CN105460917A - Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method - Google Patents
Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method Download PDFInfo
- Publication number
- CN105460917A CN105460917A CN201510900803.7A CN201510900803A CN105460917A CN 105460917 A CN105460917 A CN 105460917A CN 201510900803 A CN201510900803 A CN 201510900803A CN 105460917 A CN105460917 A CN 105460917A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped carbon
- acid
- ice bath
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a nitrogen-doped carbon nanotube adopting a hierarchical structure and a preparation method. The material is doped with nitrogen and adopts the obvious hierarchical structure, and the carbon nanotube comprises tinier nitrogen-doped carbon particles. The preparation method comprises steps as follows: aniline is uniformly dispersed in an acid solution through stirring, an aniline suspension is obtained and subjected to ice bath treatment for 20-60 min, and stirring is kept in the ice bath process; an oxidizing agent is dissolved in deionized water through stirring and subjected to ice bath treatment for 5-30 min; stirring is stopped, an oxidizing agent solution is quickly poured into an aniline suspension mixed solution and subjected to ice bath treatment for 8-28 h, centrifugal washing is performed by the aid of deionized water and ethanol until a supernatant is clarified, and a sample is dried in an oven; the dried sample is ground, subjected to heat treatment in air and naturally cooled; a treated composite is calcined at the high temperature in an inert atmosphere and naturally cooled. The nitrogen-doped carbon nanotube has the advantages of high capacity, good rate capability and good circulating performance and can be used as an anode material for a lithium ion battery.
Description
Technical field
The present invention relates to preparation method of a kind of nitrogen-doped carbon nanometer pipe and preparation method thereof.
Background technology
Graphite (comprising natural graphite, electrographite) is as conventional commercial lithium ion battery negative material, due to its theoretical capacity low (372mAh/g), the reasons such as cycle life is lower, high rate performance is poor, significantly limit its application in lithium ion battery negative material field.In order to meet the demand of high-power, heavy body energy storage device (as portable electric appts, storing base station and electromobile etc.) further, domestic and international researcher is devoted to that research and development capacity is high, good cycling stability, economic cheap lithium ion battery negative material always.Nitrogen-doped carbon not only has the lithium ion storage capacity higher than conventional commercial graphite, and it also has higher specific conductivity simultaneously, is considered to a kind of lithium ion battery negative material of great potential.But, provide a kind of and can prepare on a large scale, nitrogen-doped carbon that is with low cost, good cycling stability remains a huge challenge.
In recent years, domestic and international researchist has good high rate performance and higher specific storage by the nitrogen-doped carbon that serial of methods obtains, people (the LiX such as such as Li, etal.JournalofPowerSources, 2012,197:238-245.) obtain nitrogen-doped nanometer pipe by chemical Vapor deposition process growth, have excellent cycle performance, its specific storage doubles non-doped carbon nanometer pipe; The people such as Wang (WangZ, etal..ElectrochimicaActa, 2013,106:320-326.) obtain network structure polypyrrole nanofibers by template, logical calcining stripping obtains network structure nitrogen-doped carbon nano-fiber, has excellent lithium storage content; The people such as Li (LiZ, etal..Energy & EnvironmentalScience, 2013,6 (3): 871-878.) from protein derivatives, stripping obtains mesoporous nitrogen-doped carbon material, nitrogen content, up to more than 10%, lithium ion battery and capacitor application all has ultra-high capacity; The people such as Xiang (XiangX, etal.MaterialsResearchBulletin, 2011,46 (8): 1266-1271.) are by salt of wormwood (KC
2o
3) polyaniline nano ball prepared by process, then be aided with high-temperature calcination, obtain the nitrogen doped micropore Nano carbon balls that specific storage is higher.Although obtained certain progress about nitrogen-doped carbon lithium ion battery negative material at present, but these nitrogen-doped carbon materials described in archives patent or complex process, cost are higher, or cycle life is very short, be difficult to the application demand meeting lithium ion battery negative material.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of nitrogen-doped carbon nanometer pipe with hierarchy and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
There is provided a kind of nitrogen-doped carbon nanometer pipe, this is material doped nitrogen, and have obvious hierarchy, wherein said carbon nanotube is by more small nitrogen-doped carbon granulometric composition.
