CN107619035A

CN107619035A - A kind of preparation method of nitrogen-doped carbon nano material

Info

Publication number: CN107619035A
Application number: CN201711094898.3A
Authority: CN
Inventors: 张旺; 柴华; 刁国旺
Original assignee: Yangzhou University
Current assignee: Yangzhou University
Priority date: 2017-11-09
Filing date: 2017-11-09
Publication date: 2018-01-23

Abstract

A kind of preparation method of nitrogen-doped carbon nano material, is related to technical field of energy material, and after melamine and potassium citrate mixed grinding, grinding can be sufficiently mixed two kinds of solid powders, make solid phase dispersion uniform.It is placed in tube furnace and calcines under the protection of inert gas, after natural cooling, by the product of cooling using hydrochloric acid, water washing, obtains solid phase and dry, obtain the carbon nanomaterial of N doping.Operating method of the present invention is simple and easy, flow is shorter, raw material is easy to get, and resulting nitrogen-doped carbon nano material physico-chemical property is relatively stable, and has high specific surface area and specific capacitance, can improve the capacity of porous carbon nanosheet electrode material.

Description

A kind of preparation method of nitrogen-doped carbon nano material

Technical field

The present invention relates to technical field of energy material, more particularly to the technology of preparing of the carbon nanomaterial of N doping.

Background technology

Many researchs and calculating show that nitrogen is the element at infinity for adulterating carbon material.In the periodic table of elements, nitrogen and carbon phase Neighbour, atomic radius approach, so the doping of nitrogen-atoms can make the lattice of carbon material that distortion as small as possible occur.On nitrogen-atoms The lone pair electrons carried play a part of carrier, after porous carbon materials are doped to, the charge density increase of porous carbon materials, N-type semiconductor is formed, and then increases the electric conductivity of porous carbon materials.Introducing affirmative of the nitrogen-atoms in porous carbon materials structure Activity increase in the defects of porous carbon materials can be increased position, or electrocatalytic reaction.The increase of surface nitrogen-containing functional group then can Improve the surface hydrophilic performance of porous carbon materials, improve its biocompatibility.In a word, the porous carbon materials of N doping are more porous than pure Carbon material has more excellent properties, will greatly expand application of the carbon material in every field.

The content of the invention

There is high-specific surface area and compared with the porous carbon nanomaterial of the N doping of high specific capacitance it is an object of the present invention to provide a kind of Preparation method, the capacity of porous carbon nanosheet electrode material can be improved.

The technical solution adopted by the present invention is：After melamine and potassium citrate mixed grinding, grinding can make two kinds Solid powder is sufficiently mixed, and makes solid phase dispersion uniform.It is placed in tube furnace and calcines under the protection of inert gas, treats natural cooling Afterwards, the product of cooling is obtained solid phase and dried, obtained the carbon nanomaterial of N doping using hydrochloric acid, water washing.

Operating method of the present invention is simple and easy, flow is shorter, raw material is easy to get, resulting nitrogen-doped carbon nano material materialization Property is relatively stable, and has high specific surface area and specific capacitance, can improve the capacity of porous carbon nanosheet electrode material.

Further, the mass ratio that feeds intake of melamine and potassium citrate of the present invention is 1: 1~5.Under the ratio The nano material of formation has good porous and capacitive property.

Described inert gas is nitrogen, can effectively prevent the oxidation in material preparation process, and further reduce production Cost.

The calcining is at normal temperatures, with 0.5~5 DEG C/min heating rate, temperature to be risen into 500~1000 DEG C of progress Calcining.Under this heating rate, obtained nitrogen-doped carbon nano material can possess optimal pattern, so that it is guaranteed that it possesses most Good chemical property.Secondly, calcining can obtain the carbon material of different carbonizing degrees at different temperatures, and be forged at a temperature of this The carbon material carbonizing degree highest of burning, the chemical property possessed are preferably also.

The hydrochloric acid is the aqueous hydrochloric acid solution that mass percent is 10~50%.The hydrochloric acid corrosion resistance of various concentrations is different, choosing The impurity of required removal can not only have been removed but also not destroy the various properties for preparing material by selecting the hydrochloric acid of the concentration, can be prepared The composite of optimum profile and best electrochemical performance.

The present invention uses salt acid elution, is washed till no bubble and produces the inorganic impurity that can fully remove in material, so as to Impurity is not contained in the material for ensuring to obtain.Be washed with water by solution ph regulation to neutrality, substantially ensure that inorganic impurity and Hydrochloric acid is all washed complete, so as to obtain the purer carbon doping carbon nanomaterial of purity.

The temperature conditionss of the drying are 50~100 DEG C, and the time is 12~24 h.It can ensure that material is fully dried.

Brief description of the drawings

Fig. 1 is the scanning electron microscope (SEM) photograph of material prepared by the present invention.

Fig. 2 is the adsorption/desorption curve figure of the nitrogen of material prepared by the present invention.

Fig. 3 is the graph of pore diameter distribution of material prepared by the present invention.

Fig. 4 is the cyclic voltammetry curve of material prepared by the present invention.

Fig. 5 is the charging and discharging curve figure of material prepared by the present invention.

Embodiment

First, the preparation method of material：

Weigh 1g melamines and 1g potassium citrates are fully ground, be put under nitrogen protection in tube furnace, with 5 DEG C/min's Heating rate, 900 DEG C are risen to from normal temperature, maintains 2.0 h to be calcined.

Obtained product is washed to bubble-free generation with 1 mol/L HCl/water solution, is washed with water and washs, Ran Houli The heart, take solid phase to be dried in 60 DEG C of baking ovens, obtain the carbon nanomaterial of N doping.

2nd, interpretation of result：

The carbon nanomaterial of obtained N doping is scanned, obtains electron microscope, as can be seen from Figure 1 nitrogen-doped carbon nanometer sheet For fiber micro-tube shaped structure.

It can be seen that from the adsorption/desorption curve figure of Fig. 2 nitrogen：The absorption of nitrogen-doped carbon nanometer sheet belongs to type suction It is attached（IUPAC classifies）.

It can be seen that from Fig. 3 graph of pore diameter distribution：Nanometer sheet bore dia is less than 3 nm, and it is a large amount of micro- to illustrate that adsorbent is present Hole.

The specific capacitance of the material of visible preparation is 131 F/g from Fig. 4,5 curves, has higher specific capacitance.

Claims

A kind of 1. preparation method of nitrogen-doped carbon nano material；It is characterized in that：By melamine and potassium citrate mixed grinding Afterwards, it is placed in tube furnace and calcines under the protection of inert gas, after natural cooling, by the product of cooling using hydrochloric acid, washing Wash, take solid phase to dry, obtain the carbon nanomaterial of N doping.
2. preparation method according to claim 1, it is characterised in that：The quality that feeds intake of the melamine and potassium citrate Than for 1: 1~5.
3. preparation method according to claim 1, it is characterised in that：The inert gas is nitrogen.
4. according to the preparation method described in claim 1 or 2 or 3, it is characterised in that：The calcining be at normal temperatures, with 0.5~ 5 DEG C/min heating rate, temperature is risen to 500~1000 DEG C and calcined.
5. preparation method according to claim 1, it is characterised in that：The hydrochloric acid is that mass percent is 10~50% Aqueous hydrochloric acid solution.
6. preparation method according to claim 1, it is characterised in that：During the washing, by the product of cooling first with hydrochloric acid After washing produces to bubble-free, then with water washing.
7. preparation method according to claim 1, it is characterised in that：The temperature conditionss of the drying are 50~100 DEG C, when Between be 12~24 h.