CN105460917B - A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy - Google Patents
A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of nitrogen-doped carbon nanometer pipe with hierarchy and preparation method thereof.This is material doped nitrogen, has obvious hierarchy, described CNT is made up of more small nitrogen-doped carbon particle.Prepare：Stirring makes aniline be dispersed in acid solution, obtains aniline suspension, then ice bath 20~60 minutes, are kept stirring for during ice bath；Oxidant is dissolved in deionized water, stirring makes its dissolving, ice bath 5~30 minutes；Stirring is closed, oxidizing agent solution poured into rapidly in aniline suspension mixed liquor, ice bath 8~28 hours, distinguishes centrifuge washing with deionized water and ethanol until supernatant clarification, is put into baking oven and dries；The sample of drying is ground, is then heat-treated in atmosphere, natural cooling；Compound after aforementioned processing is subjected to high-temperature calcination, natural cooling under an inert atmosphere.It has the advantages of high power capacity, good rate capability, good cycle, can make lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen-doped carbon nanometer pipe and preparation method thereof.
Background technology
Graphite (including native graphite, electrographite) is used as conventional commercial lithium ion battery negative material, because it is theoretical
Capacity is low (372mAh/g), the reasons such as cycle life is relatively low, high rate performance is poor, significantly limit it in negative electrode of lithium ion battery
The application of Material Field.In order to further meet high-power, high power capacity energy storage device (such as portable electric appts, storage base station
With electric automobile etc.) demand, domestic and international researcher be directed to researching and developing always capacity height, good cycling stability,
Economic cheap lithium ion battery negative material.Not only there is nitrogen-doped carbon the lithium ion storage higher than conventional commercial graphite to hold
Amount, while it also has higher electrical conductivity, it is considered to be a kind of lithium ion battery negative material of great potential.However, carry
For it is a kind of can prepare on a large scale, cost is cheap, the nitrogen-doped carbon of good cycling stability is still a huge challenge.
In recent years, the nitrogen-doped carbon that domestic and international researcher is obtained by serial of methods have good high rate performance and
Higher specific capacity, for example, Li et al. (Li X, et al.Journal of Power Sources, 2012,197:238-
245.) grow to obtain nitrogen-doped nanometer pipe by chemical vapour deposition technique, there is excellent cycle performance, its specific capacity is twice
Undoped with CNT；Wang et al. (Wang Z, et al..Electrochimica Acta, 2013,106:320-326.)
Network structure polypyrrole nanofibers are made by template, logical calcining stripping obtains network structure nitrogen-doped carbon nano-fiber,
With excellent lithium storage content；Li et al. (Li Z, et al..Energy＆Environmental Science, 2013,6 (3):
871-878.) peeled off from protein derivatives and obtain mesoporous nitrogen-doped carbon material, nitrogen content is up to more than 10%, in lithium ion
Ultra-high capacity is respectively provided with battery and capacitor application；Xiang et al. (Xiang X, et al.Materials Research
Bulletin,2011,46(8):1266-1271.) pass through potassium carbonate (KC2O3) the prepared polyaniline nano ball of processing, then it is auxiliary
With high-temperature calcination, the higher nitrogen doped micropore Nano carbon balls of specific capacity are obtained.Although at present on nitrogen-doped carbon lithium ion battery
Negative material has been achieved with necessarily being in progress, but nitrogen-doped carbon material or complex process, cost described in these archives patents
It is higher, or cycle life is very short, it is difficult to meet the application demand of lithium ion battery negative material.
The content of the invention
The 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.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of nitrogen-doped carbon nanometer pipe is provided, this is material doped nitrogen, has obvious hierarchy, wherein described carbon
Nanotube is made up of more small nitrogen-doped carbon particle.
By such scheme, 50~200 nanometers of the diameter of CNT, a diameter of 10~50 nanometers of nitrogen-doped carbon particulate.
