CN104961121A - Preparation method for nitrogen-doped nuclear shell hollow carbon - Google Patents
Preparation method for nitrogen-doped nuclear shell hollow carbon Download PDFInfo
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- CN104961121A CN104961121A CN201510352231.3A CN201510352231A CN104961121A CN 104961121 A CN104961121 A CN 104961121A CN 201510352231 A CN201510352231 A CN 201510352231A CN 104961121 A CN104961121 A CN 104961121A
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Abstract
The invention belongs to the technical field of carbon material manufacturing processes and relates to a preparation method method based on preparing nitrogen-doped nuclear shell hollow carbon. The preparation method is characterized in that silicon dioxide balls are utilized as formworks, after the surfaces of the silicon dioxide balls are wrapped with phenolic resin, multilayer wrapping with mesoporous silicon dioxide and nitrogen-containing polymers is conducted, core-shell structures are formed, the calcination is controlled, pomegranate-shaped core-shell materials are formed, cores are made of nano-scale hollow fractional porous carbon, and shells are made of nitrogen-doped ultrathin mesoporous carbon. By means of the preparation method, the fractional open-framework structure, the nano-scale particle size, the high electrical conductivity and the high wetability are achieved, the method is simple, the process is easy to control, and the preparation method can be widely applied to the electrochemistry fields such as supercapacitors, capatitive type desalination and lithium ion batteries.
Description
Technical field
The invention belongs to carbon material manufacturing process technology field, relate to a kind of preparation method based on the hollow carbon of N doping nucleocapsid.The hollow carbon of N doping nucleocapsid prepared by the present invention can be widely used in the electrochemical field such as ultracapacitor, structure capacitance desalination, lithium ion battery.
Background technology
Hollow carbon, due to its high-specific surface area, unique feature such as hollow structure, low cost, is widely used as gas delivery agent, the carrier of catalyzer and the electrode materials etc. of ultracapacitor at present.The surface modification of hollow carbon improves the important method of its performance.Compared with pure carbon, the carbon material after surface modification after such as Heteroatom doping can demonstrate more superior performance in some aspects.The method of traditional surface modification is acid oxidase process, makes its surface have oxygen-containing functional group (-OH ,-COOH), is easy to the destruction of causing hollow carbon structure, such as: ball wall breaks, and caves in.At present, the doping of nitrogen element is the importance of the Research on Surface Modification of carbon material.The doping of nitrogen element can improve the electronic transmission performance of carbon material, reduces specific resistance.In addition, the doping of nitrogen element also can increase the avtive spot of carbon material surface, improves wetting ability, makes it demonstrate more wide application prospect in electrochemical field.Based on the N doping of hollow carbon, mainly by following method: the NH in (1) later stage
3process; (2) nitrogenous carbon source is polymerized at template surface, then cracking gained.But, hollow carbon before modified after pore passage structure all more single, be unfavorable for diffusion mass transfer, limit its application.In addition before modified after the internal surface of hollow carbon often cannot be utilized effectively, therefore the utilization ratio on its surface, its adsorption site is relatively less.How the structure regulating of hollow carbon and surface modification organic phase are combined, enrich its pore passage structure, increase surface utilisation and improve other surface physical properties as: wetting ability, electroconductibility etc. are still a major challenge.Solve this technical barrier, particularly important to the application of the hollow carbon of final expansion.
Summary of the invention
The present invention proposes the preparation method of the hollow carbon of nucleocapsid of N doping.The hollow carbon of gained has unique pomegranate shape nucleocapsid graded porous structure, obtains effective N doping simultaneously, therefore has high conductivity and high wettability.
