CN104961121B - 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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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 material with carbon element manufacturing process technology field, is related to a kind of preparation side based on the hollow carbon of N doping nucleocapsid
Method.The hollow carbon of N doping nucleocapsid prepared by the present invention can be widely applied to ultracapacitor, structure capacitance desalination, lithium ion battery
Etc. electrochemical field.
Background technology
The features such as hollow carbon is due to its high-specific surface area, unique hollow structure, low cost, is widely used as at present gas
Electrode material of body release agent, the carrier of catalyst and ultracapacitor etc..It is to improve its performance that the surface of hollow carbon is modified
Important method.With pure carbon phase ratio, it is surface-modified after material with carbon element after such as Heteroatom doping can show in some aspects more
Plus superior performance.The modified method in traditional surface is that acid oxidase is processed so as to which surface has oxygen-containing functional group（-
OH,-COOH）, it is easy to the destruction of hollow carbon structure is caused, such as：Ball wall ruptures, and caves in.At present, the doping of nitrogen
It is the importance of the Research on Surface Modification of material with carbon element.The doping of nitrogen can improve the electronic transmission performance of material with carbon element, reduce
Resistance coefficient.Additionally, the doping of nitrogen can also increase the avtive spot of carbon material surface, hydrophily is improved so as in electrification
Field shows more wide application prospect.Based on the N doping of hollow carbon, mainly by following method：（1）
The NH in later stage3Process；（2）Nitrogenous carbon source is polymerized in template surface, then cracks gained.But, hollow carbon before modified after duct
Structure is more single, is unfavorable for diffusion mass transfer, limits its application.In addition before modified after the inner surface of hollow carbon often cannot
It is utilized effectively, therefore the utilization rate on its surface, its adsorption site is relatively fewer.How by the structure regulating of hollow carbon and surface
Modified organic phase is combined, and is enriched its pore passage structure, is increased surface utilisation and improve other surfaces physical property such as：Hydrophily, lead
Electrical etc. is still a major challenge.This technical barrier is solved, the application to finally expanding hollow carbon is particularly important.
The content 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 core
Shell graded porous structure, while effective N doping is obtained, therefore with 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 SiO2Ball is distributed in the mixed liquor of deionized water and ethanol, and the volume ratio of deionized water and ethanol is（8-4）:
1, cetyl trimethylammonium bromide, ammoniacal liquor, resorcinol are added under magnetic stirring, after 35 DEG C of 30 min of stirring, add first
Aldehyde, above ammoniacal liquor：Jian Ben bis- Fen ︰ SiO2The mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromides is 1: 3.5:（4-8）∶5∶
20；Reaction 3-6 h, are aged a night, and centrifuge washing obtains hollow carbon matrix precursor, then to be configured to 3 wt% hollow carbon balls presomas water-soluble
Liquid；Weigh hollow carbon balls precursor water solution, cetyl trimethylammonium bromide, ammoniacal liquor is added to ethanol and deionized water
In mixed solution, the volume ratio of deionized water and ethanol is 1:（1-4）, hollow carbon balls precursor water solution: cetyl front three
Base ammonium bromide: the mass ratio of ammoniacal liquor is（1-5）: 1.6: 10, after ultrasonic 1-2 h, tetraethyl orthosilicate is dropped to into above-mentioned reaction
In liquid, above hollow carbon balls Qian Qu Ti ︰ tetraethyl orthosilicates mass ratio is 1 ︰（9.4-18.8）, room temperature strong stirring, suction filtration washes
Wash to neutrality, room temperature dries to obtain the hollow carbon matrix precursors of silica@.Finally on the hollow carbon matrix precursor surface of coated with silica
Polymerization polymer with nitrogen, then Jing calcining, etch N doping the hollow carbon of nucleocapsid.
Above-mentioned composite building-up process：Described SiO2Ball, particle diameter is 100-500 nm, ammoniacal liquor, resorcinol, SiO2
Ball, formaldehyde, the mass ratio of cetyl trimethylammonium bromide, the wall thickness of reaction time and hollow carbon, particle size and homogeneity
Correlation, beyond above range may the hollow carbon of kernel cannot be formed, so as to the N doping that this patent is referred to cannot be obtained
The hollow carbon of nucleocapsid.
Above-mentioned composite building-up process：The mass ratio of hollow carbon balls presoma and tetraethyl orthosilicate and pomegranate shape structure
Classification is related, and may result in pomegranate shape core shell structure beyond above range cannot obtain, and refer to so as to obtain this patent
N doping the hollow carbon of nucleocapsid.
Above-mentioned composite building-up process：The polymerization of the polymer with nitrogen and N doping and the formation phase of core shell structure
Close.If polymer with nitrogen cannot be aggregated in the hollow carbon matrix precursor surface of coated with silica, i.e., cannot form the core of pomegranate shape
The hollow carbon of shell.
