CN105060272B - A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT - Google Patents
A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT Download PDFInfo
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Abstract
A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT, which is carbon source mainly using artemia chorion, and nickel salts are catalyst, and potassium hydroxide is precipitating reagent, catalyzes and synthesizes nickel doped graphite material with carbon element under conditions of 600～900 DEG C；Again obtained nickel doped graphite material with carbon element is mixed with potassium hydroxide by certain mass ratio, calcining at 600～900 DEG C obtains CNT.The distinguishing feature of the present invention is to have synthesized carbon nanotubes under the conditions of atmospheric low-temperature using living beings carbon source, and the cheap, equipment with raw material is simple, reproducible, be easily achieved low-cost industrial many advantages, such as produce.CNT obtained by the method has high graphitization degree, the advantage such as good conductivity, has very high application prospect at aspects such as ultracapacitor, lithium ion battery electrode material and catalyst carriers.
Description
Technical field
The present invention relates to the preparation method of a kind of functional material, particularly synthesizing carbon nanotubes.
Background technology
CNT is widely used in ultracapacitor, lithium ion battery, fuel electricity as the important functional material of a class
The fields such as pond catalyst.The special one-dimensional graphite-structure of CNT causes such research to have great theory significance and potential
Using value.The unique structure of CNT is preferable one-dimensional material model；Huge draw ratio makes which be expected to as heavily fortified point
Tough carbon fiber, its intensity are 100 times of steel, and weight then only has the 1/6 of steel；Good conductivity, ion transmission speed are fast and hollow
These advantages of structure so as to become ultracapacitor, the ideal material of lithium ion battery and catalyst carrier etc..
In recent years, the method by the use of CVD technology using transition metal (as iron, cobalt, nickel) as catalyst preparation CNT
Research obtains huge progress.Frequently with different carbon sources, different metallic catalysts and different methods carry out synthesis performance to people
Different CNT.Such as Fan et al. ([J] .Advanced Materials, 2010,22 (33):3723-3728.) and
Wei et al. ([J] .Advanced Materials, 2014,26 (41):7051-7058) report respectively using heating using microwave and
The method that high-temperature calcination is combined, makees stone of the catalyst using graphene oxide and hydrogen reducing synthesis with sandwich structure with cobalt
Black alkene/CNT and catalyst is made with iron/molybdenum/magnesium/aluminium quaternary layered hydroxide, generated as carbon source with methane and formamide
The CNT of timbo structure.These graphitized carbon materials have shown excellent performance in terms of supercapacitor applications, but
Existing preparation technology is relative complex, and the presoma of material with carbon element needs to buy, and improves production cost, and the carbon nanometer for preparing
Pipe is difficult to mass produce.
Content of the invention
It is an object of the invention to provide a kind of reaction condition is gentle, preparation process is simple, low production cost, can scale
Production a kind of using artemia chorion as carbon source low temperature under prepare the method for CNT.The present invention is mainly with biological artemia
As the presoma of carbon, need not contain hydrocarbon atmosphere (such as methane, acetylene etc.), as carbon source, at a lower temperature, makes chorion
Catalyst uniform load need not add extra catalyst substrate material in solid carbon source, by the multistage pore canal of artemia chorion
The amorphous carbon of structure is first transformed into high-graphitized material with carbon element, then grows CNT on graphitized carbon.
