CN103170324B - A kind of metal-oxide/nitrogen-doped carbon nanometer pipe and its preparation method and application - Google Patents
A kind of metal-oxide/nitrogen-doped carbon nanometer pipe and its preparation method and application Download PDFInfo
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- CN103170324B CN103170324B CN201110439346.8A CN201110439346A CN103170324B CN 103170324 B CN103170324 B CN 103170324B CN 201110439346 A CN201110439346 A CN 201110439346A CN 103170324 B CN103170324 B CN 103170324B
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Abstract
The present invention discloses the preparation method of a kind of metal-oxide/nitrogen-doped carbon nanometer pipe composite, and it comprises the steps: that (1) ultrasonic disperse nitrogen-doped carbon nanometer pipe in the mixed solution of water and alcohol obtains solution A；(2) under agitation, solution B being added drop-wise in solution A, stirring obtains mixed liquor；Described solution B is the water containing metal ion and/or alcoholic solution；(3) mixed liquor is carried out solid-liquid separation, washing, it is dried, roasting, obtains metal-oxide/nitrogen-doped carbon nanometer pipe composite.Present invention also offers composite of being obtained by the method and application thereof.The present invention uses the liquid-phase synthesis process under room temperature condition, it is to avoid the hydro-thermal reaction of High Temperature High Pressure and solvent thermal reaction, it is possible to obtain metal-oxide and be combined more close composite with nitrogen-doped carbon nanometer pipe.The method preparation cost of the present invention is low, simple to operate, preparation condition is gentle, and reaction time is short.
Description
Technical field
The present invention relates to field of compound material, particularly relate to a kind of metal-oxide/nitrogen-doped carbon nanometer pipe and
Its preparation method and application.
Background technology
From CNT there is superior electronics and after mechanical performance is in the news, caused widely and
Concern interdisciplinary.In recent years, the method exploitation the most superior interesting carbon of performance utilizing chemical modification is received
Mitron derivant becomes one of study hotspot.Wherein, nitrogen-doped carbon nanometer pipe can be from theoretical and experimental aobvious
Work improves its structure, chemistry, conduction and thermodynamic property, thus is increasingly paid attention to by researcher.It
Not only there is the excellent mechanics of common CNT and Thermodynamically stable performance, and the existence of nitrogen-atoms makes
It introduces pi-electron cloud in carbon nano tube surface, thus adds the electric conductivity of nitrogen-doped carbon nanometer pipe,
And beneficially alien species absorption on nitrogen-doped carbon nanometer pipe.
Metal-oxide mostly is the quasiconductor with certain band structure, have multi-functional photoelectricity, catalysis,
Sensing, the performance such as magnetics and energy storage.Such as, α-Fe2O3Aoxidize as most stable of ferrum under room temperature
Thing, in terms of catalyst, pigment, magnetic material, photoelectric material, gas sensor and lithium ion battery
Have a wide range of applications.RuO2, MnO2, TiO2, SnO2And V2O2Deng transition metal oxide nano
Material then shows the highest capacitance behavior, can be as the electrode material of up-and-coming ultracapacitor.
Let us say that, modern science and technology and social development are played a very important role by metal-oxide, ooze
Thoroughly in each field of national economy and national defense industry.Formation is combined with metal-oxide based on CNT
New hybrid material can have the superior function of metal-oxide and CNT concurrently, become nano combined material
The hot fields of material research.
At present, reactive metal oxides or load or parcel are introduced the surface of CNT are required for head
First inert carbon tube-surface is chemically modified, it is common that carbon pipe is carried out strong acid treatment, this harshness
Treatment conditions not only increase the production cost of composite, environment is caused certain pollution, and
The characteristic of CNT self can be caused certain destruction.In order to overcome this shortcoming, surface is used to live
The nitrogen-doped carbon nanometer pipe sprinkled is a kind of more satisfactory method.This is because nitrogen-atoms not only changes carbon
Nitrogen-atoms in the pipe absorbability to alien species, and carbon cannon born frame carries to the load of metal-oxide
For more active sites.
At present, the composite of synthetic nitrogen doped carbon nanometer pipe and metal-oxide generally use infusion process or
Add the method (CN 200910311069.5) of precipitant, metal oxygen in the composite that infusion process obtains
Compound nanoparticle is more open with the combination of carbon pipe, and nanoparticle easily comes off from carbon tube-surface.And use
The method adding precipitant needs to use sodium hydroxide solution, ammonia or urea liquid, and this is in production process
In increase a lot of cost, in being prepared on a large scale, exist for difficulty, limit its commercial Application.
