CN105788881B - A kind of preparation method of nitrogen doped corrugated carbon nanotube - Google Patents
A kind of preparation method of nitrogen doped corrugated carbon nanotube Download PDFInfo
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- H01M4/90—Selection of catalytic material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation methods of nitrogen doped corrugated carbon nanotube, and it is that using transition metal as catalyst nitrogen doped corrugated shape multi-walled carbon nanotube is prepared by nitrogen source of glycine, and applied in energy device in carbon matrix precursor to take macroreticular resin.This method raw material sources are abundant, and of low cost, preparation process is simple, and program is brief, overcome prepare in the prior art existing for carbon nanotube it is of high cost, environment friendly is poor, is unfavorable for the technical issues of large-scale production, be conducive to industrialization production.From the point of view of properties of product, N doping multi-walled carbon nanotube degree of graphitization height, good conductivity, large specific surface area prepared by the present invention have apparent ring shape, with excellent chemical property, it can be used as fuel cell, lithium ion battery and super capacitor material.Product based on the present invention prepares and properties of product advantage, will be able to have very extensive application prospect and huge commercial value.
Description
Technical field
The invention belongs to electrochemical fields, are related to a kind of preparation method of new carbon, and in particular to a kind of N doping
The preparation method of bamboo-like carbon nano tubes, the carbon nanotube can be applied to fuel cell, lithium ion battery and ultracapacitor
Field.
Background technology
Energy and environment become the theme of world development, more with the increasingly depleted of traditional fossil energy and environmental pollution
Seriously, sustainable development becomes the common hope and the objective of the struggle of the mankind.
Therefore, it taps a new source of energy to replace the technology of the nonrenewable resources such as oil imperative.In this context, fuel
Battery is received worldwide attention as a kind of energy conversion apparatus of clean and effective；Meanwhile lithium ion battery and super capacitor
Device is received extensive attention as high-efficiency energy-storage device.The electrode material of fuel cell, lithium ion battery and ultracapacitor is
Key, it decides main performance index.Carbon nanotube is due to high intensity, high tenacity, good thermal stability and conduction
The advantages that performance is considered as excellent electrode material.
Carbon material has important application in the cathode and anode of fuel cell.Although most of no-Pt catalyst all contains
Transition metal, but recent studies indicate that some metal-free carbon-based materials itself are to show that the catalysis to hydrogen reduction is lived
Property.Wherein, the carbon-based material of nitrating is concerned because it is apparent to hydrogen reduction catalytic effect, and nitrating is more especially in nano-sized carbon
It is noticeable.
Graphite has been a kind of commercialized lithium ion battery negative material.Its stablize charge-discharge performance ensure that lithium from
The cycle performance of sub- battery.But as charge storage ability requirement is gradually increased in electrical equipment, traditional graphite cannot
Meet the requirement of high power capacity, so, as the research of lithium ion battery negative material it is also a hot spot to new carbon.
The common electrode material of ultracapacitor has porous carbon material, metal oxide and conducting polymer, wherein porous
The research of Carbon Materials is the most ripe, has obtained practical application at present.New electrode materials preparation method is studied, super capacitor is improved
The power characteristic and frequency response characteristic of device, are of great significance for the application of ultracapacitor.
Invention content
In order to overcome prepare in the prior art existing for carbon nanotube it is of high cost, environment friendly is poor, it is extensive to be not easy to
The technical issues of production, the present invention provide a kind of method that low cost prepares nitrogen doped corrugated carbon nanotube.
