CN107161978B - Preparation method of sulfur-containing hollow carbon microspheres - Google Patents
Preparation method of sulfur-containing hollow carbon microspheres Download PDFInfo
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- CN107161978B CN107161978B CN201710448014.3A CN201710448014A CN107161978B CN 107161978 B CN107161978 B CN 107161978B CN 201710448014 A CN201710448014 A CN 201710448014A CN 107161978 B CN107161978 B CN 107161978B
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention relates to a preparation method of sulfur-containing hollow carbon microspheres, which adopts a single quartz tube and a tube furnace matched with double heating furnaces; placing the porcelain boat containing the sulfur powder in the center of a first heating furnace of a tube furnace; placing the porcelain boat with the tungsten hexacarbonyl in the center of a second heating furnace of the tube furnace, placing the substrate at the rear side of a tungsten hexacarbonyl heating zone, and introducing argon; under the argon atmosphere, the internal pressure of the tube furnace is emphasized to 0.1 Pa-20 Pa, the first heating area is heated to the volatilization temperature of sulfur powder, and the second heating area is heated to the volatilization temperature of tungsten hexacarbonyl; introducing mixed gas of argon and hydrogen, opening the plasma generating device to deposit the sulfur-containing hollow carbon microspheres on the surface of the substrate, and then cooling to room temperature to obtain the sulfur-containing carbon microsphere material. The method reduces the preparation temperature of the sulfur-containing hollow carbon microspheres to 170 ℃, is simple to operate, has good repeatability, improves the yield of the microspheres, and has good application prospects in the fields of preparation of lithium ion battery cathodes, hydrogen storage and the like.
Description
Technical field
The present invention relates to a kind of preparation methods of the hollow carbosphere of sulfur-bearing, belong to carbon material preparation field.
Background technique
Hollow carbosphere has the characteristics that low density, large specific surface area, permeance property are good, in catalyst carrier, absorption
The fields such as agent, lithium ion battery, bio-pharmaceuticals and gene therapy have a wide range of applications.
With going deep into for people's research, a large amount of research achievement shows that hetero atom (N, B, P, S, F, Ni, Co etc.) doping is
The effective path for promoting carbon material chemical property.Doping carbosphere has excellent chemical property, in super electricity
The fields such as container, fuel cell have huge application potential, have attracted the concern of numerous scientific workers.It is mixed by hetero atom
Miscellaneous, doping carbosphere, which can overcome, be made of that caused surface wettability is poor, chemical property is not active enough single carbon atom, surface
The disadvantages of active site is few greatly improves to have more excellent redox catalysis activity, higher specific capacitance etc.
Promotion potential of the carbosphere in terms of new energy materials.Sulfur doping can introduce fake capacitance.Compared with undoped with Carbon Materials, sulphur member
Better electric conductivity is shown after element doping, in addition, sulfur doping can also influence aperture and the structure of porous carbon materials.This
Outside, sulfur-bearing carbosphere produces a large amount of chemical structure faults due to the introducing of sulphur atom, can bring to hollow carbosphere higher
Specific surface area.Doped hollow microballoon often has chemical vapour deposition technique, emulsion method, pyrolysismethod, template and water with preparation method
Hot carbonizatin method etc..
Chemical vapour deposition technique is one of the common method for preparing carbosphere at present.Its principle is: in gas phase reaction item
Under part, the series of chemical such as raw material is dehydrated, is degraded carbonization balling-up, the product good sphericity of acquisition.In synthesis doped carbon
When microballoon, doping agent is mixed into gas raw material, obtains corresponding heteroatomic doping microballoon by gas phase reaction high temperature pyrolysis.But
It is more demanding (>=900 DEG C) of this method to temperature, yield is lower, and surface functional group is less.
In this regard, preparing microballoon for chemical vapour deposition technique, this problem of preparation temperature height proposes plasma enhancing
The method that chemical vapour deposition technique prepares the hollow carbosphere of sulfur doping.The plasma temperature generated by radio-frequency power supply is not high,
But in the state being stimulated inside it, electron energy is enough to make molecular scission, and leads to have chemically active object
Matter (anakmetomeres, atom, ion, atomic group etc.) generates, and makes the chemical reaction for needing just to can be carried out at high temperature originally, works as place
When in plasma field, since the electrical activation of reaction gas acts on and reaction temperature is greatly reduced.
The present invention is using elemental sulfur as carbon source, using the carbonyl in tungsten carbonyl as carbon source, is prepared under the conditions of 170 DEG C
The hollow carbosphere of the high sulfur-bearing of uniform particle sizes, sphericity.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of sulfur-bearing carbosphere, directly during preparing carbosphere
It joined sulphur source, using plasma enhancing chemical vapour deposition technique is prepared for the hollow carbosphere of sulfur-bearing, opens a preparation
The high carbosphere of uniform particle sizes, quality is prepared in the variation route of the hollow carbosphere of sulfur-bearing.Its is easy to operate, reproducible, mentions
High microballoon yield, the material have a good application prospect in fields such as preparation, the hydrogen storages of negative electrode of lithium ion battery.