Therefore exploitation is prepared the new technology of metal-oxide/nitrogen-doped carbon nanometer pipe composite and is had extremely important
Meaning.
Summary of the invention
The technical problem to be solved is that overcoming existing metal-oxide/nitrogen-doped carbon receives
In mitron composite, metal-oxide is easy to fall off, and preparation method cost is high, is not suitable for high-volume raw
The defect produced, it is provided that a kind of metal-oxide/nitrogen-doped carbon nanometer pipe composite and preparation method thereof and
Application.The present invention uses the liquid-phase synthesis process under room temperature condition, it is to avoid the hydro-thermal reaction of High Temperature High Pressure
And solvent thermal reaction, it is possible to obtain metal-oxide and be combined more close composite wood with nitrogen-doped carbon nanometer pipe
Material.The method preparation cost of the present invention is low, simple to operate, preparation condition is gentle, and reaction time is short.
The invention provides the preparation method of a kind of metal-oxide/nitrogen-doped carbon nanometer pipe composite, its
Comprise the steps:
(1) in the mixed solution of water and alcohol, ultrasonic disperse nitrogen-doped carbon nanometer pipe obtains solution A；
(2) under agitation, at room temperature, solution B being added drop-wise in solution A, stirring obtains
Mixed liquor (contains the predecessor of metal-oxide/nitrogen-doped carbon nanometer pipe composite) in mixed liquor；Institute
State water and/or alcoholic solution that solution B is metal ion；
(3) described mixed liquor is carried out solid-liquid separation, washing, it is dried, roasting, obtains metal-oxide
/ nitrogen-doped carbon nanometer pipe composite.
In step (1), described nitrogen-doped carbon nanometer pipe refers to be doped with the CNT of nitrogen, the present invention
In nitrogen-doped carbon nanometer pipe except doping nitrogen in addition to, the doped chemical of other routines of also can adulterating.Described
Nitrogen-doped carbon nanometer pipe can be selected in this area multiple for preparing metal-oxide/nitrogen-doped carbon nanometer pipe
The various nitrogen-doped carbon nanometer pipes that condensation material uses, described nitrogen-doped carbon nanometer pipe is preferably many walls carbon
Nanotube, its diameter is preferably 20nm～200nm, is more preferably 20nm～60nm；Its length is relatively
It is 5 μm～40 μm goodly；Its N doping amount is preferably 5mmol/g～20mmol/g.
In step (1), the alcohol described in solution A is preferably the alcohol of carbon number 1～6, more preferably
For one or more in methanol, ethanol, isopropanol, n-butyl alcohol and n-amyl alcohol.In solution A, water with
The volume ratio of alcohol is preferably 1: 30～1: 1.
In step (1), the described ultrasonic time is so that nitrogen-doped carbon nanometer pipe is uniformly dispersed is as the criterion, relatively
It it is 0.5～6 hour goodly.Described ultrasonic frequency is preferably 20～50KHz.
In step (1), described nitrogen-doped carbon nanometer pipe concentration in solution A be preferably 1g/20mL～
1g/500mL, is more preferably 1g/40mL～1g/400mL.
In step (2), described metal ion is preferably transition metal ions, is more preferably Fe2+、
Fe3+、Ni2+、Mn4+、Mn2+、Co2+、Co3+、Ti4+、Ru4+、Cr3+、Ir4+、W6+、V5+With
Sn4+In one or more.Described metal ion is preferably with inorganic metal salt and/or metal alkyl
The form of compound is added in solution B.Described inorganic metal salt be preferably nitrate, sulfate and
One or more in chloride.Described inorganic metal salt and/or metal alkyl compound are in solution B
Concentration be preferably 0.01wt%～10wt%, be more preferably 0.5wt%～10wt%.
In step (2), the alcohol described in solution B is preferably the alcohol of carbon number 1～6, more preferably
For one or more in methanol, ethanol, isopropanol, n-butyl alcohol and n-amyl alcohol.
In step (2), solution A is preferably 1: 1～30: 1 with the volume ratio of solution B, is more preferably
1: 1～3: 1.