The process of above-mentioned carbonization：Under an inert atmosphere, it is divided into the intensification of two steps, first aim temperature is 300-400 DEG C,
In the temperature range there is Pintsch process and polymer with nitrogen cracking in phenolic resin, and second target temperature is 600-800
DEG C, in the graphitization of the hollow carbon of temperature range nucleocapsid.Inert gas is purity nitrogen or argon gas, and the heating rate that two steps heat up is
0.5-2 DEG C/min, the flow velocity of inert gas is 50-150 mL/min.
Preparation process of the present invention is simple, experimental facilities is required low, it is easy to operate.The inventive method passes through multistep template
Structure design is carried out to the hollow carbon of nucleocapsid and duct is adjusted, while effective N doping is also carried out, the stone of the final gained of the present invention
The hollow carbon of nucleocapsid of pomegranate shape can be widely used for electrochemical field.
Specific embodiment
After now the specific embodiment of the present invention is described in.
Embodiment 1
By SiO2Ball is distributed in the mixed liquor of deionized water and ethanol, and the volume ratio of deionized water and ethanol is 8:1
Cetyl trimethylammonium bromide, ammoniacal liquor, resorcinol are added under magnetic agitation, after 35 DEG C of 30 min of stirring, formaldehyde is added,
An Shui ︰ Jian Ben bis- Fen ︰ SiO2The mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromides is 1: 3.5: 4: 5: 20；3 h are reacted, it is old
Change a night, centrifuge washing obtains hollow carbon matrix precursor, then is configured to 3 wt% hollow carbon balls precursor water solutions；Weigh hollow carbon balls
Precursor water solution（3 wt%）, cetyl trimethylammonium bromide, ammoniacal liquor adds the mixed solution to ethanol and deionized water
In, the volume ratio of deionized water and ethanol is 1 ︰ 1, empty carbon ball precursor water solution: cetyl trimethylammonium bromide: ammoniacal liquor
Mass ratio is after 2: 1.6: 10 ultrasound 1-2 h, tetraethyl orthosilicate to be dropped in above-mentioned reactant liquor, above hollow carbon balls forerunner
Ti ︰ tetraethyl orthosilicates mass ratio is 1 ︰ 9.4, and the h of room temperature strong stirring 12, filtering and washing to neutrality, room temperature dries to obtain titanium dioxide
The hollow carbon matrix precursors of silicon@.By the hollow carbon matrix precursor solution of silica@, 75 mL Tris cushioning liquid（PH=8.5,10 mM）,
Ultrasonic disperse obtains uniform dispersion, and stirring adds dopamine, and the hollow carbon matrix precursors of silica@are 1 with the mass ratio of dopamine:
2, the h of room temperature reaction 24, centrifuge washing drying places product in tube furnace, under straight argon gas shielded, controls heating rate for 2
DEG C ∕ min, gas flow rate is 90 mL ∕ min, and 300 DEG C are warming up to first, 800 DEG C is warming up to after 2 h of insulation, nature after 2 h of insulation
Cooling, obtains final product the hollow carbon of N doping nucleocapsid.
Embodiment 2
By SiO2Ball is distributed in the mixed liquor of deionized water and ethanol, and the volume ratio of deionized water and ethanol is 5:1
Cetyl trimethylammonium bromide, ammoniacal liquor, resorcinol are added under magnetic agitation, after 35 DEG C of 30 min of stirring, formaldehyde is added,
An Shui ︰ Jian Ben bis- Fen ︰ SiO2The mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromides is 1: 3.5: 8: 5: 20；6 h are reacted, it is old
Change a night, centrifuge washing obtains hollow carbon matrix precursor, then is configured to 3 wt% hollow carbon balls precursor water solutions；Weigh hollow carbon balls
Precursor water solution（3 wt%）, cetyl trimethylammonium bromide, ammoniacal liquor adds the mixed solution to ethanol and deionized water
In, the volume ratio of deionized water and ethanol is 1 ︰ 1, empty carbon ball precursor water solution: cetyl trimethylammonium bromide: ammoniacal liquor
Mass ratio is after 1: 1.6: 10 ultrasound 1-2 h, tetraethyl orthosilicate to be dropped in above-mentioned reactant liquor, with overhead carbon ball forerunner
Ti ︰ tetraethyl orthosilicates mass ratio is 1 ︰ 18.8, and the h of room temperature strong stirring 6, filtering and washing to neutrality, room temperature dries to obtain titanium dioxide
The hollow carbon matrix precursors of silicon@.The hollow carbon matrix precursors of silica@are dissolved in into Tris cushioning liquid（PH=8.5,10 mM）, ultrasound point
Uniform dispersion is dissipated to obtain, stirring adds dopamine, and the hollow carbon matrix precursors of silica@are 1: 3 with the mass ratio of dopamine, room temperature
24 h are reacted, centrifuge washing drying places product in tube furnace, under straight argon gas shielded, control heating rate for 1 DEG C of ∕
Min, gas flow rate is 90 mL ∕ min, and 400 DEG C are warming up to first, and after 2 h of insulation 600 DEG C are warming up to, and is incubated naturally cold after 2 h
But, the hollow carbon of N doping nucleocapsid is obtained final product.