A kind of preparation method of nitrogen-doped carbon nanometer pipe is provided, comprised the following steps：
1) stirring makes aniline be dispersed in acid solution, obtains aniline suspension, then ice bath 20~60 minutes, ice bath
During be kept stirring for；
2) oxidant is dissolved in deionized water, stirring makes its dissolving, ice bath 5~30 minutes；
3) stirring in step 1) is closed, the oxidizing agent solution in step 2) is then poured into rapidly to the aniline of step 1)
In suspension mixed liquor, ice bath 8~28 hours, centrifuge washing is distinguished with deionized water and ethanol until supernatant clarification, is put into
Dried in baking oven；
4) sample by drying obtained by step 3) is ground, and is then heat-treated, natural cooling, obtained in atmosphere
Compound after preliminary carbonization；
5) compound after step 4) processing is subjected to high-temperature calcination under an inert atmosphere, natural cooling, obtains N doping
Carbon nano-tube material.
By such scheme, the acid described in step 1) is organic acid (oxalic acid, citric acid, phytic acid, DBSA, apple
Tartaric acid, salicylic acid and benzoic acid) and inorganic acid (hydrochloric acid, phosphoric acid, nitric acid, perchloric acid and sulfuric acid) in one kind.
By such scheme, the oxidant used in step 2) is ammonium persulfate, iron chloride, manganese dioxide, ethanedioic acid, peroxidating
Any one in hydrogen, potassium bichromate, potassium permanganate.
By such scheme, the concentration of oxidizing agent solution is 0.0625~1.25mol/L in step 2).
By such scheme, the amount ratio of the material of the aniline and acid is 8.0~15.5mmol：0.1~1.5mmol.
By such scheme, the amount ratio of the material of the aniline and oxidant is 8.0~15.5mmol：5.0~25.0mmol.
By such scheme, the milling time described in step 4) is 10~30 minutes；
By such scheme, the heat treatment described in step 4) refers to rise with 1~15 DEG C/min heating rates under air atmosphere
To target temperature, 150~280 DEG C are incubated 0.5~5 hour；
By such scheme, the high-temperature calcination described in step 5) refers in a nitrogen atmosphere, heat up with 1~15 DEG C/min fast
Rate, 5~15 hours are incubated after being raised to 500~850 DEG C of target temperature.
The advantage of the invention is that：
The present invention provide with hierarchy nitrogen-doped nanometer pipe as ion cathode material lithium take full advantage of technology into
It is ripe and industrialized carbon does main charge and discharge electric material, during can fully alleviating because of Lithium-ion embeding and abjection should
Power changes, and ensures beneficial cyclical stability；With good electric conductivity；In addition, by adulterating nitrogen, there is storage lithium using nitrogen
The function of ion, the drawbacks of carbon theoretical capacity is low is overcome, there is the advantages of high power capacity, good rate capability, good cycle.
Preparation method technique of the present invention is simple, easily operated, raw material sources extensively, inexpensive, can realize it is extensive
Production, is the effective ways for preparing the high performance lithium ion battery electrode material for being suitable for use in industrialized production.
Brief description of the drawings
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 photograph of nitrogen-doped nanometer pipe.
Embodiment
The present invention is further elaborated with reference to embodiment.Following embodiment is all merely illustrative, and is owned
Change in the present invention or equivalent the scope of the present invention is included in the invention.
Comparative example (is heat-treated) without air
1) 10.0mmol aniline is measured, 0.52mmol phytic acid is added in 50mL deionized waters, and magnetic agitation is mixed for 30 minutes
It is placed in after conjunction in ice bath 30 minutes；
2) weigh 17.3mmol ammonium persulfates to add in 50mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 12 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries.
4) step 3) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 10 hours are incubated at 500 DEG C, treats tube furnace natural cooling, obtained black powder is a kind of nitrogen-doped carbon nanometer
Tube material, resulting materials performance is as shown in Table 1.
