CN105271235B - A kind of silicon nanowire material and preparation method thereof - Google Patents
A kind of silicon nanowire material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of silicon nanowire material and preparation method thereof, the preparation method of the silicon nanowire material comprises the following steps：(1) copper-based catalysts and silicon are subjected to the 10h of the pre-heat treatment 2 under 200 500 DEG C of inert atmosphere, obtain contact；(2) contact and chloromethanes are reacted, and controls the incomplete reaction of silicon；(3) impurity in removal step (2) reaction product and unreacted silicon is separated, that is, obtains silicon nanowire material, while by-product organic silicon monomer.The preparation method technique of silicon nanowire material provided by the invention is simple, and reaction condition is gentle, preparation process cleaning, the organic silicon monomer chemicals of the high value of by-product is capable of while silicon nanowires is made, is suitable for large-scale production；And the diameter and distribution of lengths of obtained silicon nanowire material are homogeneous, and draw ratio is adjustable, solves the key issue that prior art is difficult to silicon nanowire material preparation.
Description
Technical field
The invention belongs to the preparing technical field of nano material, more particularly to a kind of silicon nanowire material and its preparation side
Method.
Background technology
Silicon nanowires is a kind of very important one-dimensional nano structure material, due to the dielectric property with uniqueness, optics
Characteristic, microelectronics compatibility and big specific surface area and draw ratio controllability, make it in bioanalysis, immune detection, illumination material
The field such as material, photoelectric device, integrated circuit, insulating materials, sensing element and sensor, solar cell and lithium ion battery tool
It is widely used.Silicon nanowires is a kind of new photoelectric semiconductor material, at room temperature with excellent luminescence generated by light and
The characteristics such as electroluminescent are compatible with existing silicon technology, it is most likely that to realize the application of the multiple fields such as silicon-based photoelectric device.
The preparation method of silicon nanowire material mainly includes following several at present：(1) metal Assisted Chemical Etching Process method, such as CN
102815701A and CN 103337455A disclose one kind and use hydrofluoric acid-silver nitrate and hydrofluoric acid-hydrogen peroxide as etching solution
Wet chemistry methods prepare silicon nanowires；US 8334216B2 disclose using after depositing noble metal particle by hydrofluoric acid-
The method of dioxygen water etching prepares silicon nanowires.(2) plasma etching method, as CN 101117208A disclose a kind of use
The method that method for etching plasma prepares silicon nanowires/point.(3) reactive ion etching method, as US 6773616B1 are used
CF4-SF6Silicon nanowires is prepared for the reactive ion etching method of etching gas.(4) chemical vapour deposition technique, such as US
20030189202A1 discloses a kind of equipment that silicon nanowires is prepared using chemical gaseous phase depositing process；US 6313015B1 are adopted
Silicon nanowires is prepared with the method for chemical vapor deposition silicon monoxide.(5) other methods, as document report can by gas-
Liquid-solid method prepares silicon nanowires (Diameter-dependent or independent:Toward a
mechanistic understanding of the vapor-liquid-solid Si nanowire growth
rate.Lu Y Y,et al.Nano letters,2012,12(8):4032-4036.)。
These preparation method generally existing costs of material reported above are high, preparation technology is complicated, equipment requirement is high, process
The problems such as condition is harsh, seriously polluted (largely using HF or accessory substance) and batch production are difficult, or performance can not meet business
Industry demand, can not industrialization production.Therefore, the preparation side of silicon nanowires can largely be synthesized by being badly in need of a kind of process easy clean
Method.
Organic silicon monomer is the stock for preparing organosilicon material, is basis and the pillar of whole silicone industry, has
Machine silicon materials have the dual property of inorganic material and organic material, have high-low temperature resistant, electric insulation, corrosion-resistant and nontoxic nothing
The excellent specific properties such as taste, it is widely used in the fields such as electronics, automobile, oil, chemical industry, building and Aero-Space.
CN 103508458A disclose a kind of porous silica material and preparation method thereof, the preparation side of the porous silica material
Method is as follows：1) under copper-based catalysts effect, silicon and chloromethanes heating response at 401-800 DEG C, and control silicon is endless to be all-trans
Should；2) after going the removal of impurity and separating unreacted silicon, porous silica material, while by-product organic silicon monomer are obtained；Wherein, it is copper-based to urge
Agent includes major catalyst CuOx, CuCl, CuCl2In one kind or two or more mixture, 0≤x≤1, and a small amount of co-catalysis
Agent.CN 102211770A disclose a kind of method for preparing porous silica material using silicon and halogenated hydrocarbons catalytic reaction, methods described
Comprise the following steps：1) under copper-based catalysts effect, silicon and gaseous state halogenated hydrocarbons heating response, and control silicon incomplete reaction can
Obtain organic silicon monomer simultaneously；2) unreacted silicon is separated, after going the removal of impurity, that is, porous silica material is prepared.But this two
The product that kind preparation method obtains is porous silicon nano material, it is impossible to obtains silicon nanowire material.