In step (2), the stirring carried out after dropping, its mixing time is preferably 0.5～5 hour.
In step (3), described solid-liquid separation uses the solid-liquid separating method of the various routine in this area to enter
OK, sucking filtration is typically used.
In step (3), described washing can be carried out according to this area conventional method, uses the most respectively
Water and ethanol wash.Described water is preferably deionized water.
In step (3), described dry employing this area conventional method is carried out, to remove washing of residual
Washing liquid, described dry temperature is preferably 50～120 DEG C.The described dry time is preferably
0.5～5 hour.
In step (3), described roasting uses this area routine roasting technique to carry out, and is usually in vacuum
Under the conditions of in 400～800 DEG C of roasting 0.5h～10h.
In step (3), described in obtained metal-oxide/nitrogen-doped carbon nanometer pipe composite
Metal-oxide is preferably transition metal oxide, is more preferably Fe2O3、Fe3O4、NiO、MnO2、
MnO、CoO、Co3O4、Co2O3、TiO2、RuO2、Cr2O3、IrO2、WO3、V2O5And SnO2
In one or more.
Present invention also offers the metal-oxide/nitrogen-doped carbon nanometer pipe prepared by described preparation method
Composite.
Present invention also offers described metal-oxide/nitrogen-doped carbon nanometer pipe composite as nanometer
Catalysis material, composite catalyst carrier, lithium ion battery negative material or the application of ultracapacitor.
In the present invention, described room temperature is the conventional understanding in this area to room temperature, generally 20-40 DEG C.
In the present invention, above-mentioned optimum condition on the basis of meeting common sense in the field can combination in any, to obtain final product
The each preferred embodiment of the present invention.
The raw material of the present invention and reagent are the most commercially.
The most progressive effect of the present invention is:
1, the preparation method of the metal-oxide of the present invention/nitrogen-doped carbon nanometer pipe composite is in gentleness
Under conditions of, complete in same liquid phase, thus have simple economy, energy consumption low, easy to operate,
It is easy to the advantage separating and facilitating implementation large-scale production.
2, metal-oxide growth in situ in the solution is to nitrogen-doped carbon nanometer pipe surface, it is not necessary to used
Nitrogen-doped carbon nanometer pipe be purified net income, thus avoid need common CNT to carry out loaded down with trivial details
Harsh pre-treatment step.
3, the preparation method of the metal-oxide of the present invention/nitrogen-doped carbon nanometer pipe composite avoids height
The hydro-thermal reaction of temperature high pressure and solvent thermal reaction.
4, the metal-oxide of the present invention/nitrogen-doped carbon nanometer pipe composite is due to the carbon nanometer of N doping
Pipe has more defective bit and more electron rich than common CNT, thus is compared to gold
Belong to oxide/common carbon nano tube compound material, more preferable electric transmission effect can be played, thus have more
Excellent photocatalysis performance and chemical property.
Accompanying drawing explanation
Fig. 1 is the SnO in embodiment 12The X ray diffracting spectrum of/nitrogen-doped carbon nanometer pipe composite
And energy dispersion X-ray collection of illustrative plates (XPS) (XRD), (A) is XRD figure, and (B) is XPS figure.
Fig. 2 is nitrogen-doped carbon nanometer pipe and TiO2The transmission electron microscope picture of/nitrogen-doped carbon nanometer pipe composite
Photo (TEM), (a) is the TEM figure of nitrogen-doped carbon nanometer pipe, and (b) is the TiO of embodiment 22/
The TEM figure of nitrogen-doped carbon nanometer pipe composite.
Fig. 3 is nitrogen-doped carbon nanometer pipe and WO3The scanning electron microscope (SEM) photograph of/nitrogen-doped carbon nanometer pipe composite
(SEM), (a) is the SEM figure of nitrogen-doped carbon nanometer pipe, and (b) is the WO of embodiment 33/ nitrogen is mixed
The SEM figure of miscellaneous carbon nano tube compound material.
Fig. 4 is the TiO in embodiment 12/ nitrogen-doped carbon nanometer pipe composite is as photocatalyst ultraviolet
The efficiency curve of light degradation rhodamine B is (with the TiO of preparation under the same terms2And TiO2/ CNT
Composite compares).
Detailed description of the invention
By embodiment, the invention will be further described below, but the present invention is not limited to this.