Embodiment 1
1) 10.0mmol aniline is measured, 0.52mmol phytic acid is added in 50mL deionized waters, and magnetic agitation is mixed for 30 minutes
It is placed in after conjunction in ice bath 30 minutes, is kept stirring for during ice bath；
2) weigh 17.3mmol ammonium persulfates to add in 50mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 12 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 5 DEG C/min's
Heating rate, 2 hours are incubated at 200 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 10 hours are incubated at 500 DEG C, treats tube furnace natural cooling, obtained black powder is nitrogen-doped carbon nanometer pipe material
Material.
With 7：2：1 mass ratio weighs nitrogen-doped carbon nanometer pipe material respectively：Acetylene black：Polytetrafluoroethylene (PTFE), add specific
The 1-METHYLPYRROLIDONE of volume is ultrasonically treated 1~2 hour, is coated uniformly on copper foil and electrode is made, use metal lithium sheet for
Positive pole, electrolyte are 1mol/L LiPF6/EC-DMC (volume ratios 1:1), polypropylene micropore diaphragm is barrier film
(Celgard2300) it is assembled into half-cell.
Fig. 1 is that nitrogen-doped carbon nanometer pipe material of the present invention does the simulated battery assembled during lithium cell negative pole and is in current density
Cycle performance figure during 4000mA/g, it can be found that the material has extraordinary cycle performance；Fig. 2 is high rate performance figure, can
Even if to find to undergo high current density discharge and recharge, when returning to low current density, its charge specific capacity can recover substantially.Figure
3 be the SEM figures of the product, it can be found that carbon nano tube structure, 50~150 nanometers of the diameter of pipe, and carbon receive expects pipe and has allusion quotation
The hierarchy of type, i.e. CNT are further made up of a diameter of 10~20 nanometers of nitrogen-doped carbon particulate.
Embodiment 2
1) 10.0mmol aniline is measured, 0.21mmol phytic acid is added in 50mL deionized waters, and magnetic agitation is mixed for 30 minutes
It is placed in after conjunction in ice bath 20 minutes, is kept stirring for during ice bath；
2) weigh 17.3mmol ammonium persulfates to add in 50mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 24 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 5 DEG C/min's
Heating rate, 5 hours are incubated at 150 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 15 DEG C/min heating
Speed, 15 hours are incubated at 500 DEG C, treats tube furnace natural cooling, the obtained black powder i.e. nitrogen with hierarchy is mixed
Miscellaneous carbon nano-tube material.80~120 nanometers of the diameter of its middle pipe, it is made up of a diameter of 10~20 nanometers of nitrogen-doped carbon particulate.
Embodiment 3
1) 10.0mmol aniline is measured, 0.89mmol sulfuric acid is added in 50mL deionized waters, and magnetic agitation is mixed for 10 minutes
It is placed in after conjunction in ice bath 60 minutes, is kept stirring for during ice bath；
2) weigh 5mmol iron chloride to add in 20mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 24 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 1 DEG C/min's
Heating rate, 5 hours are incubated at 200 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 10 hours are incubated at 700 DEG C, treats tube furnace natural cooling, the obtained black powder i.e. nitrogen with hierarchy is mixed
Miscellaneous carbon nano-tube material.100~150 nanometers of the diameter of its middle pipe, it is made up of a diameter of 40~50 nanometers of nitrogen-doped carbon particulate.
Embodiment 4
1) 15.3mmol aniline is measured, 1.0mmol oxalic acid is added in 50mL deionized waters, and magnetic agitation mixes for 30 minutes
After be placed in ice bath 45 minutes, be kept stirring for during ice bath；
2) weigh 5mmol iron chloride to add in 20mL deionized waters, ice bath 5 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 8 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 10 DEG C/min
Heating rate, be incubated 2 hours at 280 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 1 DEG C/min heating speed
Rate, 15 hours are incubated at 700 DEG C, treats tube furnace natural cooling, obtained black powder has the N doping of hierarchy
Carbon nano-tube material.50~80 nanometers of the diameter of its middle pipe, it is made up of a diameter of 5~20 nanometers of nitrogen-doped carbon particulate..