The purpose of the invention is achieved by the following technical solution：
A kind of preparation method of nitrogen doped corrugated carbon nanotube, the preparation method comprises the following steps：
S1, selection macroreticular resin are carbon matrix precursor, are pre-processed to resin；
S2, step S1 is rinsed by pretreated macroreticular resin to neutrality, it is dry；
S3, metal salt solution is added in the macroreticular resin in step S2 by drying, in N2The item of atmosphere and stirring
Under part, 5~15h is mixed, rinsing is filtered to neutrality；Then metal salt solution is added, 5~15h is mixed, rinsing is filtered into
Property, so repeatedly 5~10 times；Finally rinsing to neutral resin is obtained being adsorbed with metal in 60~80 DEG C of dry 6~12h
The macroreticular resin of ion；
S4, macroreticular resin in step S3 is put into quartz boat, in N2Under atmosphere in tube furnace, with 2~10 DEG C/min's
Heating rate is warming up to 900~1100 DEG C, keeps the temperature 30~120min, then be down to room temperature with the rate of temperature fall of 2~10 DEG C/min, obtains
To carbon dust；
S5,30mL deionized waters will be put into certain mass ratio respectively with glycine after the grinding of carbon dust that step S4 is obtained
It is stirred after middle ultrasonic mixing, is heated to 80 DEG C until evaporating water；
S6, the obtained mixtures of step S5 are put into quartz boat, in N2Be put into tube furnace under atmosphere, with 2~10 DEG C/
The heating rate of min is warming up to 800~1000 DEG C, keeps the temperature 30~120min, then be down to room with the rate of temperature fall of 2~10 DEG C/min
Temperature obtains nitrogen doped corrugated carbon nanotube.
Further, macroreticular resin described in step S1 is macroporous ion exchange resin or macroporous absorbent resin；
The macroporous ion exchange resin includes large hole cation exchanger resin or macroporous anion exchange resin.
Further, the large hole cation exchanger resin is large hole strong acid styrene system cation exchange resin or big
Hole faintly acid polystyrene (acrylic acid series) cation exchange resin；
The large hole strong acid styrene system cation exchange resin is one kind or one in D001, D002, D61 or D62
Kind or more；
Macropore faintly acid polystyrene (acrylic acid series) cation exchange resin is one kind or one in D113 or D85
Kind or more；
The macroporous anion exchange resin is macroporous strong basic styrene series anion exchange resin or macroreticular weakly base
Polystyrene (acrylic acid series) anion exchange resin；
The macroporous strong basic styrene series anion exchange resin is the one or more in D202 or D254；
Macroreticular weakly base polystyrene (acrylic acid series) anion exchange resin is one in D301, D311 or D318
Kind or more than one；
The macroporous absorbent resin is middle polarity or polar XAD series plastics are macroporous absorbent resin, AB-8 or NKA systems
One or more in row macroporous absorbent resin.
Further, described to pre-process pretreatment, the macroporous anion exchange resin for being divided into large hole cation exchanger resin
Pretreatment and macroporous absorbent resin pretreatment；
Wherein, the preprocess method of the large hole cation exchanger resin is：Under stirring conditions, by 5~20g sun from
Sub-exchange resin using 50~1000mL acid solution pretreatment 12~for 24 hours；The acid solutions are 0.5~1M；The acid
Solution is HCl solution；200~1000rpm of rotating speed of the stirring；
The preprocess method of the macroporous anion exchange resin is：Under stirring conditions, 5~20g anion are handed over
Change resin using 50-1000mL aqueous slkali pretreatment 12~for 24 hours；The alkaline concentration is 0.5~1M；The aqueous slkali is
KOH solution or NaOH solution；The rotating speed of the stirring is 200~1000rpm；
The preprocess method of the macroporous absorbent resin is：It uses first and impregnates resin for 24 hours in 95% ethanol solution；
Then under conditions of mechanical agitation, 12h first is stirred in 5%KOH, deionized water is washed to neutrality, then in 5%HCl solution
12h is stirred, deionized water is washed to neutrality；The rotating speed of the stirring is 500rpm.
Further, rinsing described in step S2 is rinsed using deionized water；The drying condition is in 60~80
DEG C dry 6~12h.
Further, a concentration of 0.1~0.9M of metal salt solution described in step S3, the metal salt solution and macropore
The amount ratio of resin is (100-500) mL：(5~20) g.
Further, when macroreticular resin described in step S3 is large hole cation exchanger resin, the metal salt solution is
FeCl2Solution, FeCl3Solution, Ni (NO3)2Solution, NiCl2Solution, Ni (CH3COO)2Solution, CoCl2Solution or Co (NO3)2It is molten
One or more of liquid；When the macroreticular resin is macroporous anion exchange resin, the metal salt solution K3[Fe(CN)6] molten
Liquid or K4[Fe(CN)6] one or more in solution；When the macroreticular resin is macroporous absorbent resin, the metal salt
Solutions Solution is FeCl2Solution, CoCl2Solution, NiCl2One or more in solution.