The nitrogen-doped carbon nanometer pipe used in following embodiment is made according to CN 200710041299.5
Standby.
Embodiment 1 SnO2/ nitrogen-doped carbon nanometer pipe composite
(1) by 0.5g nitrogen-doped carbon nanometer pipe (a diameter of 30-50nm of nitrogen-doped carbon nanometer pipe, a length of
5-15 μm, N doping amount is 5.0mmol/g) in the middle of the mixed solution of 10mL water and 10mL ethanol
Under 20KHz, ultrasonic disperse 30 minutes, obtain solution A；
(2) by 1g SnCl2·2H2O solid is dissolved in 18mL dehydrated alcohol and obtains solution B (SnCl2
Concentration be 5.58wt%)；Under agitation, at room temperature solution B is instilled in solution A, stir
Mix 2 hours, obtain mixed liquor；
(3) mixed liquor is carried out sucking filtration, and according to this by deionized water, washing with alcohol, at 80 DEG C after filtration
Being dried 5 hours in dry case, at 800 DEG C, vacuum baking 0.5 hour, obtains SnO2/ nitrogen-doped carbon nanometer
Pipe composite
SnO2The sign of/nitrogen-doped carbon nanometer pipe composite:
SnO is analyzed with powder x-ray diffraction (XRD) (Bruker D8, Cu-K α)2/ N doping
The crystal structure of carbon nano tube compound material, shown in result such as Fig. 1 (A).Wherein a is nitrogen-doped carbon
The XRD figure of nanotube, b is SnO2The XRD figure of/nitrogen-doped carbon nanometer pipe composite.From figure
It can be seen that relative to 002 and 100 peaks of nitrogen-doped carbon nanometer pipe, SnO2/ nitrogen-doped carbon nanometer pipe
Composite has shown that obvious SnO2Crystal peak, is consistent with JCPDS No.41-1445 standard spectrogram,
And 002 peak of nitrogen-doped carbon nanometer pipe and SnO2110 peaks there occurs crossover.
SnO is analyzed with energy dispersion type x-ray spectrometer (EDX) (Phoenix)2/ nitrogen-doped carbon is received
Mitron composite, shown in result such as Fig. 1 (B), its prove composite has had Sn element,
C element and O element, Cu element comes from the copper mesh of substrate.
Embodiment 2 TiO2/ nitrogen-doped carbon nanometer pipe composite
(1) by 1g nitrogen-doped carbon nanometer pipe (a diameter of 40-60nm of nitrogen-doped carbon nanometer pipe,
A length of 10-25 μm, N doping amount is 7.2mmol/g) in 8mL water and the mixing of 240mL isopropanol
Central ultrasonic disperse 1 hour under 50KHz of solution, obtains solution A；
(2) 6.82mL tetra isopropyl titanate (TPOT) is dissolved in the middle of 80mL isopropanol and obtains
To solution B (concentration of TPOT is 9.79wt%)；Under agitation, at room temperature, by solution B
Instill in solution A, stir 3 hours, obtain mixed liquor；
(3) mixed liquor is carried out sucking filtration, and use deionized water, washing with alcohol according to this, after filtration,
50 DEG C are dried 0.5 hour, and at 400 DEG C, vacuum baking 10 hours, obtain TiO2/ nitrogen-doped carbon nanometer
Pipe composite.
TiO is analyzed with transmission electron microscope (TEM) (JEOL-JEM-1005)2/ nitrogen-doped carbon nanometer pipe composite wood
The structure of material.Can be seen that, the scattered TiO of last layer is covered on the surface of nitrogen-doped carbon nanometer pipe thickly2Brilliant
Body, TiO2And combine closely between nitrogen-doped carbon nanometer pipe.
Embodiment 3 WO3/ nitrogen-doped carbon nanometer pipe composite
(1) by 0.5g nitrogen-doped carbon nanometer pipe (a diameter of 20-50nm of nitrogen-doped carbon nanometer pipe, length
For 15-40 μm, N doping amount is 20mmol/g) molten in the mixing of 20mL water and 180mL n-butyl alcohol
Central ultrasonic disperse 6 hours under 40KHz of liquid, obtain solution A；
(2) by 1.62g sodium tungstate (Na2WO4·2H2O) solid is dissolved in the middle of 200mL water and obtains
Solution B (Na2WO4Concentration be 0.76wt%)；Under agitation, at room temperature, by solution B
Instill in solution A, stir 3 hours, obtain mixed liquor；
(3) mixed liquor is carried out sucking filtration, and according to this by deionized water, washing with alcohol, at 120 DEG C after filtration
Being dried 3 hours in drying baker, at 600 DEG C, vacuum baking 5 hours, obtain TiO2/ nitrogen-doped carbon nanometer
Pipe composite.