Embodiment 3
By SiO2Ball is distributed in the mixed liquor of deionized water and ethanol, and the volume ratio of deionized water and ethanol is 5:1
Cetyl trimethylammonium bromide, ammoniacal liquor, resorcinol are added under magnetic agitation, after 35 DEG C of 30 min of stirring, formaldehyde is added,
An Shui ︰ Jian Ben bis- Fen ︰ SiO2The mass ratio of ︰ Jia Quan ︰ cetyl trimethylammonium bromides is 1: 3.5: 6: 5: 20；5 h are reacted, it is old
Change a night, centrifuge washing obtains hollow carbon matrix precursor, then is configured to 3 wt% sky carbon ball precursor water solutions；Before weighing hollow carbon balls
Drive the body aqueous solution（3 wt%）, cetyl trimethylammonium bromide, ammoniacal liquor added into the mixed solution of ethanol and deionized water,
The volume ratio of deionized water and ethanol be 1 ︰ 1, empty carbon ball precursor water solution: cetyl trimethylammonium bromide: the matter of ammoniacal liquor
Amount is than being after 3: 1.6: 10 ultrasound 1-2 h, tetraethyl orthosilicate to be dropped in above-mentioned reactant liquor, above hollow carbon balls forerunner
Ti ︰ tetraethyl orthosilicates mass ratio is 1 ︰ 13, and the h of room temperature strong stirring 9, filtering and washing to neutrality, room temperature dries to obtain titanium dioxide
The hollow carbon matrix precursors of silicon@.The hollow carbon matrix precursors of silica@are dissolved in into the dilute hydrochloric acid solution that 200 mL concentration are 1 mol/L
In, ultrasonic disperse obtains uniform dispersion, and ice bath stirring adds the mass ratio of pyrroles, the hollow carbon matrix precursors of silica@and pyrroles
For 1: 2,4.8 g potassium peroxydisulfates are stirring evenly and then adding into, product is placed tube furnace by 0-5 DEG C of 24 h of reaction, centrifuge washing drying
In, under straight argon gas shielded, it is 2 DEG C of ∕ min to control heating rate, and gas flow rate is 90 mL ∕ min, and 300 DEG C are warming up to first,
It is incubated after 2 h and is warming up to 800 DEG C, natural cooling after 2 h of insulation obtains final product the hollow carbon of N doping nucleocapsid.
Claims (7)
1. the preparation method of the hollow carbon of a kind of N doping nucleocapsid, it is characterised in that the method has following processing step：
By SiO2Ball is distributed in the mixed liquor of deionized water and ethanol, and the volume ratio of deionized water and ethanol is 8-4:1, in magnetic
Power stirring is lower to add cetyl trimethylammonium bromide, ammoniacal liquor, resorcinol, after 35 DEG C of 30 min of stirring, adds formaldehyde, the above
Ammoniacal liquor：Jian Ben bis- Fen ︰ SiO2︰ formaldehyde：The mass ratio of cetyl trimethylammonium bromide is 1: 3.5: 4-8: 5: 20；Reaction 3-6
H, is aged a night, and centrifuge washing obtains hollow carbon matrix precursor, then is configured to 3 wt% hollow carbon balls precursor water solutions；Weigh hollow
Carbon ball precursor water solution, cetyl trimethylammonium bromide, ammoniacal liquor is added into the mixed solution 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: ammoniacal liquor
Mass ratio be 1-5: 1.6: 10, after ultrasonic 1-2 h, tetraethyl orthosilicate is dropped in above-mentioned reactant liquor, above hollow carbon
Ball Qian Qu Ti ︰ tetraethyl orthosilicates mass ratio be 1 ︰ 9.4-18.8, room temperature strong stirring 6-12 h, filtering and washing to neutrality, room
Temperature dries to obtain the hollow carbon matrix precursors of silica@；Finally in the hollow carbon matrix precursor surface aggregate polymer with nitrogen of silica@,
Jing high-temperature calcinations again, etch N doping the hollow carbon of nucleocapsid.
2. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is in above-mentioned SiO2Particle diameter in 100-
500 nm。
3. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is in above-mentioned polymer with nitrogen monomer
One kind in aniline, pyrroles, dopamine.
4. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is in above-mentioned polymer with nitrogen monomer: two
The mass ratio of the hollow carbon matrix precursor of silica@nucleocapsids is 0.5-4: 1.
5. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is poly- in above-mentioned polymer with nitrogen monomer
The conjunction time is 6-24 h.
6. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, it is characterised in that the inertia of high-temperature burning process
Protective gas is pure nitrogen gas or argon gas；Calcination process need two step temperature controls realize, first step calcining heat be 300-400 DEG C, second
Step calcining heat is 600-800 DEG C, and temperature retention time is 1-3 h；Heating rate is 0.5-5 DEG C ∕ min, inert gas flow velocity
For 50-150 mL ∕ min.
7. the preparation method of the hollow carbon of N doping nucleocapsid according to right 1, its feature is in above-mentioned etching SiO2Using hydrofluoric acid
Or NaOH.
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