Technical scheme comprises the steps：
(1) artemia chorion is cleaned up, artemia egg shell powder was used 3mol/L after 6 hours by 120 DEG C of drying, ball milling successively
Hydrochloric acid and deionized water cleaning, to pH=7, to remove residual impurity, finally dry；
(2) nickel acetate is dissolved in deionized water so as to which concentration is 0.024～0.1mol/L；
(3) the artemia chorion that handles well in step (1) is added in Ni-acetate solution obtained in step (2), wherein artemia
Chorion and the mass ratio R=1 of nickel acetate:1～4:1, it is sufficiently stirred for 0.5～2 hour so that the nickel ion in Ni-acetate solution is equal
Even it is distributed in chorion carbon surface；
(4) potassium hydroxide will be added in the mixture of step (3), keep the mass ratio R=of artemia chorion and potassium hydroxide
1：1～1:4,60~High-speed stirred 3～8 hours at 80 DEG C；
(5) gained mixture in step (4) is put in tube furnace, with 1～10 DEG C/min under high-purity argon gas protection
Speed is warming up to 600～900 DEG C and is calcined, and is incubated 1～5 hour, obtains nickel doped graphite material with carbon element；
(6) gained mixture in step (5) is uniform with potassium hydroxide ground and mixed, mixture is kept with potassium hydroxide
Mass ratio R=1:1～1:4, the above-mentioned solid mixture of gained is heated up with 1～10 DEG C/min of speed under high-purity argon gas protection
Calcined to 600～900 DEG C, 1～5 hour is incubated, after the completion for the treatment of sample sintering, taken out product；
(7) product for obtaining step (6) is successively cleaned with 3mol/L hydrochloric acid and deionized water to pH=7, is filtered, is dried
Dry, obtain final product the high CNT of degree of graphitization.
The present invention is had the advantage that compared with prior art：
1st, the present invention has synthesized hollow Nano carbon using atmospheric low-temperature under inert atmosphere conditions using a kind of solid-state carbon source
Pipe, the advantages of obtained CNT has high graphitization degree, good conductivity, can be applicable to ultracapacitor, lithium ion
The aspect such as battery electrode material and catalyst carrier.
2nd, raw material are easily obtained, wide material sources, low price.
3rd, preparation method is simple, and equipment is simple, greatlys save cost, shortens production technology.
4th, reaction condition is gentle, it is easy to control and reproducible, product quality is stable, is suitable for industrial mass production.
Description of the drawings
Fig. 1 is the SEM figure of CNT prepared by the embodiment of the present invention 1.
Fig. 2 is the TEM figure of CNT prepared by the embodiment of the present invention 7.
Specific embodiment
Embodiment 1
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.024mol/L Ni-acetate solution, being sufficiently stirred for 0.5 hour.2.4 grams of hydroxides are added after dissolving
Potassium, high-speed stirred 3 hours at 60 DEG C.The mixture of gained is placed in vacuum drying pipe with 1 under the protection of high-purity argon gas
DEG C/speed of min is warming up to 600 DEG C and calcined, 1 hour is incubated, then sample is mixed simultaneously with 2.4 grams of potassium hydroxide powders
Grinding is uniform, and is put into and is warming up to 600 DEG C with the speed of 1 DEG C/min under the protection of high-purity argon gas in vacuum drying pipe and is forged
Burn, 1 hour is incubated, after the completion for the treatment of sample sintering, product is taken out, products therefrom is successively used 3mol/L salt pickling, deionized water
Wash, to pH=7, filter, dry, CNT is obtained final product, its SEM figure is as shown in figure 1, from figure it can be seen that by this embodiment
The CNT of synthesis is about several microns, and diameter is thinner.
Embodiment 2
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.05mol/L Ni-acetate solution, being sufficiently stirred for 1 hour.4.8 grams of hydroxides are added after dissolving
Potassium, high-speed stirred 4 hours at 60 DEG C.The mixture of gained is placed in vacuum drying pipe with 2 under the protection of high-purity argon gas
DEG C/min speed be warming up to 650 DEG C and calcined, be incubated 3 hours, then sample mixed with 2.4 grams of potassium hydroxide powders
And grind uniform, and be put into and 650 DEG C be warming up to 2 DEG C/min of speed under the protection of high-purity argon gas in vacuum drying pipe and enter
Row calcining, is incubated 1 hour, takes out product after the completion for the treatment of sample sintering, and products therefrom is successively used 3mol/L salt pickling, deionization
Washing, to pH=7, filters, dries, obtain final product CNT.