The preparation method of the hollow carbon of nucleocapsid of N doping provided by the present invention, comprises the following steps:
By SiO
2ball is distributed in the mixed solution of deionized water and ethanol, the volume ratio of deionized water and ethanol is (8-4): 1, adds cetyl trimethylammonium bromide, ammoniacal liquor, Resorcinol under magnetic stirring, after 35 DEG C of stirring 30 min, add formaldehyde, above ammoniacal liquor: Jian Ben bis-Fen ︰ SiO
2the mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromide is 1: 3.5: (4-8): 5: 20, reaction 3-6 h, ageing one night, centrifuge washing obtains hollow carbon matrix precursor, then is mixed with 3 wt% hollow carbon balls precursor water solution, take hollow carbon balls precursor water solution, cetyl trimethylammonium bromide, ammoniacal liquor, be added in the mixing solutions of ethanol and deionized water, the volume ratio of deionized water and ethanol is 1:(1-4), hollow carbon balls precursor water solution: cetyl trimethylammonium bromide: the mass ratio of ammoniacal liquor is (1-5): 1.6: 10, after ultrasonic 1-2 h, tetraethyl orthosilicate is dropped in above-mentioned reaction solution, above hollow carbon balls Qian Qu Ti ︰ tetraethyl orthosilicate mass ratio is 1 ︰ (9.4-18.8), room temperature strong stirring, filtering and washing is to neutral, room temperature dries to obtain the hollow carbon matrix precursor of [email protected] at the hollow carbon matrix precursor surface aggregate polymer with nitrogen of coated with silica, then through calcining, etch to obtain the hollow carbon of nucleocapsid of N doping.
Above-mentioned matrix material building-up process: described SiO
2ball, particle diameter is 100-500 nm, ammoniacal liquor, Resorcinol, SiO
2the mass ratio of ball, formaldehyde, cetyl trimethylammonium bromide, the wall thickness of reaction times and hollow carbon, size and homogeneity are relevant, exceeding above-mentioned scope may cannot being formed of the hollow carbon of kernel, thus the hollow carbon of the nucleocapsid that cannot obtain the N doping that this patent is mentioned.
Above-mentioned matrix material building-up process: hollow carbon balls presoma is relevant with pomegranate shape structure rating to the mass ratio of tetraethyl orthosilicate, exceeding above-mentioned scope may cause pomegranate shape nucleocapsid structure to obtain, thus the hollow carbon of the nucleocapsid that cannot obtain the N doping that this patent is mentioned.
Above-mentioned matrix material building-up process: the polymerization of described polymer with nitrogen is relevant to the formation of N doping and nucleocapsid structure.If polymer with nitrogen cannot be aggregated in the hollow carbon matrix precursor surface of coated with silica, the hollow carbon of nucleocapsid of pomegranate shape namely cannot be formed.
The process of above-mentioned carbonization: under an inert atmosphere, be divided into two step-up temperature, first aim temperature is 300-400 DEG C, resol generation Pintsch process and polymer with nitrogen cracking in this temperature range, second target temperature is 600-800 DEG C, in the greying of the hollow carbon of this temperature range nucleocapsid.Rare gas element is purity nitrogen or argon gas, and the temperature rise rate of two step-up temperature is 0.5-2 DEG C/min, and the flow velocity of rare gas element is 50-150 mL/min.
Preparation process of the present invention is simple, requires low, easy handling to experimental installation.The inventive method carries out structure design and duct adjustment by multistep template to the hollow carbon of nucleocapsid, and also carry out effective N doping, the hollow carbon of nucleocapsid of the pomegranate shape of the final gained of the present invention can be widely used for electrochemical field simultaneously.
Embodiment
After now specific embodiments of the invention being described in.
embodiment 1
By SiO
2ball is distributed in the mixed solution of deionized water and ethanol, and the volume ratio of deionized water and ethanol is that 8:1 adds cetyl trimethylammonium bromide, ammoniacal liquor, Resorcinol under magnetic stirring, after 35 DEG C of stirring 30 min, adds formaldehyde, An Shui ︰ Jian Ben bis-Fen ︰ SiO
2the mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromide is 1: 3.5: 4: 5: 20, react 3 h, ageing one night, centrifuge washing obtains hollow carbon matrix precursor, then is mixed with 3 wt% hollow carbon balls precursor water solution, take hollow carbon balls precursor water solution (3 wt%), cetyl trimethylammonium bromide, ammoniacal liquor, be added in the mixing solutions of ethanol and deionized water, the volume ratio of deionized water and ethanol is 1 ︰ 1, empty carbon ball precursor water solution: cetyl trimethylammonium bromide: the mass ratio of ammoniacal liquor is after 2: 1.6: 10 ultrasonic 1-2 h, tetraethyl orthosilicate is dropped in above-mentioned reaction solution, above hollow carbon balls Qian Qu Ti ︰ tetraethyl orthosilicate mass ratio is 1 ︰ 9.4, room temperature strong stirring 12 h, filtering and washing is to neutral, room temperature dries to obtain the hollow carbon matrix precursor of [email protected] hollow for silicon-dioxide@carbon matrix precursor solution; 75 mL Tris buffered soln (pH=8.5; 10 mM); ultrasonic disperse obtains uniform dispersion; stirring adds Dopamine HCL; the mass ratio of the hollow carbon matrix precursor of silicon-dioxide@and Dopamine HCL is 1: 2, room temperature reaction 24 h, and centrifuge washing is dried; product is placed in tube furnace; under pure argon protection, controlling temperature rise rate is 2 DEG C ∕ min, and gas flow rate is 90 mL ∕ min; first 300 DEG C are warming up to; be warming up to 800 DEG C after being incubated 2 h, be incubated naturally cooling after 2 h, obtain the hollow carbon of N doping nucleocapsid.