The content of the invention
The defects of existing for prior art, it is an object of the invention to provide a kind of silicon nanowire material and its preparation side
Method, the preparation method technique of the silicon nanowire material is simple, process cleans and production cost are low, is suitable for scale metaplasia
Production, the silicon nanowire material of different length, thickness, major diameter when distribution of orientations, while by-product organic silicon monomer can be obtained
Product, have broad application prospects.
To use following technical scheme up to this purpose, the present invention：
An object of the present invention is to provide a kind of preparation method of silicon nanowire material, and the preparation method is included such as
Lower step：
(1) copper-based catalysts and silicon are subjected to the pre-heat treatment 2-10h under 200-500 DEG C of inert atmosphere, obtain contact；
(2) contact and chloromethanes are reacted, and controls the incomplete reaction of silicon；
(3) impurity in removal step (2) reaction product and unreacted silicon is separated, that is, obtains silicon nanowire material, together
When by-product organic silicon monomer.
The organic silicon monomer is (CH3)3SiCl、(CH3)2SiCl2、CH3SiCl3、(CH3)2HSiCl or CH3HSiCl2In
One kind or at least two combination.
The temperature of step (1) described the pre-heat treatment can be：210℃、230℃、260℃、280℃、300℃、320℃、350
DEG C, 380 DEG C, 400 DEG C, 420 DEG C, 450 DEG C or 480 DEG C etc., the time of the preheating can be 3h, 4h, 5h, 6h, 7h, 8h or 9h
Deng.
Copper-based catalysts and silicon materials are first carried out the pre-heat treatment by the preparation method of silicon nanowire material provided by the invention,
So that the two-phase interface of silicon and cupper-based catalyst agent composition forms catalytic activity thing-cupro silicon, afterwards by cupro silicon and chlorine
Methane in-situ catalytic reaction, obtain silicon nanowire material, while by-product organic silicon monomer.
The preparation method of the silicon nanowire material solves prepared by the silicon nanowire material that prior art is difficult to
Key issue, without using the hydrofluoric acid of hypertoxicity in preparation process, the generation of fluoride waste is avoided, realizes silicon nanowire material
Cleaning prepare；The organic silicon monomer value of by-product is high；It is easy to preparation of industrialization silicon nanowire material.
Step (1) described inert atmosphere be argon gas, nitrogen or helium in one kind or at least two combination, it is typical but non-
Restricted is combined as：Argon gas and nitrogen, nitrogen and helium, argon gas, nitrogen and helium etc..
The mass ratio of silicon and copper-based catalysts is any ratio in step (1) described contact, such as 0.5:1、1:1、2:1、3:1、
4:1、5:1、6:1、7:1、8:1、10:1、20:1、30:1 or 50:1 etc., preferably 1:3-5:1.
Step (1) described copper-based catalysts include major catalyst and a small amount of co-catalyst, the major catalyst be Cu,
Cu2O, CuO, CuCl or CuCl2In one kind or at least two combination, typical but non-limiting combination can be：Cu with
Cu2O, CuO and CuCl, CuO, CuCl and CuCl2, Cu, Cu2O and CuO, Cu, Cu2O, CuO and CuCl, Cu, Cu2O、CuO、CuCl
With CuCl2。
Preferably, the co-catalyst is one kind in zinc, tin, phosphorus, ormolu or cupro silicon or at least two
Combination, typical but non-limiting combination can be：Zinc and tin, zinc, tin and phosphorus, phosphorus and ormolu, ormolu close with copper silicon
Gold.
The granular size of step (1) described copper-based catalysts is nanoscale, micron order or grade, preferably micron order.
Preferably, the pattern of step (1) described copper-based catalysts be spherical, dendroid, it is flower-shaped, sheet, powdered or solidifying
It is gluey.
The granular size of step (1) described silicon is nanoscale, micron order or grade, preferably micron order.The silicon can
Select industrial silicon.
Preferably, the pattern of step (1) described silicon is sheet or graininess.
Preferably, step (1) described silicon is non-crystalline silicon, monocrystalline silicon or polysilicon.
The temperature of step (2) described reaction be 300-800 DEG C, such as 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360
DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 395 DEG C, 410 DEG C, 430 DEG C, 450 DEG C, 550 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 780 DEG C
Deng.