Embodiment 3
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.06mol/L Ni-acetate solution, being sufficiently stirred for 1.5 hours.3.6 grams of hydroxides are added after dissolving
Potassium, high-speed stirred 5 hours at 60 DEG C.The mixture of gained is placed in vacuum drying pipe with 4 under the protection of high-purity argon gas
DEG C/min speed be warming up to 700 DEG C and calcined, be incubated 2 hours, then sample mixed with 7.2 grams of potassium hydroxide powders
And grind uniform, and be put into and 700 DEG C be warming up to 4 DEG C/min of speed under the protection of high-purity argon gas in vacuum drying pipe and enter
Row calcining, is incubated 4 hours, takes out product after the completion for the treatment of sample sintering, and products therefrom is successively used 3mol/L salt pickling, deionization
Washing, to pH=7, filters, dries, obtain final product CNT.
Embodiment 4
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.07mol/L Ni-acetate solution, being sufficiently stirred for 1 hour.7.2 grams of potassium hydroxide are added after dissolving,
High-speed stirred 6 hours at 60 DEG C.By the mixture of gained be placed in vacuum drying pipe under the protection of high-purity argon gas with 6 DEG C/
The speed of minute is warming up to 750 DEG C and is calcined, and is incubated 4 hours, then mixes and grind sample with 3.6 grams of potassium hydroxide powders
Mill is uniform, and is put into and is warming up to 750 DEG C with 6 DEG C/min of speed under the protection of high-purity argon gas in vacuum drying pipe and is forged
Burn, 4 hours are incubated, after the completion for the treatment of sample sintering, product is taken out, products therefrom is successively used 3mol/L salt pickling, deionized water
Wash, to pH=7, filter, dry, obtain final product CNT.
Embodiment 5
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.036mol/L Ni-acetate solution, being sufficiently stirred for 1.5 hours.4.8 grams of hydroxides are added after dissolving
Potassium, high-speed stirred 7 hours at 65 DEG C.The mixture of gained is placed in vacuum drying pipe with 8 under the protection of high-purity argon gas
DEG C/min speed be warming up to 800 DEG C and calcined, be incubated 3 hours, then 2.4 grams of potassium hydroxide powders of sample addition ground
Mill is uniform, and is put into and is warming up to 800 DEG C with 8 DEG C/min of speed under the protection of high-purity argon gas in vacuum drying pipe and is forged
Burn, 2 hours are incubated, after the completion for the treatment of sample sintering, product is taken out, products therefrom is successively used 3mol/L salt pickling, deionized water
Wash, to pH=7, filter, dry, obtain final product CNT.
Embodiment 6
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.08mol/L Ni-acetate solution, being sufficiently stirred for 2h.4.8 grams of potassium hydroxide of addition after dissolving, 70
High-speed stirred 5 hours at DEG C.The mixture of gained is placed in vacuum drying pipe with 9 DEG C/min under the protection of high-purity argon gas
Speed be warming up to 850 DEG C and calcined, be incubated 3 hours, then add 2.4 grams of potassium hydroxide powders grindings uniform in sample,
And be put in vacuum drying pipe and be warming up to 850 DEG C with 9 DEG C/min of speed under the protection of high-purity argon gas and calcined, insulation 2
Hour, product is taken out after the completion for the treatment of sample sintering, products therefrom is successively washed with 3mol/L salt pickling, deionization, to pH=
7, filter, dry, obtain final product CNT.
