CN101774568B - Method for preparing carbosphere through reflux method - Google Patents
Method for preparing carbosphere through reflux method Download PDFInfo
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- CN101774568B CN101774568B CN2010100313370A CN201010031337A CN101774568B CN 101774568 B CN101774568 B CN 101774568B CN 2010100313370 A CN2010100313370 A CN 2010100313370A CN 201010031337 A CN201010031337 A CN 201010031337A CN 101774568 B CN101774568 B CN 101774568B
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Abstract
The invention discloses a method for preparing carbosphere through a reflux method, which comprises the following steps that: (1) sucrose or glucose is dissolved in sulfuric acid solution with the concentration of 2 to 9mol.L-1, solution with the mass concentration of 1 to 60 percent is prepared, stirred and heated to be boiled, condensed and refluxed, reacts for 3 to 15h, is cooled to room temperature and filtered; (2) a filter cake is washed by deionized water and dried, the precursor of the carbosphere is prepared; and (3) under inert gas atmosphere, the precursor of the carbosphere is calcined for 1 to 10h at 600 to 1000DEG C; and the precursor of the carbosphere is cooled to room temperature, and the carbosphere with the particle size of 50 to 200nm is prepared. The method of the invention has the advantages of mild reaction conditions, simple process and good reproducibility. The prepared carbosphere has larger specific surface area. The carbosphere of the invention serves as the raw material of chemical reaction, a catalyst carrier, lithium-ion battery electrode material and supercapacitor electrode material, and has wide application prospect in microelectronics.
Description
Technical field
The present invention relates to the synthetic of inolrganic chemicals, relate to a kind of preparation method of carbosphere.
Background technology
Carbosphere has characteristics such as good chemical stability, thermostability and good conduction, heat conduction, is a kind of carbon material with wide application prospect.
In the forming process of research coke, find that the pitch compounds intermediate phase can take place changes the sixties in last century in heat treatment process, generate mesophase ball.Because carbonaceous mesophase spherules has the performance of many excellences, as unreactiveness, high-bulk-density, good conduction and thermal conductivity, obtain superhigh specific surface area carbon ball after treatment, it is used as new carbon, lithium ion battery negative material, high-performance liquid chromatography filler, support of the catalyst etc. more and more are subject to people's attention.But prepare the productive rate low (being generally 5%-10%) of the method gained of carbonaceous mesophase spherules, leaching process is lengthy and tedious, and the size of microballoon is also wayward, and structure is also more single.Carbosphere has caused people's extensive concern as a kind of very important material, its in the storage of nano-device, energy, separate or great application prospect all arranged as aspects such as lubricants.
For the preparation of carbosphere, mainly be to adopt thermal polycondensation process at present, emulsion process and suspension method [1-3] etc. are that starting material are produced with pitch, in addition, document [4] has been reported the method that is equipped with multi-layer nano carbon ball with the arc discharge legal system.But the preparation technology of these methods more complicated is loaded down with trivial details, and influence factor is more, and the difficulty of condition control is also bigger.For this reason, many new simple and practical methods are developed.At present, Many researchers has been reported the research [5-7] of adopting the Hydrothermal Preparation carbosphere, and document [5,7] has been reported with the method for glucose as raw material synthetic carbosphere under hydrothermal synthesizing condition.Document [6] has reported under hydrothermal synthesizing condition with sucrose to be the method for the synthetic carbosphere of carbon source.The product diameter that the use hydrothermal method obtains is about 500-1000nm, and pattern is homogeneous relatively, has good capacitive property and cycle life, but needs to use autoclave, and reaction needed is carried out under High Temperature High Pressure, and temperature 200-500 ℃, equipment is complexity.
The main reference document:
[1]Korai，Y.；Wang，Y.G.；Yoon，S.H.；Ishida，S.；Mochida?I.，Preparation?of?meso-carbonmicrobeads?with?uniform?diameter?from?AR-isotropic?pitch?in?the?presence?of?carbon?black，Carbon，1996，34：1156-1159
[2] Shen Cengmin, Xue Ruisheng, Chi Weidong, emulsion method prepare the research of MCMB, new carbon, 2004,19 (1): 21-27
[3]Tosheva，L.；Parmentier，J.；Valtchev，V.，Carbon?spheres?prepared?from?zeolite?Beta?beads，Carbon，2005，43：2474
[4]Qiao，W.M.；Song，Y.；Lim，S.Y.，Carbon?nanospheres?produced?in?an?arc-discharge?process，Carbon，2006，44：187
[5]X.M.Sun，Y.D.Li，Colloidal?carbon?spheres?and?their?Core/shell?structures?with?noble?metalnanoparticles，Angew?Chem?Int?Ed，2004，43(5)：597-601.