Preferably, the time of step (2) described reaction is 2-36h, such as 3h, 5h, 6h, 8h, 10h, 15h, 20h, 25h, 30h
Or 35h etc..
Preferably, the pressure of step (2) described reaction is 0.1-1MPa, as 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa,
0.6MPa, 0.7MPa, 0.8MPa or 0.9MPa etc..
Step (2) reaction is carried out on fixed bed, agitated bed or fluid bed.
Step (3) is described to go the removal of impurity to be：The reaction product that step (2) obtains is calcined, acid elution, neutralizing treatment and
Drying process.
It is described to go deimpurity method to be well known to those skilled in the art.The reaction product obtained due to step (2)
In contain carbon distribution in unreacted silicon, copper-based catalysts and course of reaction, it is therefore, described to go the deimpurity method to be：
Air calcination is passed through in tube furnace and removes carbon remover, after being cooled to 10-30 DEG C, one is ultrasonically treated in the concentrated nitric acid of certain temperature
The section time, metal or metal oxide are dissolved, removal metal component is cleaned repeatedly with deionized water, then in sodium hydroxide solution
Middle stirring reaction for a period of time, the silica for removing silicon nanowire material is cleaned with deionized water, in vacuum drying chamber repeatedly
Dried under middle certain temperature and obtain final silicon nanowire material for a period of time.Those skilled in the art can be according to step (2)
Reaction product actual state selection calcining heat and the time, the temperature and time of acid elution, neutralizing treatment temperature and time with
And the temperature and time of drying process.
As preferable technical scheme, the invention provides a kind of preparation method of silicon nanowire material, the preparation side
Method comprises the following steps：
(1) it is 1 by mass ratio:3-5:1 copper-based catalysts are carried out at preheating with silicon under 200-500 DEG C of inert atmosphere
2-10h is managed, obtains contact；
(2) it is 0.1-1MPa in pressure by contact and chloromethanes, temperature reacts 2-36h under the conditions of being 300-800 DEG C, and controls
The incomplete reaction of silicon processed；
(3) impurity in removal step (2) reaction product and unreacted silicon is separated, that is, obtains silicon nanowire material, together
When by-product organic silicon monomer.
The preparation method of silicon nanowire material provided by the invention, solves silicon nanowire material production cost height, technique
The problems such as complicated, seriously polluted and industrialized production is difficult.It is anti-by adjusting using silicon and chloromethanes catalytic reaction technology
Should in silica flour and the copper-based catalyst particle size of solid and mass ratio, reactor, pretreatment temperature and time, reaction temperature,
The process conditions such as reaction time and different copper-based catalysts, obtained diameter, length and the silicon of silicon nanowires can be regulated and controled
Yield, so as to prepare the adjustable silicon nanowire material of draw ratio, while the byproduct of reaction of high price value-organic can be obtained
Silicon monomer.Using more catalyst, higher reaction temperature, longer reaction time etc., thinner silicon nanometer can be obtained
Line, while the yield of silicon is relatively low；Conversely, the yield of thicker silicon nanowires and higher silicon can be obtained.
The second object of the present invention is to provide a kind of silicon nanowires material being prepared using preparation method as described above
Material, a diameter of 10nm-10 μm of the silicon nanowire material, as 20nm, 30nm, 50nm, 100nm, 300nm, 500nm, 1 μm, 3
μm, 5 μm, 7 μm or 9 μm, length be 10nm-50 μm, as 20nm, 30nm, 50nm, 500nm, 1 μm, 5 μm, 9 μm, 15 μm, 22 μm,
35 μm or 46 μm.
The draw ratio of described silicon nanowire material can be regulated and controled by the selection of reaction condition, can also pass through part oxygen
The silica changed and then surface oxidation is removed by alkali cleaning or pickling post processing is finely adjusted to the diameter and length of nano wire.