Further, mixing speed described in step S3 is 400~800rpm；The rinsing is floated using deionized water
It washes.
Further, the mass ratio of carbon material and glycine described in step S5 is 1：(2~12)；The ultrasonic time is
30~60min；The mixing time be 12~for 24 hours.
Further, the nitrogen doped corrugated carbon nanotube is applied to fuel-cell catalyst carrier, lithium ion battery
Anode and cathode catalyst carrier in cathode carrier material and electrode material for super capacitor.
The present invention has the following advantages and effects with respect to the prior art：
(1) the obtained nitrogen doped corrugated carbon nanotube of the present invention is compared with common preparation carbon nanotube, the carbon taken
Presoma is macroreticular resin, using transition metal as catalyst.Raw material sources are abundant, at low cost；
(2) preparation method of the invention is simple, directly obtains a large amount of, pure nitrogen doped corrugated shape carbon nanometer, is the energy
The further exploration of material accelerates paces.
(3) the distillation deposition carbon prepared by the present invention is that a kind of degree of graphitization height, the carbon with apparent ring shape are received
Mitron；The carbon nanotube have excellent chemical property, can improve the activity of catalyst, the capacity of lithium ion battery and
Service life and high rate performance；
(4) nitrogen doped corrugated carbon nanotube obtained by the present invention is mainly used in fuel cell, and lithium ion battery surpasses
Grade capacitor etc., has preferable market prospects and development potentiality；Equipment needed for the present invention is simple simultaneously, reaction condition
It is easy, it is at low cost, it is easy to accomplish industrialized production.
Description of the drawings
Fig. 1 (a) is the low power transmission electron microscope picture of the nitrogen doped corrugated carbon nanotube prepared in the present invention；
Fig. 1 (b) is the high-resolution-ration transmission electric-lens figure of the nitrogen doped corrugated carbon nanotube prepared in the present invention；
Fig. 2 is the Raman spectrogram of the nitrogen doped corrugated carbon nanotube prepared in the present invention；
Fig. 3 (a) be nitrogen doped corrugated carbon nanotube and business Pt/C catalyst in alkalinity (solution be 0.1M KOH,
Rotating speed is 1600rmp, sweep speed 10mV/s) linear scan comparison diagram；
Fig. 3 (b) is the H of nitrogen doped corrugated carbon nanotube and business Pt/C catalyst2O2% Yield mappings；
Fig. 3 (c) is the Tafel curve graphs of nitrogen doped corrugated carbon nanotube and business Pt/C catalyst；
Fig. 3 (d) is measured according to nitrogen doped corrugated carbon nanotube catalyst under 400~2500rmp different rotating speeds
Linear scan figure recycles 1/J made by the calculating of Koutecky-Levich (K-L) formula-1With ω-1/2Curve graph；
Fig. 4 (a)-(d) is that the nitrogen doped corrugated carbon nanotube for preparing embodiment two loads MoS2 as active material
It is assembled into the lithium cell negative pole performance characterization figure measured by button cell, wherein：Fig. 4 (a) is that the cyclic voltammetric of the negative material is bent
Line chart；Fig. 4 (b) is the charging and discharging curve figure in the case where current density is 0.1A/g；It is cycle that Fig. 4 (c), which is 0.1A/g in current density,
Stablize figure；Fig. 4 (d) is the high rate performance figure of the charge and discharge under different current densities；
Fig. 5 is a kind of flow chart of the preparation method of nitrogen doped corrugated carbon nanotube disclosed by the invention.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer and more explicit, develop simultaneously embodiment pair referring to the drawings
The present invention is further described.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
It is of the invention in limiting.