By such scheme, diameter 50 ~ 200 nanometer of carbon nanotube, the diameter of nitrogen-doped carbon particulate is 10 ~ 50 nanometers.
A kind of preparation method of nitrogen-doped carbon nanometer pipe is provided, comprises the following steps:
1) stirring makes aniline be dispersed in acid solution, obtains aniline suspension, then ice bath 20 ~ 60 minutes, keeps stirring in ice bath process;
2) oxygenant is dissolved in deionized water, stirs and make it dissolve, ice bath 5 ~ 30 minutes;
3) by step 1) in stirring close, then by step 2) in oxidizing agent solution pour step 1 into rapidly) aniline suspension mixed solution in, ice bath 8 ~ 28 hours, distinguishes centrifuge washing until supernatant liquor clarification with deionized water and ethanol, puts into baking oven and dry;
4) by step 3) gained dry sample grind, then heat-treat in atmosphere, naturally cooling, obtain the mixture after preliminary carbonization;
5) by step 4) process after mixture carry out high-temperature calcination under an inert atmosphere, naturally cooling, obtain nitrogen-doped carbon nanometer pipe material.
By such scheme, step 1) described in acid be one in organic acid (oxalic acid, citric acid, phytic acid, Witco 1298 Soft Acid, oxysuccinic acid, Whitfield's ointment and phenylformic acid) and mineral acid (hydrochloric acid, phosphoric acid, nitric acid, perchloric acid and sulfuric acid).
By such scheme, step 2) oxygenant used is any one in ammonium persulphate, iron(ic) chloride, Manganse Dioxide, oxalic acid, hydrogen peroxide, potassium bichromate, potassium permanganate.
By such scheme, step 2) in the concentration of oxidizing agent solution be 0.0625 ~ 1.25mol/L.
By such scheme, the amount of substance ratio of described aniline and acid is 8.0 ~ 15.5mmol:0.1 ~ 1.5mmol.
By such scheme, the amount of substance ratio of described aniline and oxygenant is 8.0 ~ 15.5mmol:5.0 ~ 25.0mmol.
By such scheme, step 4) described in milling time be 10 ~ 30 minutes;
By such scheme, step 4) described in thermal treatment to refer under air atmosphere with 1 ~ 15 DEG C/min temperature rise rate, be raised to target temperature 150 ~ 280 DEG C insulation 0.5 ~ 5 hour;
By such scheme, step 5) described in high-temperature calcination refer in a nitrogen atmosphere, with 1 ~ 15 DEG C/min temperature rise rate, to be raised to after target temperature 500 ~ 850 DEG C insulation 5 ~ 15 hours.
The invention has the advantages that:
The invention provides the nitrogen-doped nanometer pipe with hierarchy and take full advantage of technology maturation as ion cathode material lithium and industrialized carbon has done main discharge and recharge material, fully can alleviate because of Lithium-ion embeding and the STRESS VARIATION of deviating from process, ensure useful cyclical stability; There is good electroconductibility; In addition, by doping nitrogen, utilize nitrogen to have the function storing lithium ion, overcome the drawback that carbon theoretical capacity is low, there is the advantage of heavy body, good rate capability, good cycle.
Preparation method's technique of the present invention is simple, easy handling, raw material sources extensively, inexpensive, can scale operation be realized, be the effective ways that preparation is suitable for use in the high performance lithium ion battery electrode materials of suitability for industrialized production.
Accompanying drawing explanation
The cycle performance figure of simulated battery when Fig. 1 is nitrogen-doped nanometer pipe lithium cell negative pole;
The high rate performance figure of simulated battery when Fig. 2 is nitrogen-doped nanometer pipe lithium cell negative pole;
Fig. 3 is the SEM photo of nitrogen-doped nanometer pipe.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.Following embodiment all just illustrates, all changes in the present invention or equivalent scope of the present invention are all included in the invention.
Comparative example's (without air thermal treatment)
1) measure 10.0mmol aniline, 0.52mmol phytic acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 30 minutes;
2) weighing 17.3mmol ammonium persulphate adds in 50mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 12 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry.