Compared with prior art, beneficial effects of the present invention are：
1st, the preparation method of silicon nanowire material provided by the invention is reacted using the heatable catalytic of industrial silicon and chloromethanes
Silicon nanowire material is prepared, reaction process is simple, and reaction condition is not harsh, solves prior art and is difficult to silicon nanowires material
Expect prepare key issue, and be made silicon nanowires while the high value of by-product organic silicon monomer chemicals；
2nd, the preparation method of silicon nanowire material provided by the invention is by adjusting the dosage, size, shape of copper-based catalysts
Looks and preparation process condition can regulate and control diameter, length, the major diameter when silicon yield, and obtained silicon is received of silicon nanowire material
Nanowire material diameter and distribution of lengths are homogeneous, and diameter is between 10nm-10 μm, and length is between 10nm-50 μm；
3rd, the preparation method of silicon nanowire material provided by the invention in the preparation process of silicon nanowire material without using
The hydrofluoric acid of hypertoxicity, the generation of fluoride waste is avoided, prepared by the cleaning for realizing silicon nanowire material；
4th, the preparation method low production cost of silicon nanowire material provided by the invention, technique is simple, suitable for scale
Production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the silica flour that embodiment 1 provides；
Fig. 2 is the XRD of the silica flour that embodiment 1 provides and obtained silicon nanowires；
Fig. 3 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 2；
Fig. 5 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 3；
Fig. 6 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 4；
Fig. 7 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 5；
Fig. 8 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 6；
Fig. 9 is the scanning electron microscope (SEM) photograph of silicon nanowire material made from embodiment 7；
Figure 10 is the scanning electron microscope (SEM) photograph of porous silica material made from comparative example 1；
Figure 11 is the scanning electron microscope (SEM) photograph of porous silica material made from comparative example 2；
Figure 12 is the scanning electron microscope (SEM) photograph of porous silica material made from comparative example 3.
Embodiment
To better illustrate the present invention, technical scheme is readily appreciated, below in conjunction with the accompanying drawings and by specific
Embodiment further illustrates technical scheme.Those skilled in the art are it will be clearly understood that the embodiment is only
Help understands the present invention, is not construed as the concrete restriction to the present invention.
The preparation method that following examples prepare silicon nanowires is：In copper-based major catalyst (Cu, Cu2O, CuO, CuCl and
CuCl2In a kind or at least two combination) and the catalytic action of co-catalyst under, the reaction of elemental silicon and chloromethanes generates
Chlorosilane, remaining solid residue obtain silicon nanowire material after going the removal of impurity.Silica flour used is commercially produced product, and solid is copper-based
Catalyst prepares or is commercialized solid copper-based catalysts to be autonomous.
Embodiment 1
The preparation method of silicon nanowire material is as follows：
(1) by commercially available 10 grams of silicon power raw material (particle size range 10-100 microns), self-control sheet Cu-Cu2O-CuO powders
2.0 grams of 10 grams of material (as major catalyst, particle size range 0.5-10.0 microns), zinc powder mixed grindings are uniform, under nitrogen atmosphere,
450 DEG C of the pre-heat treatment 2h, contact is made；
(2) 22.0 grams of contacts are loaded into fixed bed reactors, is passed through methyl chloride gas (gas velocity 30mL/min), regulation pressure
Power is 1MPa, cools to 400 DEG C, after reacting 6h, reaction product is cooled into 10-30 DEG C, the gaseous products warp in course of reaction
Chemicals can be separated into as the mixture of organic silicon monomer, later stage by rectifying by crossing after condensation, and unreacted chloromethanes can return
Receive and utilize, wherein 57% silicon does not participate in reaction；
(3) step (2) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and sky is passed through in tube furnace
Gas (gas velocity 100mL/min) is warming up to 500 DEG C of calcining 1h and removes carbon distribution, is cooled to 10-30 DEG C, 90 DEG C of conditions in concentrated nitric acid
Lower supersound process 4h, clean 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction in sodium hydroxide solution
24h, the silica of 5 times removal surface of silicon nanowires is cleaned repeatedly with deionized water, in vacuum drying chamber in 80 DEG C of dry 24h
Obtain final silicon nanowire material.
X ' the Pert that silica flour and obtained silicon nanowire material are produced in Dutch Panalytical companies (PANalytical)
Material crystal formation test is carried out on PRO MPD type Multi-functional X ray diffractometers.Test result as shown in Fig. 2 in comparison diagram 2 two
Bar XRD curves understand that their peak position is almost completely the same, and the silicon nanowire material for illustrating gained is pure silicon material.
Produced by the silica flour used and using silicon nanowire material made from the above method in Japan Electronics Corporation
JSM6700 models field emission scanning electron microscope observes surface topography, and testing result is distinguished as shown in figures 1 and 3, as shown in Figure 1, silicon
Silty it is closely knit, surface is smooth；From the figure 3, it may be seen that the silicon nanowire material diameter and length that are prepared are homogeneous, nanowire diameter
Between 50 nanometers to 130 nanometers, 75 rans are concentrated mainly on, nanowire length is between 1 micron to 8 microns, mainly
Concentrate on 5 microns.
The silicon nanowire material of above-mentioned preparation is prepared into the 2001A type discharge and recharges that electrode slice produces in Wuhan Lan electricity companies
Charge-discharge test is carried out on tester, discharge capacity reaches 2655mAh/g first, first discharging efficiency 68%, after 100 times
Capability retention is 84%.
