CN102390828B - Method for preparing highly-graphitized hollow carbon nanocapsules by using low-temperature reaction - Google Patents

Method for preparing highly-graphitized hollow carbon nanocapsules by using low-temperature reaction Download PDF

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Publication number
CN102390828B
CN102390828B CN 201110219856 CN201110219856A CN102390828B CN 102390828 B CN102390828 B CN 102390828B CN 201110219856 CN201110219856 CN 201110219856 CN 201110219856 A CN201110219856 A CN 201110219856A CN 102390828 B CN102390828 B CN 102390828B
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nano carbon
low
carbide
aluminum chloride
method
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CN 201110219856
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CN102390828A (en
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白玉俊
刘瑞
伦宁
亓永新
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山东大学
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Abstract

The invention relates to a method for preparing highly-graphitized hollow carbon nanocapsules by using a low-temperature reaction. The method comprises the following steps of: reacting carbon carbide with aluminum chloride hexahydrate for 2-5h at 250-500 DEG C; or reacting the carbon carbide with cobalt chloride hexahydrate for 2-5h at 250-500 DEG C to obtain solid nanocapsules; then mixing the solid nanocapsules with anhydrous aluminum chloride; and heating to 250-500 DEG C, preserving temperature and reacting for 4-5h. The method disclosed by the invention has the advantages of low reaction temperature, short reaction time and low cost; and the prepared hollow nanocapsules have the advantages of uniform size, high graphitization degree, high purity and high yield.

Description

A kind of low-temp reaction prepares the method for high graphitization hollow Nano carbon ball

Technical field

The present invention relates to a kind of preparation method of hollow carbon sphere, particularly the method for the even and high-graphitized hollow Nano carbon ball of a large amount of preparation sizes of low-temp reaction, belong to technical field of inorganic nonmetallic materials.

Background technology

Hollow Nano carbon ball has special physical and chemical performance, as distinctive hollow structure, low density, large specific surface area, good heat-proof quality, thereby be with a wide range of applications, as the fields such as template that can be used for fuel cell electrode, lithium ion battery negative, ultracapacitor, gas storage medium, lubricant, support of the catalyst, electrochemical sensor, drug delivery device, prepare other hollow structure.

The existing a lot of reports of the preparation method of hollow Nano carbon ball, major technique comprises: impacting with high pressure compression soccerballene method, LASER HEAT method of evaporation, template, solvent-thermal method, direct reaction method, the equipment of the needs complexity that these preparation methods have, the operating process that has are complicated, power consumption that have is large, but prepared hollow Nano carbon ball degree of graphitization is lower, size is inhomogeneous, and the productive rate of hollow Nano carbon ball is lower or be difficult to as just by product separate from other carbon material that generates simultaneously.Therefore, a large amount of preparation sizes of exploration low temperature are even, purity is high and high-graphitized hollow Nano carbon playing skill art, not only have important researching value, and can expand the application of hollow Nano carbon ball.

The greying of carbon current material is often carried out at the high temperature more than 1000 ℃, and greatly mainly with magnesium-yttrium-transition metal iron, cobalt, nickel etc. as catalyzer, thereby, how to make the greying of carbon material realize that less energy-consumption, high-level efficiency are technical problems that attracts people's attention always.

Summary of the invention

The objective of the invention is the deficiency that exists in present hollow Nano carbon ball technology of preparing, and provide a kind of low-temp reaction to prepare the method for high graphitization hollow Nano carbon ball.

The technical scheme that the present invention takes is:

A kind of low-temp reaction prepares the method for high graphitization hollow Nano carbon ball, comprises that step is as follows:

(1) carbide of calcium and Aluminum Chloride Hexahydrate are placed in reactor, the sealing post-heating is incubated 2-5 hour carbide of calcium and Aluminum Chloride Hexahydrate is reacted to 250-500 ℃, then is cooled to room temperature; Perhaps first carbide of calcium and CoCL2 6H2O are placed in reactor, the sealing post-heating is to 250-500 ℃, being incubated 2-5 hour reacts carbide of calcium and CoCL2 6H2O, be cooled to room temperature, product makes solid nano carbon microsphere through washing, drying, more solid nano carbon microsphere is evenly mixed with Aluminum chloride anhydrous, is placed in reactor and is heated to seal to 250-500 ℃, insulation reaction 4-5 hour, be cooled to room temperature;

(2) with product through concentrated hydrochloric acid, washed with de-ionized water, drying makes size uniform and high-graphitized hollow Nano carbon ball.

Described low-temp reaction prepares the method for high graphitization hollow Nano carbon ball, and in step (1), the mol ratio of carbide of calcium and Aluminum Chloride Hexahydrate is 2~5: 1; The mol ratio of carbide of calcium and CoCL2 6H2O is 2~5: 1; The mass ratio of described solid nano carbon microsphere and Aluminum chloride anhydrous is 1: 0.1~1.