embodiment 2
By SiO
2ball is distributed in the mixed solution of deionized water and ethanol, and the volume ratio of deionized water and ethanol is that 5:1 adds cetyl trimethylammonium bromide, ammoniacal liquor, Resorcinol under magnetic stirring, after 35 DEG C of stirring 30 min, adds formaldehyde, An Shui ︰ Jian Ben bis-Fen ︰ SiO
2the mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromide is 1: 3.5: 8: 5: 20, react 6 h, ageing one night, centrifuge washing obtains hollow carbon matrix precursor, then is mixed with 3 wt% hollow carbon balls precursor water solution, take hollow carbon balls precursor water solution (3 wt%), cetyl trimethylammonium bromide, ammoniacal liquor, be added in the mixing solutions of ethanol and deionized water, the volume ratio of deionized water and ethanol is 1 ︰ 1, empty carbon ball precursor water solution: cetyl trimethylammonium bromide: the mass ratio of ammoniacal liquor is after 1: 1.6: 10 ultrasonic 1-2 h, tetraethyl orthosilicate is dropped in above-mentioned reaction solution, be 1 ︰ 18.8 to drive body ︰ tetraethyl orthosilicate mass ratio before the carbon ball of overhead, room temperature strong stirring 6 h, filtering and washing is to neutral, room temperature dries to obtain the hollow carbon matrix precursor of [email protected] for silicon-dioxide@carbon matrix precursor is dissolved in Tris buffered soln (pH=8.5; 10 mM); ultrasonic disperse obtains uniform dispersion; stirring adds Dopamine HCL; the mass ratio of the hollow carbon matrix precursor of silicon-dioxide@and Dopamine HCL is 1: 3; room temperature reaction 24 h; centrifuge washing is dried, and is placed by product in tube furnace, under pure argon protection; controlling temperature rise rate is 1 DEG C ∕ min; gas flow rate is 90 mL ∕ min, is first warming up to 400 DEG C, is warming up to 600 DEG C after being incubated 2 h; be incubated naturally cooling after 2 h, obtain the hollow carbon of N doping nucleocapsid.
embodiment 3
By SiO
2ball is distributed in the mixed solution of deionized water and ethanol, and the volume ratio of deionized water and ethanol is that 5:1 adds cetyl trimethylammonium bromide, ammoniacal liquor, Resorcinol under magnetic stirring, after 35 DEG C of stirring 30 min, adds formaldehyde, An Shui ︰ Jian Ben bis-Fen ︰ SiO
2the mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromide is 1: 3.5: 6: 5: 20, react 5 h, ageing one night, centrifuge washing obtains hollow carbon matrix precursor, then is mixed with 3 wt% empty carbon ball precursor water solution, take hollow carbon balls precursor water solution (3 wt%), cetyl trimethylammonium bromide, ammoniacal liquor, be added in the mixing solutions of ethanol and deionized water, the volume ratio of deionized water and ethanol is 1 ︰ 1, empty carbon ball precursor water solution: cetyl trimethylammonium bromide: the mass ratio of ammoniacal liquor is after 3: 1.6: 10 ultrasonic 1-2 h, tetraethyl orthosilicate is dropped in above-mentioned reaction solution, above hollow carbon balls Qian Qu Ti ︰ tetraethyl orthosilicate mass ratio is 1 ︰ 13, room temperature strong stirring 9 h, filtering and washing is to neutral, room temperature dries to obtain the hollow carbon matrix precursor of [email protected] is in the dilute hydrochloric acid solution of 1 mol/L that hollow for silicon-dioxide@carbon matrix precursor is dissolved in 200 mL concentration, ultrasonic disperse obtains uniform dispersion, ice bath stirs and adds pyrroles, the mass ratio of the hollow carbon matrix precursor of silicon-dioxide@and pyrroles is 1: 2, 4.8 g Potassium Persulphates are added after stirring, 0-5 DEG C of reaction 24 h, centrifuge washing is dried, product is placed in tube furnace, under pure argon protection, controlling temperature rise rate is 2 DEG C ∕ min, gas flow rate is 90 mL ∕ min, first 300 DEG C are warming up to, 800 DEG C are warming up to after being incubated 2 h, be incubated naturally cooling after 2 h, obtain the hollow carbon of N doping nucleocapsid.