Embodiment 2
The preparation method of silicon nanowire material is as follows：
(1) by commercially available 8 grams of silicon power raw material (particle size range 5-50 microns) and commercially available spherical Cu2O powder materials
Expect that 5 grams of 2.0 grams of (as major catalyst, particle size range 1-5 microns), zinc powder mixed grindings are uniform, under argon gas atmosphere, 250 DEG C pre-
9h is heat-treated, contact is made；
(2) 15.0 grams of contacts are loaded into fixed bed reactors, is passed through methyl chloride gas (gas velocity 30mL/min), regulation pressure
Power is 1MPa, is warming up to 370 DEG C, after reacting 18h, is cooled to 10-30 DEG C, the gaseous products in course of reaction after condensation into
For the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, wherein
43% silicon does not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 200mL/min) 600 DEG C of calcining 2h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
The JSM6700 models that obtained nano-material is produced in obtained silicon nanowire material in Japan Electronics Corporation
Field emission scanning electron microscope observes surface topography, as a result as shown in figure 4, the diameter of the silicon nanowire material prepared arrives at 30 nanometers
100 nanometers, 60 rans are concentrated mainly on, length is concentrated mainly on 7 microns at 3 microns to 10 microns.
The silicon nanowire material of above-mentioned preparation is measured into silicon nanowires on the type ultraviolet-uisible spectrophotometer of Hitachi -850
The photoluminescence property of material, excitation wavelength 256.6nm, it is 600-800nm to measure its photic wavelength of transmitted light.
Embodiment 3
The preparation method of silicon nanowires is as follows：
(1) commercially available 20 grams of silicon power raw material (particle size range 1-20 microns), flower-shaped 5 grams of the Cu powder body materials of self-control (are made
For major catalyst, particle size range 0.5-10 microns), 0.8 gram of mixed grinding of zinc powder it is uniform, under helium atmosphere, 360 DEG C of the pre-heat treatments
5h, contact is made；
(2) 25.8 grams of contacts are loaded into fixed bed reactors, is passed through methyl chloride gas (gas velocity 40mL/min), regulation pressure
Power is 0.7MPa, is warming up to 550 DEG C, after reacting 8h, is cooled to 10-30 DEG C, and the gaseous products in course of reaction are after condensation
As the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, its
In 55% silicon do not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 100mL/min) 500 DEG C of calcining 1h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result as shown in figure 5, it can be seen that the diameter of the silicon nanowire material prepared is received at 30 nanometers to 120
Rice, is concentrated mainly on 65 rans, length is concentrated mainly on 3 microns at 1 micron to 7 microns.
Embodiment 4
The preparation method of silicon nanowires is as follows：
(1) by commercially available 10 grams of silicon power raw material (particle size range 20-100 microns) and commercially available CuO-CuCl powders
0.2 gram of 20 grams of material (as major catalyst, particle size range 0.2-2.5 microns), 2.0 grams of zinc powder, cupro silicon mixed grinding are equal
It is even, under nitrogen atmosphere, 300 DEG C of the pre-heat treatment 7h, contact is made；
(2) 32.2 grams of contacts are loaded into fluidized-bed reactor, is passed through methyl chloride gas (gas velocity 50mL/min), regulation pressure
Power is 1MPa, is warming up to 450 DEG C, after reacting 11h, is cooled to 10-30 DEG C, the gaseous products in course of reaction after condensation into
For the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, wherein
30% silicon does not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 100mL/min) 700 DEG C of calcining 2h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result as shown in fig. 6, it can be seen that a diameter of 50 nanometers of the silicon nanowire material prepared are received to 80
Rice, 60 rans are concentrated mainly on, length is 1 micron to 5 microns, is concentrated mainly on 3 microns.
Embodiment 5
The preparation method of silicon nanowires is as follows：
(1) by commercially available 30 grams of silicon power raw material (particle size range 1-30 microns) and commercially available CuO powder body materials 20
0.01 gram of gram (as major catalyst, particle size range 0.5-5 microns), 2.0 grams of zinc powder, glass putty mixed grinding are uniform, argon gas atmosphere
Under, 500 DEG C of the pre-heat treatment 2h, contact is made；
(2) 52.01 grams of contacts are loaded into fluidized-bed reactor, is passed through methyl chloride gas (gas velocity 45mL/min), adjusted
Pressure is 0.6MPa, after 500 DEG C are reacted 20h, is cooled to 10-30 DEG C, the gaseous products in course of reaction after condensation into
For the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, wherein
48% silicon does not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 200mL/min) 600 DEG C of calcining 1h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result as shown in fig. 7, it can be seen that the diameter of the silicon nanowire material prepared is received at 40 nanometers to 80
Rice, is concentrated mainly on 50 rans, length is concentrated mainly on 1 microns at 0.5 micron to 2 microns.