Embodiment 7
Artemia chorion is cleaned up, 120 DEG C of drying, ball milling 6 hours, by artemia egg shell powder successively with excessive 3mol/L
Hydrochloric acid is cleaned, then deionized water is cleaned up, and to pH=7, is finally dried；Take 2.4 grams of above-mentioned treated artemia chorions
100ml concentration is added to for, in 0.1mol/L Ni-acetate solution, being sufficiently stirred for 2 hours.9.6 grams of potassium hydroxide are added after dissolving,
High-speed stirred 8 hours at 80 DEG C.By the mixture of gained be placed in vacuum drying pipe under the protection of high-purity argon gas with 10 DEG C/
The speed of minute is warming up to 900 DEG C and is calcined, and is incubated 5 hours, then sample is added 9.6 grams of potassium hydroxide powders grindings all
Even, and be put in vacuum drying pipe and be warming up to 900 DEG C with 10 DEG C/min of speed under the protection of high-purity argon gas and calcined,
Insulation 5 hours, takes out product after the completion for the treatment of sample sintering, products therefrom is successively washed till pH with 3mol/L hydrochloric acid and deionized water
=7, filter, dry, CNT is obtained final product, its TEM figure is as shown in Fig. 2 from figure it can be seen that synthesized by this embodiment
CNT pattern is different, and if any spirality, linear pattern etc., and the diameter of pipe is also different.
Claims (1)
1. a kind of using artemia chorion as carbon source low temperature under prepare the method for CNT, it is characterised in that：
(1) artemia chorion is cleaned up, 120 DEG C of drying, ball milling are after 6 hours, clear with 3mol/L hydrochloric acid and deionized water successively
PH=7 is washed till, is finally dried；
(2) nickel acetate is dissolved in deionized water so as to which concentration is 0.024～0.1mol/L；
(3) the artemia chorion that handles well in step (1) is added in Ni-acetate solution obtained in step (2), wherein artemia chorion
Mass ratio R=1 with nickel acetate:1～4:1, stir so that in catalyst solution, metal ion is evenly distributed on ovum
Shell carbon surface；
(4) potassium hydroxide is added to the product of step (3), it is R=1 with the mass ratio of potassium hydroxide to keep the chorion of step (3):
1～1:4, pasty state is evenly stirred until at 60～80 DEG C；
(5) gained mixture in step (4) is put in tube furnace, with 1～10 DEG C/min of speed under high-purity argon gas protection
It is warming up to 600～900 DEG C to be calcined, is incubated 1～5 hour；
(6) gained mixture in step (5) is uniform with potassium hydroxide ground and mixed, keep the quality of mixture and potassium hydroxide
Ratio is R=1:1～1:4, the above-mentioned solid mixture of gained is heated up with 1～10 DEG C/min of speed under high-purity argon gas protection
Calcined to 600～900 DEG C, 1～5 hour is incubated, after the completion for the treatment of sample sintering, taken out product；
(7) product for obtaining step (6) is successively cleaned with 3mol/L hydrochloric acid and deionized water to pH=7, is filtered, is dried, i.e.,
Obtain the high CNT of degree of graphitization.
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| CN1397488A (en) * | 2001-07-18 | 2003-02-19 | 中国科学院成都有机化学研究所 | Post-processing process for increasing specific surface area of carbon nanotube |
| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| CN101780949A (en) * | 2009-01-19 | 2010-07-21 | 中国科学院化学研究所 | Method for preparing multi-walled carbon nano-tube |
| CN103183329A (en) * | 2013-03-19 | 2013-07-03 | 燕山大学 | Preparation method of multistage-channel carbon electrode material |
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| CN104220168B (en) * | 2012-05-11 | 2018-10-19 | Lg化学株式会社 | Prepare the method for the core-shell particles being supported on carrier and the thus obtained core-shell particles being supported on carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1397488A (en) * | 2001-07-18 | 2003-02-19 | 中国科学院成都有机化学研究所 | Post-processing process for increasing specific surface area of carbon nanotube |
| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| CN101780949A (en) * | 2009-01-19 | 2010-07-21 | 中国科学院化学研究所 | Method for preparing multi-walled carbon nano-tube |
| CN103183329A (en) * | 2013-03-19 | 2013-07-03 | 燕山大学 | Preparation method of multistage-channel carbon electrode material |
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