Claims (7)
1. a preparation method for the hollow carbon of N doping nucleocapsid, is characterized in that the method has following processing step:
By SiO
2ball is distributed in the mixed solution of deionized water and ethanol, the volume ratio of deionized water and ethanol is 8-4:1, adds cetyl trimethylammonium bromide, ammoniacal liquor, Resorcinol under magnetic stirring, after 35 DEG C of stirring 30 min, add formaldehyde, above ammoniacal liquor: Jian Ben bis-Fen ︰ SiO
2︰ formaldehyde: the mass ratio of cetyl trimethylammonium bromide is 1: 3.5: 4-8: 5: 20, reaction 3-6 h, ageing one night, centrifuge washing obtains hollow carbon matrix precursor, then is mixed with 3 wt% empty carbon ball precursor water solution, take hollow carbon balls precursor water solution, cetyl trimethylammonium bromide, ammoniacal liquor, be added in the mixing solutions of ethanol and deionized water, the volume ratio of deionized water and ethanol is 1:1-4, hollow carbon balls precursor water solution: cetyl trimethylammonium bromide: the mass ratio of ammoniacal liquor is 1-5: 1.6: 10, after ultrasonic 1-2 h, tetraethyl orthosilicate is dropped in above-mentioned reaction solution, above hollow carbon balls Qian Qu Ti ︰ tetraethyl orthosilicate mass ratio is 1 ︰ 9.4-18.8, room temperature strong stirring 6-12 h, filtering and washing is to neutral, room temperature dries to obtain the hollow carbon matrix precursor of silicon-dioxide@, last at silicon-dioxide@hollow carbon matrix precursor surface aggregate polymer with nitrogen, then through high-temperature calcination, etch to obtain the hollow carbon of nucleocapsid of N doping.
2. the preparation method of the hollow carbon of N doping nucleocapsid hollow carbon nucleocapsid according to right 1, its feature is at above-mentioned SiO
2particle diameter at 100-500 nm.
3. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is the one in aniline, pyrroles, Dopamine HCL at above-mentioned polymer with nitrogen monomer.
4. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is at above-mentioned polymer with nitrogen monomer: the mass ratio of the hollow carbon matrix precursor of silicon-dioxide@nucleocapsid is 0.5-4: 1.
5. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is 6-24 h in the above-mentioned polymer with nitrogen monomer polymerization time.
6. the preparation method based on the hollow carbon of N doping nucleocapsid according to right 1, is characterized in that, the inert protective gas of high-temperature burning process is pure nitrogen gas or argon gas; Calcination process needs two step temperature controls to realize, and the first step calcining temperature is 300-400 DEG C, and second step calcining temperature is 600-800 DEG C, and soaking time is 1-3 h; Temperature rise rate is 0.5-5 DEG C of ∕ min, and rare gas element flow velocity is 50-150 mL ∕ min.
7. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is at above-mentioned etching SiO
2adopt hydrofluoric acid or sodium hydroxide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050032635A1 (en) * | 2003-08-06 | 2005-02-10 | Yu Jong Sung | HCMS carbon capsule, electrocatalysts for fuel cell supported by HCMS carbon capsule, and method of preparing the same |
| CN101618869A (en) * | 2009-07-28 | 2010-01-06 | 中国科学院上海硅酸盐研究所 | Method for preparing small-size meso-porous hollow carbon sphere |
-
2015
- 2015-06-24 CN CN201510352231.3A patent/CN104961121B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050032635A1 (en) * | 2003-08-06 | 2005-02-10 | Yu Jong Sung | HCMS carbon capsule, electrocatalysts for fuel cell supported by HCMS carbon capsule, and method of preparing the same |
| CN101618869A (en) * | 2009-07-28 | 2010-01-06 | 中国科学院上海硅酸盐研究所 | Method for preparing small-size meso-porous hollow carbon sphere |
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