Embodiment 6
The preparation method of silicon nanowires is as follows：
(1) by commercially available 26 grams of silicon power raw material (particle size range 5-50 microns) and commercially available Cu-Cu2O powder materials
0.01 gram of material 30 grams (as major catalysts, particle size range 0.5-10 microns), 2.0 grams of zinc powder, 0.01 gram of glass putty, phosphorus powder mixing are ground
Mill is uniform, under nitrogen atmosphere, 280 DEG C of the pre-heat treatment 8h, contact is made；
(2) 58.02 grams of contacts are loaded into agitated bed reactor, is passed through methyl chloride gas (gas velocity 30mL/min), adjusted
Pressure is 1MPa, is warming up to 800 DEG C, after reacting 26h, is cooled to 10-30 DEG C, and the gaseous products in course of reaction are after condensation
As the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, its
In 41% silicon do not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 100mL/min) 500 DEG C of calcining 2h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result as shown in figure 8, it can be seen that a diameter of 30 nanometers of the silicon nanowire material prepared are received to 80
Rice, 60 rans are concentrated mainly on, length is 1 micron to 6 microns, is concentrated mainly on 3 microns.
Embodiment 7
The preparation method of silicon nanowires is as follows：
(1) by commercially available 35 grams of silicon power raw material (particle size range 1-20 microns), homemade dendroid CuCl powder body materials
0.01 gram of 10 grams (as major catalysts, particle size range 1-5 microns), 2.0 grams of zinc powder, 0.01 gram of glass putty, ormolu mixing are ground
Mill is uniform, under nitrogen atmosphere, 450 DEG C of the pre-heat treatment 4h, contact is made；
(2) 47.02 grams of contacts are loaded into agitated bed reactor, is passed through methyl chloride gas (gas velocity 60mL/min), adjusted
Pressure is 1MPa, is warming up to 700 DEG C, after reacting 30h, is cooled to 10-30 DEG C, and the gaseous products in course of reaction are after condensation
As the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, its
In 52% silicon do not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 100mL/min) 700 DEG C of calcining 1h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result as shown in figure 9, it can be seen that a diameter of 40 nanometers of the silicon nanowire material prepared are received to 200
Rice, 100 rans are concentrated mainly on, length is 40 nanometers to 500 nanometers, is concentrated mainly on 300 rans.
Embodiment 8
The preparation method of silicon nanowires is as follows：
(1) by commercially available 18 grams of silicon power raw material (particle size range 10-200 microns), self-control CuCl210 grams of powder body material
0.01 gram of (as major catalyst, particle size range 1-10 microns), 1.0 grams of zinc powder, 0.1 gram of cupro silicon, phosphorus powder mixed grinding are equal
It is even, under argon gas atmosphere, 500 DEG C of the pre-heat treatment 5h, contact is made；
(2) 29.11 grams of contacts are loaded into fixed bed reactors, is passed through methyl chloride gas (gas velocity 40mL/min), adjusted
Pressure is 1MPa, is warming up to 600 DEG C, after reacting 18h, is cooled to 10-30 DEG C, and the gaseous products in course of reaction are after condensation
As the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, its
In 45% silicon do not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 200mL/min) 500 DEG C of calcining 1h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result for：A diameter of 20 nanometers to 5 microns of the silicon nanowire material silicon nanowire material of preparation, it is main to concentrate
In 3 microns, length is 15 microns to 50 microns, is concentrated mainly on 30 microns.
Embodiment 9
The preparation method of silicon nanowires is as follows：
(1) by commercially available 10 grams of silicon power raw material (particle size range 10-200 microns), commercially available Cu-CuO-CuCl powder
0.01 gram of 4 grams of body material (as major catalyst, particle size range 1-20 microns), 0.5 gram of zinc powder, 0.02 gram of glass putty, phosphorus powder mixing
Grinding is uniform, under nitrogen atmosphere, 300 DEG C of the pre-heat treatment 9h, contact is made；
(2) 14.53 grams of contacts are loaded into fluidized-bed reactor, is passed through methyl chloride gas (gas velocity 60mL/min), adjusted
Pressure is 1MPa, is warming up to 700 DEG C, after reacting 36h, is cooled to 10-30 DEG C, and the gaseous products in course of reaction are after condensation
As the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, its
In 53% silicon do not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 200mL/min) 600 DEG C of calcining 2h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained nano-material is observed into table in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Face pattern, as a result for：A diameter of 500 nanometers to 9 microns of obtained silicon nanowire material, are concentrated mainly on 7 microns, long
Spend for 15 microns to 40 microns, be concentrated mainly on 30 microns.