WO is analyzed with scanning electron microscope (SEM) (Hitachi 4800)3/ nitrogen-doped carbon nanometer pipe composite
Structure.Can be seen that the surface of nitrogen-doped carbon nanometer pipe thick cover the scattered WO of last layer3Crystal.
Effect example 1 TiO2/ nitrogen-doped carbon nanometer pipe composite (TiO2/ CNx) in photocatalysis
Application
The degraded of dyestuff is carried out on XPA-7 type photochemical reaction instrument (Xujiang Electromechanical Plant, Nanjing, China) device,
Using rhodamine B (RhB) as substrate, under ultraviolet light irradiates, evaluate the activity of photocatalyst.Luo Dan
The initial concentration of bright B aqueous solution is 10mg/L, in the quartz test tube of the 50mL outside Photoreactor chuck
Add the rhodamine B aqueous solution of 30mL 10mg/L, under magnetic agitation, be added thereto to 20mg embodiment 2
In TiO2/ nitrogen-doped carbon nanometer pipe composite (as photocatalyst), is placed in the suspension obtained
More than dark place magnetic agitation about half an hour, balance at the adsorption/desorption of catalyst surface reaching rhodamine B.
Then suspension is placed under the ultraviolet light irradiation of 300w.A quartz ampoule is taken out according to the regular hour,
Suspension is placed in centrifuge tube and separates (Town in Shanghai booth scientific instrument, TGL-16G type with centrifuge
Whizzer, 10000rpm, 10min) the clarification centrifugal liquid that obtains, at Shimadzu UV-2550
Uv-visible absorption spectra (the sweep limits of clear liquid is recorded on ultraviolet-uisible spectrophotometer
200-800nm).As can be seen from Fig. 4, relative to simple TiO2And TiO2/ carbon nano tube compound material
(TiO2/ CNTs), the TiO that the present invention prepares2/ nitrogen-doped carbon nanometer pipe the composite fall to rhodamine B
Solution ability is optimal.
Effect example 2
SnO2The application in the lithium ion battery of/nitrogen-doped carbon nanometer pipe composite
SnO2The Electrochemical Characterization of/nitrogen-doped carbon nanometer pipe composite: its electrochemical Characterization uses
Button cell CR2430 type, with lithium sheet for electrode, using barrier film is Celgard 2300PP/PE/PP
Three layers of microporous compound film, with 1M LiPF6/EC+DMC+EMC solution as supporting electrolyte.Will be real
Execute the SnO in example2/ nitrogen-doped carbon nanometer pipe composite, binding agent, conductive agent with 8: 1: 1 ratio
Example fits in slurry, is then applied on copper-foil conducting electricity, 120 DEG C of dry 2h, uses roller press, at 10MPa
Pressure under roll forming.After positive, negative electrode plate and barrier film are stacked assembling, punching press is sealed.All dresses
Join process all to carry out in the dry glove box of full argon.
The lithium ion battery of above-mentioned structure allows to be incubated at room temperature overnight.Utilize Arbin punching/discharge test
Instrument test battery charging and discharging performance.The discharge and recharge interval of test is 0.005-2V, with the electricity of 100mA/g
Stream is at room temperature tested.