4) by step 3) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, 10 hours are incubated at 500 DEG C, treat tube furnace naturally cooling, the black powder obtained is a kind of nitrogen-doped carbon nanometer pipe material, and resulting materials performance as shown in Table 1.
Embodiment 1
1) measure 10.0mmol aniline, 0.52mmol phytic acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 30 minutes, keeps stirring in ice bath process;
2) weighing 17.3mmol ammonium persulphate adds in 50mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 12 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 5 DEG C/min, at 200 DEG C be incubated 2 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, and then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 500 DEG C, be incubated 10 hours, treat tube furnace naturally cooling, the black powder obtained is nitrogen-doped carbon nanometer pipe material.
Nitrogen-doped carbon nanometer pipe material is taken respectively: acetylene black: tetrafluoroethylene with the mass ratio of 7:2:1, add the N-Methyl pyrrolidone supersound process 1 ~ 2 hour of designated volume, evenly be coated on Copper Foil and make electrode, employing metal lithium sheet is positive pole, electrolytic solution is 1mol/LLiPF6/EC-DMC (volume ratio is 1:1), and polypropylene micropore diaphragm is that barrier film (Celgard2300) is assembled into half-cell.
Fig. 1 is the cycle performance figure of simulated battery when current density is 4000mA/g that nitrogen-doped carbon nanometer pipe material of the present invention is assembled when doing lithium cell negative pole, can find that this material has extraordinary cycle performance; Fig. 2 is high rate performance figure, even if can find the discharge and recharge of experience high current density, when returning to low current density, its charge specific capacity can recover substantially.Fig. 3 be this product SEM figure, can carbon nanotube structure be found, diameter 50 ~ 150 nanometer of pipe, and carbon receive material pipe there is typical hierarchy, the nitrogen-doped carbon particulate that namely carbon nanotube is 10 ~ 20 nanometers by diameter is further formed.
Embodiment 2
1) measure 10.0mmol aniline, 0.21mmol phytic acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 20 minutes, keeps stirring in ice bath process;
2) weighing 17.3mmol ammonium persulphate adds in 50mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 24 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 5 DEG C/min, at 150 DEG C be incubated 5 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 15 DEG C/min, at 500 DEG C, 15 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 80 ~ 120 nanometer of pipe, the nitrogen-doped carbon particulate being 10 ~ 20 nanometers by diameter is formed.
Embodiment 3
1) measure 10.0mmol aniline, 0.89mmol sulfuric acid joins in 50mL deionized water, and magnetic agitation 10 minutes mixing to be placed in ice bath 60 minutes, keeps stirring in ice bath process;
2) weighing 5mmol iron(ic) chloride adds in 20mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 24 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 1 DEG C/min, at 200 DEG C be incubated 5 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 700 DEG C, 10 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 100 ~ 150 nanometer of pipe, the nitrogen-doped carbon particulate being 40 ~ 50 nanometers by diameter is formed.
Embodiment 4
1) measure 15.3mmol aniline, 1.0mmol oxalic acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 45 minutes, keeps stirring in ice bath process;
2) weighing 5mmol iron(ic) chloride adds in 20mL deionized water, ice bath 5 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 8 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 10 DEG C/min, at 280 DEG C be incubated 2 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 1 DEG C/min, at 700 DEG C, 15 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 50 ~ 80 nanometer of pipe, the nitrogen-doped carbon particulate being 5 ~ 20 nanometers by diameter is formed.。
Embodiment 5
1) measure 15.3mmol aniline, 1.2mmol nitric acid joins in 50mL deionized water, and magnetic agitation 15 minutes mixing to be placed in ice bath 30 minutes, keeps stirring in ice bath process;
2) weigh 25mmol Manganse Dioxide, add in 80mL deionized water, ice bath 20 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 28 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 10 DEG C/min, at 280 DEG C be incubated 5 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 5 DEG C/min, at 600 DEG C, 5 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 100 ~ 180 nanometer of pipe, the nitrogen-doped carbon particulate being 20 ~ 40 nanometers by diameter is formed.