Embodiment one
A kind of preparation method of nitrogen doped corrugated carbon nanotube, specifically includes following steps：
S1, selection macroreticular resin are carbon matrix precursor, are pre-processed to resin；
S2, step S1 is rinsed by pretreated macroreticular resin to neutrality, it is dry；
S3, metal salt solution is added in the macroreticular resin in step S2 by drying, in N2The item of atmosphere and stirring
Under part, 5~15h is mixed, rinsing is filtered to neutrality；Then metal salt solution is added, 5~15h is mixed, rinsing is filtered into
Property, so repeatedly 5~10 times；Finally rinsing to neutral resin is obtained being adsorbed with metal in 60~80 DEG C of dry 6~12h
The macroreticular resin of ion；
S4, macroreticular resin in step S3 is put into quartz boat, in N2Under atmosphere in tube furnace, with 2~10 DEG C/min's
Heating rate is warming up to 900~1100 DEG C, keeps the temperature 30~120min, then be down to room temperature with the rate of temperature fall of 2~10 DEG C/min, obtains
To carbon dust；
S5,30mL deionized waters will be put into certain mass ratio respectively with glycine after the grinding of carbon dust that step S4 is obtained
It is stirred after middle ultrasonic mixing, is heated to 80 DEG C until evaporating water；
S6, the obtained mixtures of step S5 are put into quartz boat, in N2Be put into tube furnace under atmosphere, with 2~10 DEG C/
The heating rate of min is warming up to 800~1000 DEG C, keeps the temperature 30~120min, then be down to room with the rate of temperature fall of 2~10 DEG C/min
Temperature obtains nitrogen doped corrugated carbon nanotube.
In concrete application, the macroreticular resin described in step S1 is macroporous ion exchange resin or macroporous absorbent resin；Institute
It includes large hole cation exchanger resin or macroporous anion exchange resin to state macroporous ion exchange resin；The macroporous cation is handed over
It is large hole strong acid styrene system cation exchange resin or macropore faintly acid polystyrene (acrylic acid series) cation to change resin
Exchanger resin.
The large hole strong acid styrene system cation exchange resin is one kind or one in D001, D002, D61 or D62
Kind or more；
Macropore faintly acid polystyrene (acrylic acid series) cation exchange resin is one kind or one in D113 or D85
Kind or more.
The macroporous anion exchange resin is macroporous strong basic styrene series anion exchange resin or macroreticular weakly base
Polystyrene (acrylic acid series) anion exchange resin.
The macroporous strong basic styrene series anion exchange resin is the one or more in D202 or D254；
Macroreticular weakly base polystyrene (acrylic acid series) anion exchange resin is one in D301, D311 or D318
Kind or more than one.
The macroporous absorbent resin is middle polarity or polar XAD series plastics are macroporous absorbent resin, AB-8 or NKA systems
One or more in row macroporous absorbent resin.
It is described pretreatment be divided into the pretreatment of large hole cation exchanger resin, the pretreatment of macroporous anion exchange resin and
Macroporous absorbent resin pre-processes；
The preprocess method of the large hole cation exchanger resin is that under stirring conditions, 5~20g cations are exchanged
Resin using 50~1000mL acid solution pretreatment 12~for 24 hours；The acid solutions are 0.5~1M；The acid solution is
HCl solution；200~1000rpm of rotating speed of the stirring；
The preprocess method of the macroporous anion exchange resin is：Under stirring conditions, 5~20g anion are handed over
Change resin using 50-1000mL aqueous slkali pretreatment 12~for 24 hours；The alkaline concentration is 0.5~1M；The aqueous slkali is
KOH solution or NaOH solution；The rotating speed of the stirring is 200~1000rpm.
The preprocess method of the macroporous absorbent resin is：It uses first and impregnates resin for 24 hours in 95% ethanol solution.
Then under conditions of mechanical agitation (rotating speed of stirring is 500rpm), 12h first is stirred in 5%KOH, deionized water is washed in
Property, then 12h is stirred in 5%HCl solution, deionized water is washed to neutrality.Above-mentioned steps are repeated 3 times.
Rinsing described in step S2 is rinsed using deionized water；The drying condition be in 60~80 DEG C dry 6~
12h。
A concentration of 0.1~0.9M of metal salt solution described in step S3, the use of the metal salt solution and macroreticular resin
Amount is than being (100-500) mL：(5~20) g；
When ion exchange resin described in step S3 is large hole cation exchanger resin, the metal salt solution is FeCl2
Solution, FeCl3Solution, Ni (NO3)2Solution, NiCl2Solution, Ni (CH3COO)2Solution, CoCl2Solution or Co (NO3)2In solution
More than one；When the ion exchange resin is macroporous anion exchange resin, the metal salt solution K3[Fe(CN)6] molten
Liquid or K4[Fe(CN)6] one or more in solution；When the macroreticular resin is macroporous absorbent resin, the metal salt
Solutions Solution is FeCl2Solution, CoCl2Solution, NiCl2One or more in solution.