[6]Q.Wang，H.Li，L.Q.Chen?et?al.，Monodispersed?hard?carbon?spherules?with?uniformnanopores，Carbon，2001，39：2211-2214.
[7]Mi，Y.Z.；Hu，W.B.；Dan，Y.M.；Liu，Y.L.Synthesis?of?carbon?micro-spheres?by?a?glucosehydrothermal?method，Materials?Letters，2008(62)：1194-1196
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide that a kind of production unit is simple, technology is simple, the method for a kind of preparing carbosphere through reflux method that can be continuously produced.
Technical scheme of the present invention is summarized as follows:
A kind of method of preparing carbosphere through reflux method comprises the steps:
(1) sucrose or glucose being dissolved in concentration is 2-9molL
-1Aqueous sulfuric acid in, make the solution that mass concentration is 1%-60%, stir, be heated to solution boiling and condensing reflux, reaction 3-15h is cooled to room temperature, filters;
(2) filter cake deionized water wash; Drying obtains the presoma of carbosphere;
(3) under inert gas atmosphere, at 600～1000 ℃ of calcining 1-10h; Be cooled to room temperature, obtain the carbosphere that particle diameter is 50-200nm.
Described step (1) is preferably: it is 2-9molL that sucrose or glucose are dissolved in concentration
-1Aqueous sulfuric acid in, make the solution that mass concentration is 10%-40%, stir, be heated to solution boiling and condensing reflux, reaction 6-10h is cooled to room temperature, suction filtration.
Rare gas element preferred nitrogen or argon gas.
Preparation method of the present invention has the reaction conditions gentleness, and technology is simple, and has good circulation ratio.The carbosphere diameter of preparation has bigger specific surface area (800～1000m at 50～200nm
2G
-1).Carbosphere of the present invention is as the chemical reaction raw material, support of the catalyst, and lithium ion battery electrode material, electrode material for super capacitor, the microtronics aspect has wide application prospect.
Description of drawings
Fig. 1 is the TEM figure of the carbosphere of the embodiment of the invention 1 preparation.
Fig. 2 is the TEM figure of the carbosphere of the embodiment of the invention 2 preparations.
Fig. 3 is the TEM figure of the carbosphere of the embodiment of the invention 3 preparations.
Fig. 4 is the TEM figure of the carbosphere of the embodiment of the invention 4 preparations.
Fig. 5 is the TEM figure of the carbosphere of the embodiment of the invention 5 preparations.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
A kind of method of preparing carbosphere through reflux method comprises the steps:
With the 1g sucrose dissolved at the good 99g6molL of configured in advance
-1H
2SO
4In the aqueous solution, behind the sucrose acidic aqueous solution of at room temperature abundant stirring formation 1%, solution is joined in the reflux, be heated to solution boiling and condensing reflux, reaction 15h is cooled to room temperature then, filter also and use the deionized water wash filter cake, dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, at N
2Calcine 1h at 1000 ℃ under the atmosphere; Be cooled to room temperature then, obtain carbosphere, its TEM figure sees Fig. 1.
Embodiment 2
A kind of method of preparing carbosphere through reflux method comprises the steps:
10g glucose is dissolved in the good 90g 7molL of configured in advance
-1H
2SO
4The aqueous solution in, at room temperature fully stir form 10% the acid aqueous solution of glucose after, solution is joined in the reflux, be heated to solution boiling and condensing reflux, reaction 10h is cooled to room temperature then, filters and also uses the deionized water wash filter cake; Dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, under argon gas atmosphere, calcine 10h at 600 ℃; Be cooled to room temperature then, obtain carbosphere, its TEM figure sees Fig. 2.
Embodiment 3
A kind of method of preparing carbosphere through reflux method comprises the steps:
With the 30g sucrose dissolved at the good 70g 2molL of configured in advance
-1H
2SO
4The aqueous solution in, at room temperature fully stir form 30% sucrose acidic aqueous solution after, solution is joined in the reflux, be heated to the solution boiling and reflux, reaction 9h is cooled to room temperature then, filters and also uses the deionized water wash filter cake; Dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, at N
2Calcine 4h at 800 ℃ under the atmosphere; Be cooled to room temperature then, obtain carbosphere, its TEM figure sees Fig. 3.
Embodiment 4
A kind of method of preparing carbosphere through reflux method comprises the steps:
With the 5g sucrose dissolved at the good 95g 3molL of configured in advance
-1H
2SO
4The aqueous solution in, at room temperature fully stir form 5% sucrose acidic aqueous solution after, solution is joined in the reflux, be heated to the solution boiling and reflux, reaction 10h is cooled to room temperature then, filters and also uses the deionized water wash filter cake; Dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, under argon gas atmosphere, calcine 10h at 600 ℃; Be cooled to room temperature then, obtain carbosphere, its TEM figure sees Fig. 4.