Embodiment 6
1) measure 15.3mmol aniline, 1.2mmol perchloric acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 30 minutes, keeps stirring in ice bath process;
2) claim 25mmol Manganse Dioxide, add in 60mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 24 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 5 DEG C/min, at 200 DEG C be incubated 0.5 hour, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 700 DEG C, 15 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 80 ~ 180 nanometer of pipe, the nitrogen-doped carbon particulate being 15 ~ 30 nanometers by diameter is formed.
Embodiment 7
1) measure 15.3mmol aniline, 1.5mmol perchloric acid joins in 50mL deionized water, and magnetic agitation 20 minutes mixing to be placed in ice bath 30 minutes, keeps stirring in ice bath process;
2) weighing 25mmol Manganse Dioxide adds in 50mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 12 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 5 DEG C/min, at 150 DEG C be incubated 4 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 850 DEG C, 5 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 40 ~ 120 nanometer of pipe, the nitrogen-doped carbon particulate being 5 ~ 20 nanometers by diameter is formed.
Embodiment 8
1) measure 8.2mmol aniline, 0.89mmol nitric acid joins in 50mL deionized water, and magnetic agitation 10 minutes mixing to be placed in ice bath 20 minutes, keeps stirring in ice bath process;
2) weigh 8.6mmol ammonium persulphate, add in 80mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 12 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 15 DEG C/min, at 200 DEG C be incubated 2 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 500 DEG C, 10 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 50 ~ 150 nanometer of pipe, the nitrogen-doped carbon particulate being 10 ~ 30 nanometers by diameter is formed.
Embodiment 9
1) measure 8.2mmol aniline, 0.10mmol hydrochloric acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 20 minutes, keeps stirring in ice bath process;
2) weigh 8.6mmol ammonium persulphate, add in 50mL deionized water, ice bath 10 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 18 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 15 DEG C/min, at 150 DEG C be incubated 0.5 hour, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 850 DEG C, 5 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 100 ~ 150 nanometer of pipe, the nitrogen-doped carbon particulate being 25 ~ 40 nanometers by diameter is formed.
Embodiment 10
1) measure 8.2mmol aniline, 0.56mmol phytic acid joins in 50mL deionized water, and magnetic agitation 30 minutes mixing to be placed in ice bath 30 minutes, keeps stirring in ice bath process;
2) weighing 12.5mmol ammonium persulphate adds in 50mL deionized water, ice bath 30 minutes;
3) by step 1) in magnetic agitation close, then by step 2) solution pours step 1 into rapidly) in mixed solution, be placed in step 1) ice bath 28 hours under equal conditions, after washing 3 times respectively with deionized water and ethanol, put into baking oven and dry;
4) by step 3) gained dry sample grind, then in the tube furnace being full of air, with the temperature rise rate of 10 DEG C/min, at 150 DEG C be incubated 5 hours, treat tube furnace naturally cooling, take out products obtained therefrom;
5) by step 4) products obtained therefrom grinds, then in the tube furnace being full of nitrogen, with the temperature rise rate of 10 DEG C/min, at 850 DEG C, 5 hours are incubated, treat tube furnace naturally cooling, namely the black powder obtained has the nitrogen-doped carbon nanometer pipe material of hierarchy.Wherein diameter 50 ~ 200 nanometer of pipe, the nitrogen-doped carbon particulate being 15 ~ 35 nanometers by diameter is formed.
The method of the nitrogen-doped carbon nanometer pipe reference example 1 of embodiment 2-10 is prepared into electrode, carries out battery performance test, the results are shown in following table 1.
Claims (10)
1. a nitrogen-doped carbon nanometer pipe, is characterized in that: this is material doped nitrogen, and have obvious hierarchy, wherein said carbon nanotube is by more small nitrogen-doped carbon granulometric composition.
2. nitrogen-doped carbon nanometer pipe according to claim 1, is characterized in that: diameter 50 ~ 200 nanometer of carbon nanotube, and the diameter of nitrogen-doped carbon particulate is 10 ~ 50 nanometers.
3. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, is characterized in that: comprise the following steps:
1) stirring makes aniline be dispersed in acid solution, obtains aniline suspension, then ice bath 20 ~ 60 minutes, keeps stirring in ice bath process;
2) oxygenant is dissolved in deionized water, stirs and make it dissolve, ice bath 5 ~ 30 minutes;
3) by step 1) in stirring close, then by step 2) in oxidizing agent solution pour step 1 into rapidly) aniline suspension mixed solution in, ice bath 8 ~ 28 hours, distinguishes centrifuge washing until supernatant liquor clarification with deionized water and ethanol, puts into baking oven and dry;
4) by step 3) gained dry sample grind, then heat-treat in atmosphere, naturally cooling, obtain the mixture after preliminary carbonization;
5) by step 4) process after mixture carry out high-temperature calcination under an inert atmosphere, naturally cooling, obtain nitrogen-doped carbon nanometer pipe material.
4. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, is characterized in that: step 1) described in acid be organic acid oxalic acid, citric acid, phytic acid, Witco 1298 Soft Acid, oxysuccinic acid, Whitfield's ointment and phenylformic acid and the mineral acid (one in hydrochloric acid, phosphoric acid, nitric acid, perchloric acid and sulfuric acid;
Step 2) oxygenant used is any one in ammonium persulphate, iron(ic) chloride, Manganse Dioxide, oxalic acid, hydrogen peroxide, potassium bichromate, potassium permanganate.
5. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, is characterized in that: step 2) in the concentration of oxidizing agent solution be 0.0625 ~ 1.25mol/L.
6. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, is characterized in that: the amount of substance ratio of described aniline and acid is 8.0 ~ 15.5mmol:0.1 ~ 1.5mmol.
7. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, is characterized in that: the amount of substance ratio of described aniline and oxygenant is 8.0 ~ 15.5mmol:5.0 ~ 25.0mmol.
8. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, is characterized in that: step 4) described in milling time be 10 ~ 30 minutes.
9. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, is characterized in that: step 4) described in thermal treatment to refer under air atmosphere with 1 ~ 15 DEG C/min temperature rise rate, be raised to target temperature 150 ~ 280 DEG C insulation 0.5 ~ 5 hour.
10. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 3, it is characterized in that: step 5) described in high-temperature calcination refer in a nitrogen atmosphere, with 1 ~ 15 DEG C/min temperature rise rate, after being raised to target temperature 500 ~ 850 DEG C, be incubated 5 ~ 15 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510900803.7A CN105460917B (en) | 2015-12-08 | 2015-12-08 | A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510900803.7A CN105460917B (en) | 2015-12-08 | 2015-12-08 | A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105460917A true CN105460917A (en) | 2016-04-06 |
| CN105460917B CN105460917B (en) | 2017-12-29 |
Family
ID=55599146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510900803.7A Expired - Fee Related CN105460917B (en) | 2015-12-08 | 2015-12-08 | A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105460917B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106206078A (en) * | 2016-07-27 | 2016-12-07 | 河南师范大学 | A kind of manufacture method of ultracapacitor |
| CN106219515A (en) * | 2016-07-27 | 2016-12-14 | 河南师范大学 | There is the synthetic method of the empty spherical nitrogen-doped carbon material of special crosslinking |
| CN106299282A (en) * | 2016-08-31 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | A kind of nitrogen-doped carbon nanometer pipe sulfur composite and preparation method |
| CN106315552A (en) * | 2016-08-11 | 2017-01-11 | 东北师范大学 | Multilevel porous carbon material and preparation method and application thereof |
| CN106848197A (en) * | 2017-03-22 | 2017-06-13 | 中国科学院长春应用化学研究所 | A kind of lithium ion secondary battery negative pole and preparation method thereof, lithium rechargeable battery |
| CN107541996A (en) * | 2016-06-25 | 2018-01-05 | 董晓 | A kind of preparation method of modified carbon nano-tube electromagnetic shielding paper |