Mixing speed described in step S3 is 400~800rpm；The rinsing is rinsed using deionized water.
The mass ratio of carbon material and glycine described in step S5 is 1：(2~12)；The ultrasonic time be 30~
60min；The mixing time be 12~for 24 hours.
Embodiment two
A kind of nitrogen doped corrugated carbon nanotube is prepared by following preparation method：
S1, under conditions of mechanical agitation (rotating speed of stirring be 600rpm), by 10g cation exchange resins, (macropore is weak
Acid polystyrene (acrylic acid series) cation exchange resin D113) using HCl (500mL) the pretreatments 18h of 1M；
S2, pretreated resin cation in step S1 is rinsed with deionized water, filtered to neutral, in 70 DEG C of dryings
8h；
S3, by 300mL FeCl2Solution (a concentration of 0.45M) is added in step S2 by dry cation exchange tree
In fat, in N2Under conditions of atmosphere and stirring (rotating speed of stirring is 600rpm), 8h is exchanged, is filtered into deionized water rinsing
Property；Then equal amount FeCl is added2Solution exchanges 8h, is rinsed with deionized water, filtered to neutral, is so repeated 7 times；Finally
By rinsing to neutral resin in 70 DEG C of dry 8h, exchanger resin is obtained；
S4, exchanger resin in 8g steps S3 is packed into quartzy porcelain boat, be put into tube furnace, in N2Under atmosphere, with 5 DEG C/min
Heating rate be warming up to 1100 DEG C, keep the temperature 60min, then room temperature is down to the rate of temperature fall of 5 DEG C/min, obtain carbon dust；
S5, it mixes, respectively obtains mixed with three kinds of different content glycine respectively after being ground the carbon dust in step S4
Close 1 (carbon dust of object：The mass ratio of glycine is 1：2), 2 (carbon dust of mixture：The mass ratio of glycine is 1：And 3 (carbon of mixture 4)
Powder：The mass ratio of glycine is 1：8)；4 (carbon dust of mixture：The mass ratio of glycine is 1：12)；Three kinds of mixtures are added respectively
Enter and be stirred after ultrasonic mixing into 30mL deionized waters, is heated to 80 DEG C up to evaporating water, places into tube furnace,
N2Under atmosphere, 900 DEG C are warming up to the heating rate of 5 DEG C/min, keeps the temperature 60min, then room is down to the rate of temperature fall of 5 DEG C/min
Temperature, difference nitrogen doped corrugated carbon nanotube 1, nitrogen doped corrugated carbon nanotube 2, nitrogen doped corrugated carbon nanotube 3 and nitrogen
Doped corrugated carbon nanotube 4.
For the structural characterization of prepared nitrogen doped corrugated carbon nanotube as shown in Fig. 1~2, these materials are used for fuel cell
When with lithium ion battery, the performance test results are as shown in figs. 34.
Fig. 1 is prepared 2 transmission electron microscope picture of nitrogen doped corrugated carbon nanotube.From Fig. 1 it may be clearly seen that catalysis is split
It is Bamboo-shaped that change, which obtains nanotube, and caliber is about 30nm, and section length is about 31nm；Tube wall constitutes by 10~20 layers of graphite
Fig. 2 is the Raman spectrogram of nitrogen doped corrugated carbon nanotube 2.As can be seen from Figure 2, nitrogen doped corrugated carbon nanotube
All there are one the apparent peaks D, the peaks G and the peaks 2D.And the intensity ratio at the peaks the D peaks G is more than 1, illustrates the N doping prepared by the present invention
Bamboo-like carbon nano tubes contain more defect.
Fig. 3 is the nitrogen doped corrugated carbon nanotube 2 of the invention prepared as fuel battery negative pole oxygen reduction catalyst
Polarization curve.It is found that nitrogen doped corrugated carbon nanotube of the present invention has good oxygen reduction activity from Fig. 3 (a), rise
Beginning current potential and limiting current density all reach the level close with business Pt/C catalyst.It is generated in (b) reaction process according to fig. 3
H2O2% is less than 20%, illustrates that the hydrogen reduction process is four electron reaction mechanism；Fig. 3 (c) Tafel curves find out N doping bamboo
Nodular carbon nanotube and business Pt/C catalyst Tafel slopes having the same are 83mv/dec, illustrate prepared N doping
Bamboo-like carbon nano tubes have faster kinetic reaction rate；It is calculated by K-L curves in Fig. 3 (d) nitrogen doped corrugated
The electron transfer number of shape carbon nanotube and business Pt/C catalyst, it is four electron backs to further demonstrate its catalytic reaction process all
Answer process.Nitrogen doped corrugated carbon nanotube prepared by the present invention is completely without metal, and more without noble metal, cost is relatively low.