Described low-temp reaction prepares the method for high graphitization hollow Nano carbon ball, and the washing in step (1) is first to clean with concentrated hydrochloric acid, then uses washed with de-ionized water.

Above-mentioned concentrated hydrochloric acid mass concentration scope 20~37.5%.

Above-mentioned drying is to dry 8~10 hours at 50 ℃~100 ℃ temperature.

The advantage of method of the present invention is:

(1) carbide of calcium is industrial material for the preparation of acetylene, and is cheap, need not catalyzer, and raw materials cost is low;

(2) temperature of reaction is low, and the reaction times is short, save energy;

(3) reaction process is simple to operate, and the byproduct of reaction easy-clear is conducive to a large amount of productions of hollow Nano carbon ball;

(3) the hollow Nano carbon ball size uniform of preparation, degree of graphitization is high, and purity is high, and productive rate high (according to the carbon content in carbide of calcium, carbide of calcium and Aluminum Chloride Hexahydrate were 500 ℃ of reactions 5 hours, and the productive rate of hollow Nano carbon ball reaches 54%).

Low-temp reaction of the present invention prepares the method for high graphitization hollow Nano carbon ball, x-ray diffraction pattern such as Fig. 1 of the hollow Nano carbon ball that obtains, and in figure, each diffraction peak and graphite mould carbon material coincide.The pattern of product such as Fig. 2, Fig. 3, Fig. 4, Fig. 5, shown in Figure 6.

Description of drawings

Fig. 1 is x-ray diffraction pattern and the Raman spectrum that the embodiment of the present invention 1 makes product;

Fig. 2 is the transmission electron microscope shape appearance figure that the embodiment of the present invention 1 makes hollow Nano carbon ball;

Fig. 3 is the transmission electron microscope shape appearance figure that the embodiment of the present invention 2 makes hollow Nano carbon ball;

Fig. 4 is the transmission electron microscope shape appearance figure of solid nano carbon microsphere in the middle of the embodiment of the present invention 5 makes;

Fig. 5 is the transmission electron microscope shape appearance figure that the embodiment of the present invention 5 makes hollow Nano carbon ball;

Fig. 6 is the transmission electron microscope shape appearance figure that the embodiment of the present invention 6 makes hollow Nano carbon ball;

Fig. 7 is the transmission electron microscope shape appearance figure of Comparative Examples product.

Embodiment

Further illustrate the present invention below by embodiment and embodiment.

Embodiment 1

By carbide of calcium and Aluminum Chloride Hexahydrate reaction preparation hollow Nano carbon ball.Weigh in the balance and get 11.0g carbide of calcium, the 8.9g Aluminum Chloride Hexahydrate in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 500 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, makes reactor naturally cool to room temperature in stove.Reaction product is divided into two-layer, the upper strata is spongiform atrament, and lower floor is the mixture of grey, and product is through concentrated hydrochloric acid, washed with de-ionized water, in cleaning process, the black product swims on liquid level, and the product after cleaning is 2.11g at the black powder that about 50 ℃ oven dry obtained after 8 hours.

Embodiment 2

By carbide of calcium and Aluminum Chloride Hexahydrate reaction preparation nano-sized carbon hollow ball.Weigh in the balance and get 11.0g carbide of calcium, the 8.9g Aluminum Chloride Hexahydrate in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 250 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, makes reactor naturally cool to room temperature in stove.Reaction product is divided into two-layer, the upper strata is spongiform atrament, and lower floor is the mixture of grey, and product is through concentrated hydrochloric acid, washed with de-ionized water, in cleaning process, the black product swims on liquid level, and the product after cleaning is 0.41g at the black powder that about 60 ℃ oven dry obtained after 6 hours.

Embodiment 3

By carbide of calcium and Aluminum Chloride Hexahydrate reaction preparation nano-sized carbon hollow ball.Weigh in the balance and get 11.0g carbide of calcium, the 8.9g Aluminum Chloride Hexahydrate in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 250 ℃ of left and right in process furnace, be incubated and close process furnace after 1 hour, makes reactor naturally cool to room temperature in stove.Reaction product is divided into two-layer, the upper strata is spongiform atrament, and lower floor is the mixture of grey, and product is through concentrated hydrochloric acid, washed with de-ionized water, in cleaning process, the black product swims on liquid level, and the product after cleaning is 0.32g at the black powder that about 50 ℃ oven dry obtained after 8 hours.

Embodiment 4

By carbide of calcium and the solid nano carbon microsphere of CoCL2 6H2O reaction preparation.Weigh in the balance and get 9.0g carbide of calcium, the 8.0g CoCL2 6H2O in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 500 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, makes reactor naturally cool to room temperature in stove.Reaction product is not stratified, and product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning is solid nano carbon microsphere at the black powder 0.92g that about 50 ℃ oven dry obtained after 8 hours;

Solid nano carbon microsphere 0.3g mixes in the stainless steel cauldron of packing into the 0.3g Aluminum chloride anhydrous, after reactor is tamping, be heated to 500 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, make reactor naturally cool to room temperature in stove, product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning obtains black powder about 50 ℃ oven dry after 8 hours.