The charge/discharge capacity of test lithium ion battery and starting efficiency, and repeat above-mentioned discharge and recharge operation, enter
The circulation of the row discharge and recharge of 20 weeks, test result is shown in Table 1, and electrical property is labeled as SnO2/CNT。
Simple SnO is evaluated by identical electrical performance evaluation step2The electrical property of granule, as and SnO2/
The comparison data of nitrogen-doped carbon nanometer pipe composite is shown in Table 1, and electrical property is labeled as SnO2。
Table 1
| SnO2/CNT | SnO2 | |
| Initial discharge capacity mAh/g | 660.8 | 950.2 |
| 20 weeks discharge capacities mAh/g | 620.4 | 480.8 |
| Efficiency % first | 74.3 | 62.5 |
Claims (19)
1. a preparation method for metal-oxide/nitrogen-doped carbon nanometer pipe composite, it includes following
Step:
(1) in the mixed solution of water and alcohol, ultrasonic disperse nitrogen-doped carbon nanometer pipe obtains solution A；Solution
In A, water is 1:30～1:1 with the volume ratio of alcohol；
(2) under agitation, at room temperature, solution B being added drop-wise in solution A, stirring obtains
Mixed liquor；Described solution B is the water containing metal ion and/or alcoholic solution；
(3) described mixed liquor is carried out solid-liquid separation, washing, it is dried, roasting, obtains metal-oxide
/ nitrogen-doped carbon nanometer pipe composite.
2. preparation method as claimed in claim 1, it is characterised in that: in step (1), described
Nitrogen-doped carbon nanometer pipe is multi-walled carbon nano-tubes；Described nitrogen-doped carbon nanometer pipe concentration in solution A is
1g/20mL～1g/500mL.
3. preparation method as claimed in claim 2, it is characterised in that: described multi-walled carbon nano-tubes
A diameter of 20nm～200nm, a length of 5 μm～40 μm, N doping amount is 5mmol/g～20mmol/g；
Described nitrogen-doped carbon nanometer pipe concentration in solution A is 1g/40mL～1g/400mL.
4. preparation method as claimed in claim 3, it is characterised in that: described multi-walled carbon nano-tubes
A diameter of 20nm～60nm.
5. the preparation method as described in any one of Claims 1 to 4, it is characterised in that: solution A and molten
Alcohol described in liquid B is separately the alcohol of carbon number 1～6.
6. preparation method as claimed in claim 5, it is characterised in that: institute in solution A and solution B
The alcohol stated is one or more in methanol, ethanol, isopropanol, n-butyl alcohol and n-amyl alcohol.
7. the preparation method as described in any one of Claims 1 to 4, it is characterised in that: step (1)
In, the described ultrasonic time is 0.5～6 hour；Described ultrasonic frequency is 20～50KHz.
8. the preparation method as described in any one of Claims 1 to 4, it is characterised in that: described metal
Ion is transition metal ions.
9. preparation method as claimed in claim 8, it is characterised in that: described metal ion is Fe2+、
Fe3+、Ni2+、Mn4+、Mn2+、Co2+、Co3+、Ti4+、Ru4+、Cr3+、Ir4+、W6+、V5+With
Sn4+In one or more.
10. preparation method as claimed in claim 8, it is characterised in that: described metal ion is with nothing
The form of machine slaine and/or metal alkyl compound is added in solution B；Described inorganic metal salt and/
Or the concentration that metal alkyl compound is in solution B is 0.01wt%～10wt%.
11. preparation methoies as claimed in claim 10, it is characterised in that: described inorganic metal salt
For one or more in nitrate, sulfate and chloride.
12. preparation methoies as claimed in claim 10, it is characterised in that: described inorganic metal salt and/
Or the concentration that metal alkyl compound is in solution B is 0.5wt%～10wt%.
13. preparation methoies as described in any one of Claims 1 to 4, it is characterised in that: solution A with
The volume ratio of solution B is 1:1～30:1.
14. preparation methoies as claimed in claim 13, it is characterised in that: solution A and solution B
Volume ratio is 1:1～3:1.
15. preparation methoies as described in any one of Claims 1 to 4, it is characterised in that: step (2)
In, the stirring carried out after dropping, its mixing time is 0.5～5 hour.
16. preparation methoies as described in any one of Claims 1 to 4, it is characterised in that: step (3)
In, described washing is washed with water and ethanol respectively.
17. preparation methoies as described in any one of Claims 1 to 4, it is characterised in that: step (3)
In, described dry temperature is 50～120 DEG C, and the described dry time is 0.5～5 hour；And/or,
Described roasting is under vacuum in 400～800 DEG C of roasting 0.5h～10h.
18. metal-oxide/the nitrogen prepared by the preparation method according to any one of claim 1～17 are mixed
Miscellaneous carbon nano tube compound material.
Metal-oxide described in 19. claim 18/nitrogen-doped carbon nanometer pipe composite is as nanometer
Catalysis material, composite catalyst carrier, lithium ion battery negative material or the application of ultracapacitor.
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