Reach and catalytic activity as precious metal in the case of so low cost, it was demonstrated that the nitrogen doped corrugated shape carbon that the present invention obtains
Nanotube has powerful some commercial potential.
Fig. 4 will load MoS for the nitrogen doped corrugated carbon nanotube of the preparation of the present invention2It is recycled as active material lithium electricity
Volt-ampere curve, charge-discharge performance curve, cycle performance curve and high rate performance curve.From Fig. 4 (a) and Fig. 4 (b) it is found that for the first time
Charge and discharge can form SEI films, lead to the greater loss of charge/discharge capacity, but tend to stablize after second.From Fig. 4 (c)
In it is found that nitrogen doped corrugated carbon nanotube load MoS2Stabilization charge/discharge capacity in 800mAhg-1Left and right；It can from Fig. 4 (d)
Know, nitrogen doped corrugated carbon nanotube loads MoS2Good charge-discharge performance still can be kept under different current densities.From
Nitrogen doped corrugated carbon nanotube prepared by the present invention known to the performance map of the above lithium electricity can also be further used as a kind of good
Carbon material carrier, to load negative material of the different materials as lithium ion battery, and with higher charge/discharge capacity,
Excellent cyclical stability and high rate performance.
New carbon is due to it is with special nanostructure, excellent electric conductivity and good chemical property new
Energy field shows huge application potential.Nitrogen doped corrugated carbon nanotube disclosed by the invention can be urged in fuel cell
Application in agent carrier, lithium ion battery negative material and electrode material for super capacitor.
Nitrogen doped corrugated carbon nanotube prepared by the present invention is a kind of multi-walled carbon nanotube with ring shape；Carbon
Nanotube can be used for fuel-cell catalyst and lithium ion battery negative material, and activity, the lithium ion battery of catalyst can be improved
Capacity and cycle life.
Nitrogen doped corrugated carbon nanotube prepared by the present invention makes it contain more defect due to introducing nitrogen-atoms.
The defect has a great impact for fuel-cell catalyst performance, because the active sites of the oxygen reduction catalytic activity of carbon material are come
From the defect of material itself.Defect is more, is more possible to construct more active sites on the carbon nanotubes, to improve catalyst
Activity.For lithium ion battery, it is embedded and de- that the defect of negative material and larger storage lithium space also contribute to lithium ion
The reduction of the reduction of electronics transfer resistance and bulk effect during going out, to conducive to the raising of capacity and the raising in service life.
In a fuel cell, nitrogen doped corrugated carbon nanotube of the invention can be used for making anode and cathode catalyst load
Body is expected have higher since nitrogen doped corrugated carbon nanotube has certain degree of graphitization using it as the catalyst of carrier
Electrochemical environment in stability.Carbon dust introduces oxygen reduction activity position after glycine is handled, in the rejected region of carbon dust,
The nanotube of formation is just provided with oxygen reduction activity in the case of not carried noble metal, in lithium ion battery negative material,
Being loaded other materials with storage lithium performance contributes to the insertion of more lithium ions to improve the charge and discharge of lithium electricity
Capacity.Small using nitrogen doped corrugated carbon nanotube density in supercapacitor applications, the big feature of surface area improves super
The energy density of capacitor, one-dimensional carbon nanotube have more faster electron propagation ducts.