Embodiment 5
1) 15.3mmol aniline is measured, 1.2mmol nitric acid is added in 50mL deionized waters, and magnetic agitation mixes for 15 minutes
After be placed in ice bath 30 minutes, be kept stirring for during ice bath；
2) 25mmol manganese dioxide is weighed, is added in 80mL deionized waters, ice bath 20 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 28 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 10 DEG C/min
Heating rate, be incubated 5 hours at 280 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 5 DEG C/min heating speed
Rate, 5 hours are incubated at 600 DEG C, treats tube furnace natural cooling, obtained black powder has the nitrogen-doped carbon of hierarchy
Nano-tube material.100~180 nanometers of the diameter of its middle pipe, it is made up of a diameter of 20~40 nanometers of nitrogen-doped carbon particulate.
Embodiment 6
1) 15.3mmol aniline is measured, 1.2mmol perchloric acid is added in 50mL deionized waters, and magnetic agitation is mixed for 30 minutes
It is placed in after conjunction in ice bath 30 minutes, is kept stirring for during ice bath；
2) claim 25mmol manganese dioxide, add in 60mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 24 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 5 DEG C/min's
Heating rate, 0.5 hour is incubated at 200 DEG C, treats tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 15 hours are incubated at 700 DEG C, treats tube furnace natural cooling, the obtained black powder i.e. nitrogen with hierarchy is mixed
Miscellaneous carbon nano-tube material.80~180 nanometers of the diameter of its middle pipe, it is made up of a diameter of 15~30 nanometers of nitrogen-doped carbon particulate.
Embodiment 7
1) 15.3mmol aniline is measured, 1.5mmol perchloric acid is added in 50mL deionized waters, and magnetic agitation is mixed for 20 minutes
It is placed in after conjunction in ice bath 30 minutes, is kept stirring for during ice bath；
2) weigh 25mmol manganese dioxide to add in 50mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 12 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 5 DEG C/min's
Heating rate, 4 hours are incubated at 150 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 5 hours are incubated at 850 DEG C, treats tube furnace natural cooling, obtained black powder has the N doping of hierarchy
Carbon nano-tube material.40~120 nanometers of the diameter of its middle pipe, it is made up of a diameter of 5~20 nanometers of nitrogen-doped carbon particulate.
Embodiment 8
1) 8.2mmol aniline is measured, 0.89mmol nitric acid is added in 50mL deionized waters, and magnetic agitation mixes for 10 minutes
After be placed in ice bath 20 minutes, be kept stirring for during ice bath；
2) 8.6mmol ammonium persulfates are weighed, are added in 80mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 12 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 15 DEG C/min
Heating rate, be incubated 2 hours at 200 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 10 hours are incubated at 500 DEG C, treats tube furnace natural cooling, the obtained black powder i.e. nitrogen with hierarchy is mixed
Miscellaneous carbon nano-tube material.50~150 nanometers of the diameter of its middle pipe, it is made up of a diameter of 10~30 nanometers of nitrogen-doped carbon particulate.
Embodiment 9
1) 8.2mmol aniline is measured, 0.10mmol hydrochloric acid is added in 50mL deionized waters, and magnetic agitation mixes for 30 minutes
After be placed in ice bath 20 minutes, be kept stirring for during ice bath；
2) 8.6mmol ammonium persulfates are weighed, are added in 50mL deionized waters, ice bath 10 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 18 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 15 DEG C/min
Heating rate, be incubated 0.5 hour at 150 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 5 hours are incubated at 850 DEG C, treats tube furnace natural cooling, obtained black powder has the N doping of hierarchy
Carbon nano-tube material.100~150 nanometers of the diameter of its middle pipe, it is made up of a diameter of 25~40 nanometers of nitrogen-doped carbon particulate.