Embodiment 10
The preparation method of silicon nanowires is as follows：
(1) by commercially available 20 grams of silicon power raw material (particle size range 1-200 microns) and 8 grams commercially available of Cu powder body materials
0.5 gram of (as major catalyst, particle size range 0.1-1 microns), zinc powder mixed grinding are uniform, under nitrogen atmosphere, at 380 DEG C of preheatings
6.5h is managed, contact is made；
(2) 28.5 grams of contacts are loaded into fixed bed reactors, is passed through methyl chloride gas (gas velocity 30mL/min), regulation pressure
Power is 1MPa, is warming up to 420 DEG C, after reacting 25h, is cooled to 10-30 DEG C, the gaseous products in course of reaction after condensation into
For the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, wherein
65% silicon does not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 100mL/min) 500 DEG C of calcining 1h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
Obtained silicon nanowire material is observed in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Surface topography, as a result for：A diameter of 2 microns to 10 microns of obtained silicon nanowire material, are concentrated mainly on 5 microns,
Length is 9 microns to 30 microns, is concentrated mainly on 20 microns.
Embodiment 11
The preparation method of silicon nanowires is as follows：
(1) by commercially available 20 grams of silicon power raw material (particle size range 1-200 microns) and 8 grams commercially available of Cu powder body materials
0.5 gram of (as major catalyst, particle size range 0.1-1 microns), zinc powder mixed grinding are uniform, under nitrogen and helium atmosphere, 200 DEG C
The pre-heat treatment 10h, contact is made；
(2) 28.5 grams of contacts are loaded into fixed bed reactors, is passed through methyl chloride gas (gas velocity 30mL/min), regulation pressure
Power is 0.1MPa, is warming up to 300 DEG C, after reacting 2h, is cooled to 10-30 DEG C, and the gaseous products in course of reaction are after condensation
As the mixture of organic silicon monomer, the later stage can be separated into chemicals by rectifying, unreacted chloromethanes recoverable, its
In 70% silicon do not participate in reaction；
(3) reacted solid residue contains silicon, copper-based catalysts and carbon distribution, and air (gas velocity is passed through in tube furnace
For 100mL/min) 500 DEG C of calcining 1h removing carbon distributions are warming up to, 10-30 DEG C is cooled to, it is ultrasonic under the conditions of 90 DEG C in concentrated nitric acid
4h is handled, cleans 5 times removal copper-based catalysts repeatedly with deionized water, then the stirring reaction 24h in sodium hydroxide solution, is used
Deionized water cleans the silica of 5 times removal surface of silicon nanowires repeatedly, is obtained most in 80 DEG C of dry 24h in vacuum drying chamber
Whole silicon nanowire material.
The JSM6700 models that obtained nano-material is produced in obtained silicon nanowire material in Japan Electronics Corporation
Field emission scanning electron microscope observe surface topography, as a result for：A diameter of 10 nanometers to 50 nanometers of obtained silicon nanowire material, it is main
20 rans are concentrated on, length is 10 nanometers to 30 nanometers, is concentrated mainly on 25 rans.
Comparative example 1
In addition in step (1) without the pre-heat treatment, remaining is same as Example 1.
Obtained product is observed into surface shape in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Looks, product made from discovery are porous silica material (as shown in Figure 10), rather than silicon nanowire material.
Comparative example 2
In addition to the pre-heat treatment in step (1) is carried out at 150 DEG C, remaining is same as Example 1.
Obtained product is observed into surface shape in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Looks, product made from discovery are porous silica material (as shown in figure 11).
Comparative example 3
In addition to the pre-heat treatment in step (1) is carried out at 550 DEG C, remaining is same as Example 1.
Obtained product is observed into surface shape in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Looks, product made from discovery are silicon grain material (as shown in figure 12).
Comparative example 4
In addition to the time of the pre-heat treatment in step (1) is 1.5h, remaining is same as Example 1.
Obtained product is observed into surface shape in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Looks, product made from discovery are porous silica material.
Comparative example 5
In addition to the time of the pre-heat treatment in step (1) is 10.5h, remaining is same as Example 1.
Obtained product is observed into surface shape in the JSM6700 models field emission scanning electron microscope that Japan Electronics Corporation produces
Looks, product made from discovery are porous silica material.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.