| CN109713307A (en) * | 2018-12-05 | 2019-05-03 | 盐城工学院 | A kind of preparation method and application of double miscellaneous porous carbon nano rod negative electrode materials of element doping |
| CN110240140A (en) * | 2019-06-13 | 2019-09-17 | 苏州科技大学 | Nitrogen-doped porous carbon material and its preparation method and application |
| CN110586115A (en) * | 2019-09-29 | 2019-12-20 | 内蒙古骏成新能源科技有限公司 | High-rate carbon nanotube catalyst, carbon nanotube and preparation method thereof |
| CN110858651A (en) * | 2018-08-24 | 2020-03-03 | 清华大学 | Carbon nanotube composite structure and preparation method thereof |
| CN111799451A (en) * | 2020-05-27 | 2020-10-20 | 广西华政新能源科技有限公司 | High-rate lithium battery negative plate and lithium battery |
| CN112786900A (en) * | 2021-02-03 | 2021-05-11 | 江西理工大学 | Zinc-air cell with embedded Fe2Nitrogen-rich phosphorus carbon spheres of P nanocrystalline and preparation method thereof |
| CN114477176A (en) * | 2022-01-25 | 2022-05-13 | 南京智汇环境气象产业研究院有限公司 | Apple-derived activated carbon material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101882479A (en) * | 2010-06-10 | 2010-11-10 | 北京化工大学 | Electrode material of polyaniline-based nitrogen-containing carbon nano-tube super-capacitor, and preparation method thereof |
| CN103165911A (en) * | 2013-02-01 | 2013-06-19 | 武汉理工大学 | Fuel cell cathode nonmetal catalyst with nano sandwich structure and preparation method thereof |
| CN103400991A (en) * | 2013-08-13 | 2013-11-20 | 天奈(镇江)材料科技有限公司 | Water-based carbon nanotube slurry and preparation method thereof |
| CN103708436A (en) * | 2013-12-17 | 2014-04-09 | 北京化工大学 | Nitrogen-containing carbon nanotube with high heat resistance and preparation method of carbon nanotube |
| EP2876710A1 (en) * | 2013-07-29 | 2015-05-27 | Huawei Technologies Co., Ltd. | Negative active material of lithium-ion secondary battery and preparation method therefor, negative plate of lithium-ion secondary battery, and lithium-ion secondary battery |
-
2015
- 2015-12-08 CN CN201510900803.7A patent/CN105460917B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101882479A (en) * | 2010-06-10 | 2010-11-10 | 北京化工大学 | Electrode material of polyaniline-based nitrogen-containing carbon nano-tube super-capacitor, and preparation method thereof |
| CN103165911A (en) * | 2013-02-01 | 2013-06-19 | 武汉理工大学 | Fuel cell cathode nonmetal catalyst with nano sandwich structure and preparation method thereof |
| EP2876710A1 (en) * | 2013-07-29 | 2015-05-27 | Huawei Technologies Co., Ltd. | Negative active material of lithium-ion secondary battery and preparation method therefor, negative plate of lithium-ion secondary battery, and lithium-ion secondary battery |
| CN103400991A (en) * | 2013-08-13 | 2013-11-20 | 天奈(镇江)材料科技有限公司 | Water-based carbon nanotube slurry and preparation method thereof |
| CN103708436A (en) * | 2013-12-17 | 2014-04-09 | 北京化工大学 | Nitrogen-containing carbon nanotube with high heat resistance and preparation method of carbon nanotube |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541996A (en) * | 2016-06-25 | 2018-01-05 | 董晓 | A kind of preparation method of modified carbon nano-tube electromagnetic shielding paper |
| CN106219515A (en) * | 2016-07-27 | 2016-12-14 | 河南师范大学 | There is the synthetic method of the empty spherical nitrogen-doped carbon material of special crosslinking |
| CN106206078A (en) * | 2016-07-27 | 2016-12-07 | 河南师范大学 | A kind of manufacture method of ultracapacitor |
| CN106206078B (en) * | 2016-07-27 | 2018-08-24 | 河南师范大学 | A kind of production method of ultracapacitor |
| CN106315552A (en) * | 2016-08-11 | 2017-01-11 | 东北师范大学 | Multilevel porous carbon material and preparation method and application thereof |
| CN106315552B (en) * | 2016-08-11 | 2018-06-26 | 东北师范大学 | A kind of classifying porous carbon material and its preparation method and application |
| CN106299282B (en) * | 2016-08-31 | 2020-04-03 | 合肥国轩高科动力能源有限公司 | Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof |
| CN106299282A (en) * | 2016-08-31 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | A kind of nitrogen-doped carbon nanometer pipe sulfur composite and preparation method |
| CN106848197A (en) * | 2017-03-22 | 2017-06-13 | 中国科学院长春应用化学研究所 | A kind of lithium ion secondary battery negative pole and preparation method thereof, lithium rechargeable battery |
