step (2),
Under normal pressure or vacuum, 25-150 DEG C of heat drying 1-36h.
10. a kind of method that nano-silicon is prepared by silicon tetrahalogen as claimed in claim 1, it is characterised in that also include：Step
(2) obtain after nano-silicon, the HF solution etches for being 0.1%wt-40%wt with weight percent concentration, remove surface oxide layer,
Under washing, normal pressure or vacuum, 25-150 DEG C of heat drying 1-100h obtains the pure nano-silicon of surface non-oxidation layer.
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Cited By (4)
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| CN110540207A (en) * | 2019-09-18 | 2019-12-06 | 上海应用技术大学 | method for preparing high-purity nano silicon material by using industrial waste |
| CN115215341A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Preparation method of nano silicon |
| CN115215340A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Nano silicon wire and preparation method thereof |
| CN115231554A (en) * | 2022-07-15 | 2022-10-25 | 哈尔滨工程大学 | Preparation method of self-synthesized nano silicon-carbon composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540207A (en) * | 2019-09-18 | 2019-12-06 | 上海应用技术大学 | method for preparing high-purity nano silicon material by using industrial waste |
| CN110540207B (en) * | 2019-09-18 | 2023-02-10 | 上海应用技术大学 | Method for preparing high-purity nano silicon material by using industrial waste |
| CN115215341A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Preparation method of nano silicon |
| CN115215340A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Nano silicon wire and preparation method thereof |
| CN115231554A (en) * | 2022-07-15 | 2022-10-25 | 哈尔滨工程大学 | Preparation method of self-synthesized nano silicon-carbon composite material |
| CN115231554B (en) * | 2022-07-15 | 2023-12-29 | 哈尔滨工程大学 | Preparation method of self-synthesized nano silicon-carbon composite material |
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