Embodiment 5
A kind of method of preparing carbosphere through reflux method comprises the steps:
With the 20g sucrose dissolved at the good 80g 9molL of configured in advance
-1H
2SO
4The aqueous solution in, at room temperature fully stir form 20% sucrose acidic aqueous solution after, solution is joined in the reflux, be heated to the solution boiling and reflux, reaction 3h is cooled to room temperature then, filters and also uses the deionized water wash filter cake; Dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, at N
2Calcine 5h at 700 ℃ under the atmosphere; Be cooled to room temperature then, obtain carbosphere, its TEM figure sees Fig. 5.
Embodiment 6
A kind of method of preparing carbosphere through reflux method comprises the steps:
60g glucose is dissolved in the good 40g 5molL of configured in advance
-1H
2SO
4The aqueous solution in, at room temperature fully stir form 60% the acid aqueous solution of glucose after, solution is joined in the reflux, be heated to the solution boiling and reflux, reaction 6h is cooled to room temperature then, filters and also uses the deionized water wash filter cake; Dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, under argon gas atmosphere, calcine 5h at 850 ℃; Be cooled to room temperature then, obtain carbosphere.
Embodiment 7
A kind of method of preparing carbosphere through reflux method comprises the steps:
40g glucose is dissolved in the good 60g 8molL of configured in advance
-1H
2SO
4The aqueous solution in, at room temperature fully stir form 40% the acid aqueous solution of glucose after, solution is joined in the reflux, be heated to the solution boiling and reflux, reaction 8h is cooled to room temperature then, filters and also uses the deionized water wash filter cake; Dry cake obtains the presoma of carbosphere; Get the presoma of carbosphere, under argon gas atmosphere, calcine 3h at 1000 ℃; Be cooled to room temperature then, obtain carbosphere.
Claims (3)
1. the method for a preparing carbosphere through reflux method is characterized in that comprising the steps:
(1) sucrose or glucose being dissolved in concentration is 2-9molL
-1Aqueous sulfuric acid in, make the solution that mass concentration is 1%-60%, stir, be heated to solution boiling and condensing reflux, reaction 3-15h is cooled to room temperature, filters;
(2) filter cake deionized water wash; Drying obtains the presoma of carbosphere;
(3) under inert gas atmosphere, at 600～1000 ℃ of calcining 1-10h; Be cooled to room temperature, obtain the carbosphere that particle diameter is 50-200nm.
2. the method for a kind of preparing carbosphere through reflux method according to claim 1 is characterized in that described step (1) is: it is 2-9molL that sucrose or glucose are dissolved in concentration
-1Aqueous sulfuric acid in, make the solution that mass concentration is 10%-40%, stir, be heated to solution boiling and condensing reflux, reaction 6-10h is cooled to room temperature, suction filtration.
3. the method for a kind of preparing carbosphere through reflux method according to claim 1 is characterized in that described rare gas element is nitrogen or argon gas.
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| CN101935033B (en) * | 2010-09-07 | 2012-01-11 | 湖南大学 | Preparation method and application of water-soluble carbon nano particles |
| CN109173999A (en) * | 2018-10-10 | 2019-01-11 | 佛山科学技术学院 | A kind of preparation method and applications of biology carbon microspheres |
| CN110404501A (en) * | 2019-08-08 | 2019-11-05 | 宝鸡文理学院 | A kind of preparation method of nucleocapsid structure layered double hydroxide compound particle |
| CN111762770A (en) * | 2020-05-25 | 2020-10-13 | 浙江工业大学 | Preparation method of oxygen-containing functional group functionalized porous carbon spheres |
| CN112076801B (en) * | 2020-08-31 | 2023-04-07 | 江苏大学 | Carbon microsphere catalyst, preparation method and application |
| CN112357904B (en) * | 2020-11-11 | 2022-09-16 | 曲阜师范大学 | Biomass carbon microsphere, preparation method, supercapacitor and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254913A (en) * | 2008-04-03 | 2008-09-03 | 天津大学 | Method for preparing carbon nano-tube or rod by hydrothermal process |
| CN101538034A (en) * | 2009-04-24 | 2009-09-23 | 江苏大学 | Preparation method of one-step synthesis carbon ball |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254913A (en) * | 2008-04-03 | 2008-09-03 | 天津大学 | Method for preparing carbon nano-tube or rod by hydrothermal process |
| CN101538034A (en) * | 2009-04-24 | 2009-09-23 | 江苏大学 | Preparation method of one-step synthesis carbon ball |
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