Embodiment 5

By carbide of calcium and the solid nano carbon microsphere of CoCL2 6H2O reaction preparation.Weigh in the balance and get 11.0g carbide of calcium, the 9.0g CoCL2 6H2O in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 500 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, makes reactor naturally cool to room temperature in stove.Reaction product is not stratified, and product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning is solid nano carbon microsphere at the black powder 1.05g that about 50 ℃ oven dry obtained after 8 hours;

Solid nano carbon microsphere 0.3g mixes in the stainless steel cauldron of packing into the 0.1g Aluminum chloride anhydrous, after reactor is tamping, be heated to 250 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, make reactor naturally cool to room temperature in stove, product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning obtains black powder about 50 ℃ oven dry after 8 hours.

Embodiment 6

By carbide of calcium and the solid nano carbon microsphere of CoCL2 6H2O reaction preparation.Weigh in the balance and get 9.0g carbide of calcium, the 8.0g CoCL2 6H2O in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 250 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, makes reactor naturally cool to room temperature in stove.Reaction product is not stratified, and product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning is solid nano carbon microsphere at the black powder 0.42g that about 50 ℃ oven dry obtained after 8 hours;

Solid nano carbon microsphere 0.3g mixes in the stainless steel cauldron of packing into 0.3 g Aluminum chloride anhydrous, after reactor is tamping, be heated to 500 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, make reactor naturally cool to room temperature in stove, product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning obtains black powder about 50 ℃ oven dry after 8 hours.

Comparative Examples

Weigh in the balance and get 11.0g carbide of calcium, the 4.9g Aluminum chloride anhydrous in the stainless steel cauldron of packing into, after reactor is tamping, is heated to 500 ℃ of left and right in process furnace, be incubated and close process furnace after 5 hours, makes reactor naturally cool to room temperature in stove.Reaction product is not stratified, and product is through concentrated hydrochloric acid, washed with de-ionized water, and the product after cleaning is 1.27g at the black powder that about 60 ℃ oven dry obtained after 6 hours; Can not get hollow Nano carbon ball.

Claims (3)

1. a low-temp reaction prepares the method for high graphitization hollow Nano carbon ball, it is characterized in that, comprises that step is as follows:
(1) carbide of calcium and Aluminum Chloride Hexahydrate are placed in reactor, the sealing post-heating is incubated 2-5 hour carbide of calcium and Aluminum Chloride Hexahydrate is reacted to 250-500 ℃, then is cooled to room temperature;
(2) with product through concentrated hydrochloric acid, washed with de-ionized water, drying makes size uniform and high-graphitized hollow Nano carbon ball.
2. low-temp reaction according to claim 1 prepares the method for high graphitization hollow Nano carbon ball, it is characterized in that, in step (1), the mol ratio of carbide of calcium and Aluminum Chloride Hexahydrate is 2 ~ 5:1.
3. low-temp reaction according to claim 1 prepares the method for high graphitization hollow Nano carbon ball, it is characterized in that, the drying in step (1) and (2) is to dry 8~10 hours at 50 ℃~100 ℃ temperature.
CN 201110219856 2011-08-03 2011-08-03 Method for preparing highly-graphitized hollow carbon nanocapsules by using low-temperature reaction CN102390828B (en)

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US9701539B2 (en) 2013-03-15 2017-07-11 West Virginia University Research Corporation Process for pure carbon production
CN103183342B (en) * 2013-04-02 2014-11-12 中国矿业大学 Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures
BR112017008279A2 (en) 2014-10-21 2018-06-19 West Virginia Univ Research Corporation methods and apparatus for the production of carbon, carbide electrodes and carbon compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101181990A (en) * 2006-10-24 2008-05-21 三星Sdi株式会社 Method of preparing a carbonaceous material for an emitter of an electron emission device
CN101224883A (en) * 2008-02-03 2008-07-23 山东大学 Method for preparing hollow carbon balls
CN101323444A (en) * 2007-06-15 2008-12-17 中国科学院化学研究所 Carbon or carbon composite hollow ball and preparation thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101181990A (en) * 2006-10-24 2008-05-21 三星Sdi株式会社 Method of preparing a carbonaceous material for an emitter of an electron emission device
CN101323444A (en) * 2007-06-15 2008-12-17 中国科学院化学研究所 Carbon or carbon composite hollow ball and preparation thereof
CN101224883A (en) * 2008-02-03 2008-07-23 山东大学 Method for preparing hollow carbon balls

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