| CN110858651A (en) * | 2018-08-24 | 2020-03-03 | 清华大学 | Carbon nanotube composite structure and preparation method thereof |
| CN110858651B (en) * | 2018-08-24 | 2021-04-02 | 清华大学 | Carbon nanotube composite structure and preparation method thereof |
| CN109713307A (en) * | 2018-12-05 | 2019-05-03 | 盐城工学院 | A kind of preparation method and application of double miscellaneous porous carbon nano rod negative electrode materials of element doping |
| CN110240140A (en) * | 2019-06-13 | 2019-09-17 | 苏州科技大学 | Nitrogen-doped porous carbon material and its preparation method and application |
| CN110586115A (en) * | 2019-09-29 | 2019-12-20 | 内蒙古骏成新能源科技有限公司 | High-rate carbon nanotube catalyst, carbon nanotube and preparation method thereof |
| CN110586115B (en) * | 2019-09-29 | 2022-08-12 | 成都科汇机电技术有限公司 | High-rate carbon nanotube catalyst, carbon nanotube and preparation method thereof |
| CN111799451A (en) * | 2020-05-27 | 2020-10-20 | 广西华政新能源科技有限公司 | High-rate lithium battery negative plate and lithium battery |
| CN111799451B (en) * | 2020-05-27 | 2021-05-18 | 广西华政新能源科技有限公司 | High-rate lithium battery negative plate and lithium battery |
| CN112786900A (en) * | 2021-02-03 | 2021-05-11 | 江西理工大学 | Zinc-air cell with embedded Fe2Nitrogen-rich phosphorus carbon spheres of P nanocrystalline and preparation method thereof |
| CN114477176A (en) * | 2022-01-25 | 2022-05-13 | 南京智汇环境气象产业研究院有限公司 | Apple-derived activated carbon material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105460917B (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105460917B (en) | A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy | |
| US10770720B2 (en) | Composite negative electrode material and method for preparing composite negative electrode material, negative electrode plate of lithium ion secondary battery, and lithium ion secondary battery | |
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN103367719B (en) | The preparation method of Yolk-shell structure tin dioxide-nitrogen-dopcarbon carbon material | |
| CN107946576B (en) | High-rate graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN109326784B (en) | Phosphorus doped MoS2Preparation method and application of loaded graphene nanosheet | |
| CN106450265B (en) | A kind of situ Nitrogen Doping carbon coating lithium titanate combination electrode material and preparation method thereof | |
| CN104617281A (en) | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| CN106960954A (en) | A kind of preparation method and application of Prussian blue/graphene/sulphur composite | |
| CN109244378A (en) | A kind of preparation method of porous nano Si-C composite material | |
| CN108666543B (en) | Sponge-like C-SiC composite material and preparation method thereof | |
| CN107331839A (en) | A kind of preparation method of carbon nanotube loaded nano titanium oxide | |
| CN106654192A (en) | Tin sulfide/graphene sodium ion battery composite cathode material and preparation method thereof | |
| WO2016202173A1 (en) | Method for preparing high-purity lithium titanate negative electrode material and use thereof | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN104282894B (en) | A kind of preparation method of porous Si/C complex microsphere | |
| CN103972508A (en) | Inorganic doped/coated modification natural graphite, as well as preparation method and application thereof | |
| CN105655561A (en) | Synthesis method of lithium manganese phosphate nanosheets | |
| CN107658461B (en) | Method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material | |
| CN104393275A (en) | Preparation method of carbon-coated lithium titanate battery material | |
| CN104466182A (en) | Nitrogen-doped nanocarbon coated/oxidized modified graphite composite material and preparation method thereof | |
| CN105047870A (en) | Nitrogen-doped carbon-coated silicon composite material and preparation method thereof | |
| CN104577090A (en) | Method for preparing carbon and oxide composite modified lithium titanate material | |
| CN104362318B (en) | A kind of method of the lithium ferrosilicon silicate/carbon composite cathode material preparing micropore spherical structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171229 Termination date: 20181208 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |