CN109748282A - A kind of method of low temperature preparation nanometer silicon carbide - Google Patents
A kind of method of low temperature preparation nanometer silicon carbide Download PDFInfo
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Abstract
The invention proposes a kind of methods of low temperature preparation nanometer silicon carbide, this method uses " double confinements " process, the compound of silicon/carbon dioxide is prepared by pyrolytic silicon dioxide/polymer compound first, then by obtained compound and magnesium metal or calcium mechanical mixture, it is heat-treated in closed reactor, nanostructure SiC can be obtained finally, successively being cleaned with hydrochloric acid and hydrofluoric acid.Carbon skeleton in this synthetic route in silicon/carbon dioxide compound provides the first confinement effect, limits growing up for nano SiC, and closed reactor provides the second confinement effect, reduces the temperature of carbon thermal reduction.The nanometer silicon carbide of this method preparation has big specific surface area and hole abundant, can be used as carrier to load metal silver catalyst, and be used for lithium ion battery negative material.Nano silicon carbide silicon preparation method provided by the invention, technical process is simple, is easy to implement large-scale production.
Description
Technical field
The invention belongs to field of material preparation, are related to a kind of method of low temperature preparation nanometer silicon carbide.
Background technique
Silicon carbide (SiC) is commonly called as diamond dust, is sent out after first generation semiconductor material and second generation compound semiconductor materials
The novel semiconductor material that exhibition is got up has many advantages, such as that band gap wide (2.3eV-3.3eV), thermal conductivity are high, electron mobility is fast, because
This is very suitable for making high temperature, high-power and High Density Integration electronic device.In addition, SiC also has excellent chemical stabilization
Property, good mechanical performance and thermal shock resistance, and become the ideal of the filtering material and catalyst carrier under harsh conditions
Candidate material.Nanostructure SiC performance is better than traditional SiC powder, can reach the strict demand of more high-tech sector, in energy
There is wider application in the fields such as source storage and catalyzed conversion.Carbothermic method, which prepares SiC, is considered making most mature conjunction
At method, i.e., SiC is made in the silica in hot conditions, reduction with carbon quartz sand, and this method reaction temperature is higher, is difficult
Obtain nanostructure SiC.Carbothermic method is improved, researcher is using microwave as heat source, with phenolic resin and high-purity
SiO2Nano particle as carbon source and silicon source, lower temperature and obtained in the short time partial size be 5-80nm, purity 98%
Nano SiC.The nano SiC material synthesized in this way mainly exists in the form of nano whisker, nano particle etc., use process
In easily reunite, cause specific surface area to reduce.Chemical vapour deposition technique is also frequently used to the synthesis of nano SiC, this method
It is so that reaction product steam is formed higher supersaturation vapor pressure under conditions of being higher than theoretical reaction temperature, causes it automatic
It is condensed into nucleus, is then gathered into particle.Common silane and hydro carbons are raw material, can synthesize purity is high, partial size is 10-100nm's
Particle.However this method requires material purity high, it is wider and easy to reunite to obtain product particle size distribution, yield also compared with
It is low.So how to find a kind of simple process, high yield, high-purity, the method for preparing nano SiC of partial size and structure-controllable
It is still a major challenge.
Summary of the invention
The object of the present invention is to provide the preparation methods of low temperature preparation nano SiC, using " double confinements " (double
Confinements) process realizes the nanosizing of SiC structure.It is prepared first by pyrolytic silicon dioxide/polymer compound
Then the compound of silicon/carbon dioxide mixes obtained compound with metallic reducing agent, in closed reactor at heat
Reason, can be obtained nanostructure SiC finally, successively being cleaned with mixed acid and deionized water.In this synthetic route silica/
Carbon skeleton in carbon complex provides the first confinement effect, limits growing up for nano SiC, and closed reactor provides the second confinement
Effect reduces the temperature of carbon thermal reduction.
The technical scheme is that
A kind of method of low temperature preparation nanometer silicon carbide, comprises the following steps that
(1) using polymer and nano-scale silica as raw material, by the mass ratio of polymer and silica
Mechanical mixture is carried out between 1:5-0.5；
(2) mixture prepared by (1) is pyrolyzed in 500-900 DEG C 1-4h, generates silicon/carbon dioxide compound；It is described
Pyrolysis atmosphere is argon gas or nitrogen, and throughput is 0.2-3 L/min, and heating rate is 1-10 DEG C/min；
(3) the silicon/carbon dioxide compound for obtaining (2) and metallic reducing agent carry out mechanical mixture, are then transferred into close
It closes in reactor, is then heat-treated；Heat treatment temperature is 400-750 DEG C；Obtain carbon thermal reduction product；
(4) (3) carbon thermal reduction product is placed in mixed acid, stand 3-48h, after be washed with deionized, be finally placed in
Nanometer silicon carbide is made in oven drying；The mixed acid is the hydrofluoric acid and concentrated hydrochloric acid of 1:1-5 volume ratio mixing, hydrogen in nitration mixture
Ion concentration is 0.1-1.0 M/L.
Further, heat treatment temperature is preferably 400-650 DEG C in (3).
Further, polymer described in above-mentioned (1) is polymer of the carbon content in 30wt% or more.
Further, polymer is phenolic resin, starch, cellulose, chitin, one in Lauxite in above-mentioned (1)
Kind or two or more mixing.
Further, the pattern of nano-scale silica is ball-type and rodlike in above-mentioned (1), and partial size is in 5-80nm model
In enclosing.
Further, metallic reducing agent described in above-mentioned (3) is one of sodium, magnesium or calcium；The material of closed reactor
For stainless steel or copper.
Further, 80 DEG C of drying temperature in above-mentioned (4), dry 4-10h.
Further, mechanical mixture mode is ball milling or mechanical stirring in above-mentioned (1) and (3).
The present invention also provides the nanometer silicon carbides of the method for the present invention preparation in cell negative electrode material and catalyst carrier
Using.This kind of material because of its large specific surface area, further can largely adulterate heterogeneous element for supercapacitor, hydrogen storage material and
The application such as gas sensing；High porosity is conducive to gas absorption, storage and the transmitting of electrolyte, effectively increases gas biography
Sense, storage and electric property.
Technical effect of the invention: providing the low-temperature synthetic method of structure structure silicon carbide, by pyrolytic silicon dioxide/poly-
It closes object and " double confinements " effect reduction method generates SiC, the various structures nano SiC such as mesoporous, ball-type can be obtained.It is obtained to receive
The pattern and pore structure of rice SiC is consistent with the pattern of raw material and pore structure." double confinements " effect provided by the invention can be with
The reunion for limiting SiC nano particle, can prepare nano SiC at a lower temperature, it is made to be easy to maintain nanostructure.This hair
The nano silicon carbide silicon preparation method of bright offer, technical process is simple, is easy to implement large-scale production.
Detailed description of the invention
Fig. 1 (a, b) be using partial size for 16nm silica as silicon source, cellulose be carbon source preparation silica/charcoal
Scanning electron microscope (SEM) image under compound different amplification, (c, d) and power spectrum (EDX) Surface scan Si and the C distribution for scheming b
Image.
The XRD diffracting spectrum of nano SiC under Fig. 2 difference reduction temperature.
Fig. 3 reduction temperature is (a) low power and (b) high power transmission electron microscope picture of nano SiC at 650 DEG C.
Fig. 4 reduction temperature is scanning electron microscope (SEM) image of nano SiC at 650 DEG C.
Fig. 5 reduction temperature is (a) nitrogen adsorption isotherm and (b) pore-size distribution of nano SiC at 650 DEG C.
Fig. 6 reduction temperature is the performance of lithium ion battery test of nano SiC at 650 DEG C: (a) charge-discharge curve；(b) 1
A g-1Cycle performance under current density.
Fig. 7 reduction temperature is transmission electron microscope picture of the nano SiC as catalyst carrier loaded Ag at 650 DEG C.
Specific embodiment
Embodiment 1
First confinement effect: a certain amount of cellulose and nano silica (mass ratio 3:1) are weighed, 100ml is placed in
In ball grinder, then mixture is placed in pyrolysis processing in tube furnace by 450rpm ball milling 2h.Treatment temperature is 600 DEG C, and the time is
4h heating rate is 5 DEG C of min-1.Obtained sample cooled to room temperature obtains silicon/carbon dioxide compound.Fig. 1 (a) and
It (b) is the scanning electron microscopic picture of silicon/carbon dioxide compound manufactured in the present embodiment, from the power spectrum Surface scan of Fig. 1 (c) and (d)
It can be seen that silicon is uniformly distributed on carbon skeleton in image, good composite structure is formd with carbon skeleton.
Second confinement effect: by silicon/carbon dioxide compound obtained above and magnesium metal according to certain mass ratio (1:
1) mechanical mixture is carried out, mixture is then transferred to stainless steel reactor, finally place reactor and is heated in tube furnace
To 550 DEG C, 4h is stopped.The compound taken out in reactor after cooled to room temperature is placed in hydrochloric acid and hydrofluoric acid mixed acid,
The volume ratio of nitration mixture is 1:1, and hydrogen ion concentration is 0.5 M/L.Compound stood in nitration mixture be washed with deionized after 5h to
Neutrality is placed in 80 DEG C of oven drying 10h.Fig. 2 is the XRD diffraction spectrogram of nanometer silicon carbide manufactured in the present embodiment, with standard card
Piece JCPDS29-1129 control, 2 θ=35.6 °, 60 ° and 71.7 ° (111) for corresponding respectively to SiC, (220) and (311) crystalline substance
Face.
Embodiment 2
First confinement effect: same as Example 1.
Second confinement effect: reduction temperature is 650 DEG C, and other conditions are the same as embodiment 1, the XRD diffraction pattern of gained nano SiC
For spectrum as shown in Fig. 2, compareing with standard card JCPDS29-1129,2 θ=35.6 °, 60 ° and 71.7 ° correspond respectively to SiC's
(111), (220) and (311) crystal face.(a) and (b) is respectively sample TEM picture in Fig. 3, be can see under low resolution
Sample has certain pore structure, and this is mainly due to SiO in reduction process2The hole that deoxidation leaves after reacting with carbon skeleton
Gap.(111) interplanar distance that SiC can be measured in high-resolution-ration transmission electric-lens picture is 0.252nm.Fig. 4 is the surface sweeping of the sample
Electron microscope picture, it can be seen that there is apparent meso-hole structure.Fig. 5 (a) is nitrogen suction-desorption isotherm of the sample,
Its structure is typical IV type thermoisopleth, has apparent lag winding, is meso-hole structure.Specific surface area SBET=267.3m2/
G, total pore volume Vtotal=0.41cm3/ g (b) is corresponding pore-size distribution, has the aperture relatively concentrated, about 10nm.
Embodiment 3
First confinement effect: same as Example 1.
Second confinement effect: reduction temperature is 400 DEG C, and other conditions are the same as embodiment 1, the XRD diffraction pattern of gained nano SiC
For spectrum as shown in Fig. 2, compareing with standard card JCPDS29-1129,2 θ=35.6 °, 60 ° and 71.7 ° correspond respectively to SiC's
(111), (220) and (311) crystal face.
Using 1:
It is that electrochemistry is carried out at half-cell to electrode assembling with lithium piece using the lower sample prepared of embodiment 2 as active material
Performance test.The inclined tetrafluoroethene 1g mixed grinding of sample 6g, conductive carbon black 3g and binder prepared at 650 DEG C is weighed first,
N-Methyl pyrrolidone 80mL, magnetic agitation 10h is added.The slurry mixed up is coated on copper foil, electrode slice is made, sliced, pressure
It is used as with lithium piece to electrode after piece, CR2025 type button cell is assembled into glove box.The electrolyte of button cell is 1.0M
Lithium hexafluoro phosphate (LiPF6) it is dissolved in the ethylene carbonate (EC) that mass ratio is 1:1:1: dimethyl carbonate (DMC): carbonic acid first
In base ethyl ester (EMC).Electrochemical property test is carried out in constant current charge-discharge system with the rate of 1A/g.Battery assembly behaviour
Make water oxygen content be below 0.1ppm glove box in carry out.The voltage of 0.5V or so is flat in the discharge curve for the first time of Fig. 6
Platform corresponds to the formation of solid electrolyte interface (SEI) film, and coulombic efficiency is 79% for the first time.Have in 100 times subsequent circulations
Good capacity retention ratio, indicate battery have good cycle performance, specific capacity is about 320mAh/g.
Using 2:
Using the lower silicon carbide prepared of embodiment 2 as catalyst carrier, the elemental silver of 10wt% is impregnated using wetness impregnation,
And it is tested applied in paranitrophenol reduction reaction, there is preferable catalytic activity.The transmission electron microscope of Ag/SiC catalyst is such as
Shown in Fig. 7, Ag grain diameter is about 10nm or so.
Claims (9)
1. a kind of method of low temperature preparation nanometer silicon carbide, which is characterized in that comprise the following steps that
(1) using polymer and nano-scale silica as raw material, by the mass ratio of polymer and silica 1:
5-0.5 mechanical mixture is carried out between；
(2) mixture prepared by (1) is pyrolyzed in 500-900 DEG C 1-4h, generates silicon/carbon dioxide compound；The pyrolysis
Atmosphere is argon gas or nitrogen, and throughput 0.2-3L/min, heating rate is 1-10 DEG C/min；
(3) the silicon/carbon dioxide compound for obtaining (2) and metallic reducing agent carry out mechanical mixture, are then transferred into closed anti-
It answers in device, is then heat-treated；Heat treatment temperature is 400-750 DEG C；Obtain carbon thermal reduction product；
(4) (3) carbon thermal reduction product is placed in mixed acid, stand 3-48h, after be washed with deionized, be finally placed in baking oven
It is dry, nanometer silicon carbide is made；The mixed acid is the hydrofluoric acid and concentrated hydrochloric acid of 1:1-5 volume ratio mixing, hydrogen ion in nitration mixture
Concentration is 0.1-1.0M/L.
2. a kind of method of low temperature preparation nanometer silicon carbide according to claim 1, which is characterized in that (1) described in
Polymer is polymer of the carbon content in 30wt% or more.
3. a kind of method of low temperature preparation nanometer silicon carbide according to claim 2, which is characterized in that (1) polymer in
For the mixing of one or more of phenolic resin, starch, cellulose, chitin, Lauxite.
4. a kind of method of low temperature preparation nanometer silicon carbide according to claim 1 or 2 or 3, which is characterized in that (3) in
Heat treatment temperature is 400-550 DEG C.
5. a kind of method of low temperature preparation nanometer silicon carbide according to claim 1 or 2 or 3, which is characterized in that (1) in
The pattern of nano-scale silica is ball-type and rodlike, and partial size is within the scope of 5-80nm.
6. a kind of method of low temperature preparation nanometer silicon carbide according to claim 1 or 2 or 3, which is characterized in that (3) in
The metallic reducing agent is one of sodium, magnesium or calcium；The material of closed reactor is stainless steel or copper.
7. a kind of method of low temperature preparation nanometer silicon carbide according to claim 1 or 2 or 3, which is characterized in that (4) in
80 DEG C of drying temperature, dry 4-10h.
8. a kind of method of low temperature preparation nanometer silicon carbide according to claim 1 or 2 or 3, which is characterized in that (1) and
(3) mechanical mixture mode is ball milling or mechanical stirring in.
9. the application of the nanometer silicon carbide of any the method preparation of claim 1-8, which is characterized in that the nanometer of meso-hole structure
Silicon carbide is applied to lithium ion battery electrode material and catalyst carrier.
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| CN111360280A (en) * | 2020-04-09 | 2020-07-03 | 大连海事大学 | Raman enhancement material and rapid preparation method thereof |
| CN111484017A (en) * | 2020-06-22 | 2020-08-04 | 黑龙江冠瓷科技有限公司 | Method for preparing SiC nanoparticles based on silica microspheres @ C |
| CN112028075A (en) * | 2020-09-03 | 2020-12-04 | 天能帅福得能源股份有限公司 | Preparation method of nano SiC used as lithium ion battery cathode material |
| CN112573895A (en) * | 2020-12-25 | 2021-03-30 | 唐山北方瓷都陶瓷集团卫生陶瓷有限责任公司 | High-strength ceramic biscuit and preparation process thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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