Claims (18)
1. a kind of preparation method of silicon nanowire material, it is characterised in that the preparation method comprises the following steps：
(1) copper-based catalysts and silicon are subjected to the pre-heat treatment 2-10h under 200-500 DEG C of inert atmosphere, obtain contact, it is described
The mass ratio of silicon and copper-based catalysts is any ratio in contact；
(2) contact and chloromethanes are reacted, and controls the incomplete reaction of silicon；
(3) impurity in removal step (2) reaction product and unreacted silicon is separated, that is, obtains silicon nanowire material, at the same it is secondary
Produce organic silicon monomer.
2. preparation method according to claim 1, it is characterised in that step (1) described inert atmosphere be argon gas, nitrogen or
One kind or at least two combination in helium.
3. preparation method according to claim 1, it is characterised in that silicon and copper-based catalysts in step (1) described contact
Mass ratio be 1:3-5:1.
4. preparation method according to claim 1, it is characterised in that step (1) described copper-based catalysts include main catalytic
Agent and a small amount of co-catalyst, the major catalyst are Cu, Cu2O, CuO, CuCl or CuCl2In one kind or at least two group
Close.
5. preparation method according to claim 4, it is characterised in that the co-catalyst is zinc, tin, phosphorus, ormolu
Or one kind in cupro silicon or at least two combination.
6. preparation method according to claim 1, it is characterised in that the granular size of step (1) described copper-based catalysts
For nanoscale, micron order or grade.
7. preparation method according to claim 1, it is characterised in that the granular size of step (1) described copper-based catalysts
For micron order.
8. preparation method according to claim 1, it is characterised in that the pattern of step (1) described copper-based catalysts is ball
Shape, dendroid, flower-shaped, sheet, powdered or gel.
9. preparation method according to claim 1, it is characterised in that the granular size of step (1) described silicon be nanoscale,
Micron order or grade.
10. preparation method according to claim 1, it is characterised in that the granular size of step (1) described silicon is micron
Level.
11. preparation method according to claim 1, it is characterised in that the pattern of step (1) described silicon is sheet or particle
Shape.
12. preparation method according to claim 1, it is characterised in that step (1) described silicon be non-crystalline silicon, monocrystalline silicon or
Polysilicon.
13. preparation method according to claim 1, it is characterised in that the temperature of step (2) described reaction is 300-800
℃。
14. preparation method according to claim 1, it is characterised in that the time of step (2) described reaction is 2-36h.
15. preparation method according to claim 1, it is characterised in that the pressure of step (2) described reaction is 0.1-
1MPa。
16. preparation method according to claim 1, it is characterised in that step (2) reaction is in fixed bed, agitated bed
Or carried out on fluid bed.
17. preparation method according to claim 1, it is characterised in that step (3) is described to go the removal of impurity to be：By step (2)
Obtained reaction product is calcined, acid elution, neutralizing treatment and drying process.
18. preparation method according to claim 1, it is characterised in that the preparation method comprises the following steps：
(1) it is 1 by mass ratio:3-5:1 copper-based catalysts carry out the pre-heat treatment 2- with silicon under 200-500 DEG C of inert atmosphere
10h, obtain contact；
(2) it is 0.1-1MPa in pressure by contact and chloromethanes, temperature reacts 2-36h under the conditions of being 300-800 DEG C, and controls silicon
Incomplete reaction；
(3) impurity in removal step (2) reaction product and unreacted silicon is separated, that is, obtains silicon nanowire material, at the same it is secondary
Produce organic silicon monomer.
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| CN109607542B (en) * | 2018-12-11 | 2022-06-17 | 廊坊绿色工业技术服务中心 | Silicon nano-particle and preparation method and application thereof |
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| CN109850843B (en) * | 2019-03-14 | 2021-01-15 | 南京大学 | Batch preparation method of suspended nanowire manipulator |
| CN112279255B (en) * | 2020-10-27 | 2022-07-29 | 燕山大学 | Preparation method of Si nanowire with high length-diameter ratio |
| CN112599758B (en) * | 2021-03-03 | 2021-07-06 | 拓米(成都)应用技术研究院有限公司 | Nano silicon aggregate composite negative electrode material and preparation method thereof |
| CN115036496B (en) * | 2021-03-05 | 2024-02-13 | 中国科学院过程工程研究所 | Silicon nanowire-based flexible self-supporting electrode material and preparation method thereof |
| 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 |
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| CN103508458A (en) * | 2013-09-16 | 2014-01-15 | 中国科学院过程工程研究所 | Porous silicon material and preparation method thereof |
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