Embodiment 10
1) 8.2mmol aniline is measured, 0.56mmol phytic acid is added in 50mL deionized waters, and magnetic agitation mixes for 30 minutes
After be placed in ice bath 30 minutes, be kept stirring for during ice bath；
2) weigh 12.5mmol ammonium persulfates to add in 50mL deionized waters, ice bath 30 minutes；
3) magnetic agitation in step 1) is closed, then step 2) solution is poured into rapidly in step 1) mixed liquor, put
Ice bath 28 hours under step 1) equal conditions, after washing 3 times respectively with deionized water and ethanol, it is put into baking oven and dries；
4) sample by drying obtained by step 3) is ground, then in the tube furnace full of air, with 10 DEG C/min
Heating rate, be incubated 5 hours at 150 DEG C, treat tube furnace natural cooling, take out products obtained therefrom；
5) step 4) products obtained therefrom is ground, then in the tube furnace full of nitrogen, with 10 DEG C/min heating
Speed, 5 hours are incubated at 850 DEG C, treats tube furnace natural cooling, obtained black powder has the N doping of hierarchy
Carbon nano-tube material.50~200 nanometers of the diameter of its middle pipe, it is made up of a diameter of 15~35 nanometers of nitrogen-doped carbon particulate.
The method of embodiment 2-10 nitrogen-doped carbon nanometer pipe reference implementation example 1 is prepared into electrode, carries out battery performance
Test, as a result see the table below 1.
Claims (7)
1. the preparation method of nitrogen-doped carbon nanometer pipe, it is characterised in that：Comprise the following steps：
（1）Stirring makes aniline be dispersed in acid solution, obtains aniline suspension, then ice bath 20~60 minutes, ice bath mistake
It is kept stirring in journey；
（2）Oxidant is dissolved in deionized water, stirring makes its dissolving, ice bath 5~30 minutes；
（3）By step（1）In stirring close, then by step（2）In oxidizing agent solution pour into step 1 rapidly）Aniline
In suspension mixed liquor, ice bath 8~28 hours, centrifuge washing is distinguished with deionized water and ethanol until supernatant clarification, is put into
Dried in baking oven；
（4）By step（3）The sample of gained drying is ground, and is then heat-treated in atmosphere, natural cooling, is obtained just
Compound after step processing, described heat treatment refer to be raised to target under air atmosphere with 1~15 DEG C/min heating rates
150~280 DEG C of temperature is incubated 0.5~5 hour；
（5）By step（4）Compound after processing carries out high-temperature calcination under an inert atmosphere, natural cooling, obtains nitrogen-doped carbon
Nano-tube material.
2. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, it is characterised in that：Step（1）Described acid
For organic acid oxalic acid, citric acid, phytic acid, DBSA, malic acid, salicylic acid and benzoic acid and inorganic acid hydrochloric acid,
One kind in phosphoric acid, nitric acid, perchloric acid and sulfuric acid；
Step（2）Oxidant used is ammonium persulfate, iron chloride, manganese dioxide, ethanedioic acid, hydrogen peroxide, potassium bichromate, height
Any one in potassium manganate.
3. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, it is characterised in that：Step（2）Middle oxidant
The concentration of solution is 0.0625~1.25mol/L.
4. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, it is characterised in that：The aniline and acid
The amount ratio of material is 8.0~15.5 mmol：0.1~1.5 mmol.
5. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, it is characterised in that：The aniline and oxidation
The amount ratio of the material of agent is 8.0~15.5 mmol：5.0~25.0 mmol.
6. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, it is characterised in that：Step（4）Described grinds
Consume time as 10~30 minutes.
7. the preparation method of nitrogen-doped carbon nanometer pipe according to claim 1, it is characterised in that：Step（5）Described height
Temperature calcining refers in a nitrogen atmosphere, with 1~15 DEG C/min heating rates, 5 are incubated after being raised to 500~850 DEG C of target temperature
~15 hours.
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