Technical scheme is as follows:
Elemental sulfur is placed in one warm area of tube furnace, tungsten carbonyl is placed in another warm area, is warming up to sulphur powder and six respectively
The boiling point of tungsten carbonyl obtains sulfur-bearing carbosphere by the effect of argon plasma under the conditions of 0.1Pa~20Pa；Pass through this method
The material being prepared, the application prospect with hydrogen storage direction.
The present invention is realized by the following technical scheme:
A kind of preparation method of the hollow carbosphere of sulfur-bearing, feature includes following procedure:
(1) single quartz ampoule is used, the tube furnace of double furnace is cooperated；The porcelain boat for being placed with sulphur powder is placed in the of tube furnace
One heating furnace center；The porcelain boat for being placed with tungsten carbonyl is put in second heating furnace center of tube furnace again, substrate is placed in
On rear side of tungsten carbonyl heating zone, it is passed through argon gas；
(2) under an argon atmosphere, tube furnace internal pressure is emphasized to 0.1Pa~20Pa, the first heating zone is warming up to sulphur powder
Volatilization temperature, the second heating zone is warming up to the volatilization temperature of tungsten carbonyl；Be passed through the gaseous mixture of argon gas and hydrogen, open etc. from
Daughter generating device makes the hollow carbosphere of sulfur-bearing be deposited on substrate surface, is then down to room temperature, just obtains sulfur-bearing carbosphere material
Material.
It is preferred that 160 DEG C of the volatilization temperature of sulphur powder；
It is preferred that 170 DEG C of three tungsten carbonyl volatilization temperature；
It is preferred that tungsten carbonyl and the mass ratio of sulphur powder are 1~2:500；
It is preferred that the power of plasma producing apparatus is 100~300W.
Preferred substrate is monocrystalline silicon piece, copper foil, any in sheet glass.
This method makes elemental sulfur volatilize respectively with tungsten carbonyl, in argon respectively under the boiling point of elemental sulfur and tungsten carbonyl
Under action of plasma, the S -- Ss of the cyclic structures such as S5, S6, S7, S8 of elemental sulfur, the backdonation of carbonyl and cooperateing with for δ key
Key is opened, after centered on tungsten ion, recombination obtain the hollow carbosphere of sulfur-bearing.
Increase carbon source dosage by fixed sulphur source dosage, the partial size of the hollow carbosphere of obtained sulfur-bearing becomes smaller, be due to
Caused by nucleating point increases.By fixed sulphur source and carbon source dosage, increases the power of plasma generator, do not find to product
Pattern and structure have an impact.
The preparation temperature of the hollow carbosphere of sulfur-bearing is reduced to 170 DEG C by this method, easy to operate, reproducible, is improved
Microballoon yield, the material have a good application prospect in fields such as preparation, the hydrogen storages of negative electrode of lithium ion battery.
Detailed description of the invention:
Fig. 1 is the optical photograph of the hollow carbosphere of sulfur-bearing obtained in embodiment 1；
Fig. 2 is the stereoscan photograph of the hollow carbosphere of sulfur-bearing obtained in embodiment 2；
(a) is the transmission electron microscope photo of the hollow carbosphere of sulfur-bearing obtained in embodiment 3 in Fig. 3, (b) for microballoon progress
The result that elemental analysis obtains.
Specific embodiment
Specific embodiments of the present invention are given below, be to further explanation of the invention, rather than limit it is of the invention
Range.
Embodiment 1:
The device that this example uses is the BTF-1200C-S-SSL-PECVD of Anhui Bei Yike equipment and technology Co., Ltd production
Type tube furnace.
(1) it takes 500mg elemental sulfur to be placed in cillin bottle, is put into the first heating zone；3mg tungsten carbonyl powder is taken to be placed in XiLin
In bottle, it is put into the second heating zone；Monocrystalline silicon piece substrate is placed on rear side of the second heating zone；
(2) it is passed through argon gas before starting to warm up and drains quartzy inner air tube, then in 10sccm argon gas, 10sccm hydrogen atmosphere
It is lower by pressure tune 20Pa；By the first temperature-raising region temperature raising to 160 DEG C, by the second temperature-raising region temperature raising to 170 DEG C；By plasma producing apparatus
It is adjusted to 100W, 10min is reacted, is then down to room temperature, just obtains sulfur-bearing carbosphere.
The optical photograph of sample is as shown in Figure 1, it can be seen from the figure that the sulfur-bearing carbosphere being prepared in the embodiment
Uniform particle sizes, for diameter in 1 microns, the sphericity of microballoon is higher.
Embodiment 2:
(1) it takes 500mg elemental sulfur to be placed in cillin bottle, is put into the first heating zone；1.5mg tungsten carbonyl powder is taken to be placed in west
In woods bottle, it is put into the second heating zone；Glass sheet substrate is placed on rear side of the second heating zone；
(2) it is passed through argon gas before starting to warm up and drains quartzy inner air tube, then in 10sccm argon gas, 10sccm hydrogen atmosphere
It is lower by pressure tune 10Pa；By the first temperature-raising region temperature raising to 160 DEG C, by the second temperature-raising region temperature raising to 170 DEG C；By plasma producing apparatus
It is adjusted to 200W, 10min is reacted, is then down to room temperature, just obtains sulfur-bearing carbosphere.
The electron scanning micrograph of sample by figure as shown in Fig. 2, obtained in the embodiment, and the surface of the microballoon is more
Smooth, microspherulite diameter is in 2 microns.
Embodiment 3:
(1) it takes 500mg elemental sulfur to be placed in cillin bottle, is put into the first heating zone；1mg tungsten carbonyl powder is taken to be placed in XiLin
In bottle, it is put into the second heating zone；Copper foil substrate is placed on rear side of the second heating zone；
(2) it is passed through argon gas before starting to warm up and drains quartzy inner air tube, then in 10sccm argon gas, 10sccm hydrogen atmosphere
It is lower by pressure tune 0.1Pa；By the first temperature-raising region temperature raising to 160 DEG C, by the second temperature-raising region temperature raising to 170 DEG C；Plasma is filled
It sets and is adjusted to 300W, react 10min, be then down to room temperature, just obtain sulfur-bearing carbosphere.
In the embodiment in the transmission electron microscope photo such as Fig. 3 of sample shown in (a), as seen from the figure, microballoon is hollow knot
Structure, in Fig. 3 shown in (b), the atomic percent that analysis obtains carbon in the sample is 64.08, the atomic percent of oxygen element
Than being 14.45, the atomic percent of element sulphur is 21.53, not tungstenic in sample.
Claims (3)
1. a kind of preparation method of the hollow carbosphere of sulfur-bearing, it is characterized in that elemental sulfur is placed in one warm area of tube furnace, six carbonyls
Tungsten is placed in another warm area, is warming up to the volatilization temperature of sulphur powder and tungsten carbonyl respectively, passes through argon etc. under the conditions of 0.1Pa~20Pa
The effect of gas ions obtains sulfur-bearing carbosphere；
(1) single quartz ampoule is used, the tube furnace of double furnace is cooperated；The porcelain boat for being placed with sulphur powder is placed in first of tube furnace
Heating furnace center；The porcelain boat for being placed with tungsten carbonyl is put in second heating furnace center of tube furnace again, substrate is placed in six carbonyls
On rear side of base tungsten heating zone, it is passed through argon gas；
(2) under an argon atmosphere, tube furnace internal pressure is emphasized to 0.1Pa~20Pa, the first heating zone is warming up to waving for sulphur powder
Temperature is sent out, the second heating zone is warming up to the volatilization temperature of tungsten carbonyl；It is passed through the gaseous mixture of argon gas and hydrogen, open plasma
Generating device makes the hollow carbosphere of sulfur-bearing be deposited on substrate surface, is then down to room temperature, just obtains sulfur-bearing carbosphere material；
160 DEG C of the volatilization temperature of the sulphur powder；170 DEG C of the tungsten carbonyl volatilization temperature, the plasma generation
The power of device is 100~300W.
2. the method as described in claim 1, it is characterized in that the mass ratio of the tungsten carbonyl and sulphur powder is 1~2:500.
3. the method as described in claim 1, it is characterized in that the substrate is monocrystalline silicon piece, any in copper foil, sheet glass.
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| CN108133827B (en) * | 2017-12-14 | 2020-02-14 | 三峡大学 | Preparation method of molybdenum disulfide and sulfur-doped carbon sphere composite electrode |
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| CN104561937A (en) * | 2015-01-05 | 2015-04-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing WS2 film having solid lubrication function by means of atomic layer deposition |
| CN105129748A (en) * | 2015-08-24 | 2015-12-09 | 南京邮电大学 | Method for preparing quantum dot of transitional metal chalcogenide compound |
| CN105870253A (en) * | 2016-04-25 | 2016-08-17 | 华中科技大学 | Preparation method for WS<2>/Si heterojunction solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104561937A (en) * | 2015-01-05 | 2015-04-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing WS2 film having solid lubrication function by means of atomic layer deposition |
| CN105129748A (en) * | 2015-08-24 | 2015-12-09 | 南京邮电大学 | Method for preparing quantum dot of transitional metal chalcogenide compound |
| CN105870253A (en) * | 2016-04-25 | 2016-08-17 | 华中科技大学 | Preparation method for WS<2>/Si heterojunction solar cell |
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