In conclusion it is carbon matrix precursor that the present invention, which takes macroreticular resin, using transition metal as catalyst, using glycine as nitrogen
Nitrogen doped corrugated shape multi-walled carbon nanotube is prepared in source, and is applied in energy device.This method raw material sources are abundant,
Of low cost, preparation process is simple, and program is brief, overcomes and prepares of high cost, environment existing for carbon nanotube in the prior art
Friendly is poor, is unfavorable for the technical issues of large-scale production, is very beneficial for industrialization production.From the point of view of properties of product, this hair
Bright prepared N doping multi-walled carbon nanotube degree of graphitization height, large specific surface area, has apparent laemodipodiform at good conductivity
Shape has excellent chemical property, is made for the further exploration of fuel cell, lithium ion battery and super capacitor material
Contribution.Prepared by the product of the present invention and properties of product advantage makes it have very extensive application and huge commercial value.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of nitrogen doped corrugated carbon nanotube, which is characterized in that the preparation method comprises the following steps：
S1, selection macroreticular resin are carbon matrix precursor, are pre-processed to resin；Wherein, the macroreticular resin is macroporous absorption tree
Fat, the macroporous absorbent resin is middle polarity or polar XAD series plastics are macroporous absorbent resin, and AB-8 or NKA series are big
One or more in macroporous adsorbent resin；
S2, step S1 is rinsed by pretreated macroreticular resin to neutrality, it is dry；
S3, metal salt solution is added in the macroreticular resin in step S2 by drying, in N2Under conditions of atmosphere and stirring,
5~15h is mixed, rinsing is filtered to neutrality；Then metal salt solution is added, 5~15h is mixed, rinsing is filtered to neutrality, so
It repeats 5~10 times；Finally rinsing to neutral resin is obtained being adsorbed with the big of metal ion in 60~80 DEG C of dry 6~12h
Hole resin；
S4, macroreticular resin in step S3 is put into quartz boat, in N2Under atmosphere in tube furnace, with the heating speed of 2~10 DEG C/min
Rate is warming up to 900~1100 DEG C, keeps the temperature 30~120min, then be down to room temperature with the rate of temperature fall of 2~10 DEG C/min, obtains carbon
Powder；
S5, it will be put into 30mL deionized waters and surpassed with certain mass ratio respectively with glycine after the grinding of step S4 is obtained carbon dust
It is stirred after sound mixing, is heated to 80 DEG C until evaporating water；
S6, the obtained mixtures of step S5 are put into quartz boat, be put into tube furnace under n 2 atmosphere, with 2~10 DEG C/min's
Heating rate is warming up to 800~1000 DEG C, keeps the temperature 30~120min, then be down to room temperature with the rate of temperature fall of 2~10 DEG C/min, obtains
To nitrogen doped corrugated carbon nanotube.
2. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
The preprocess method of the macroporous absorbent resin is：It uses first and impregnates resin for 24 hours in 95% ethanol solution；Then
Under conditions of mechanical agitation, 12h first is stirred in 5%KOH, deionized water is washed to neutrality, then is stirred in 5%HCl solution
12h, deionized water are washed to neutrality；The rotating speed of the stirring is 500rpm.
3. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
Rinsing described in step S2 is rinsed using deionized water；The drying condition is in 60~80 DEG C of dry 6~12h.
4. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
A concentration of 0.1~0.9M of metal salt solution described in step S3, the amount ratio of the metal salt solution and macroreticular resin
For (100-500) mL：(5~20) g.
5. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
When macroreticular resin described in step S3 is large hole cation exchanger resin, the metal salt solution is FeCl2Solution, FeCl3
Solution, Ni (NO3)2Solution, NiCl2Solution, Ni (CH3COO)2Solution, CoCl2Solution or Co (NO3)2One kind in solution or one
Kind or more；When the macroreticular resin is macroporous anion exchange resin, the metal salt solution K3[Fe(CN)6] solution or K4[Fe
(CN)6] one or more in solution；When the macroreticular resin is macroporous absorbent resin, the metal salt solution solution
For FeCl2Solution, CoCl2Solution, NiCl2One or more in solution.
6. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
Mixing speed described in step S3 is 400~800rpm；The rinsing is rinsed using deionized water.
7. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
The mass ratio of carbon dust and glycine described in step S5 is 1：(2~12)；The ultrasonic time is 30~60min；It is described
Mixing time be 12~for 24 hours.
8. a kind of preparation method of nitrogen doped corrugated carbon nanotube according to claim 1, which is characterized in that
The nitrogen doped corrugated carbon nanotube be applied to fuel-cell catalyst carrier, negative electrode of lithium ion battery carrier material and
Anode and cathode catalyst carrier in electrode material for super capacitor.
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