CN110510599B - Thin-wall amorphous carbon nanotube and preparation method and application thereof - Google Patents
Thin-wall amorphous carbon nanotube and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a thin-wall amorphous carbon nanotube and a preparation method and application thereof, belonging to the technical field of functional materials. The invention uses sulfonated polymer nano-tube-SiO 2 The composite material is calcined, the polymer nano tube shrinks in the calcining process, and SiO embedded into the tube wall of the polymer nano tube 2 The particles are formed and can generate physical extrusion effect on the polymer nano tube to obtain the carbon nano tube-SiO 2 The composite material is etched by hydrofluoric acid to remove SiO 2 Finally, the thin-wall amorphous carbon nano tube is prepared. The preparation method provided by the invention is simple to operate, a special device and an expensive reagent are not needed, and the prepared thin-wall amorphous carbon nanotube shows excellent electrochemical performance when being used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a thin-wall amorphous carbon nanotube and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, low price, no memory effect, environmental friendliness and the like, and is widely applied to the fields of portable electronic equipment, electric vehicles, aerospace and the like. The negative electrode material is important to the specific capacity and the cycle life of the lithium ion battery. However, the commercial graphite material as the negative electrode material of the lithium ion battery has the problems of poor safety, low specific capacity, unobvious rate performance and the like, and can not meet the requirements of people on the high-performance lithium ion battery.
The amorphous carbon has disordered structure, large number of defects and large interlayer space, and is beneficial to Li + The lithium battery has the advantages of high natural abundance, simple preparation process, stable structure and the like, and is considered to be one of negative electrode materials with development prospects in recent years. However, the disordered structure of amorphous carbon results in poor electrical conductivity, which is disadvantageous for its application in high power output. The one-dimensional tubular structure can provide a directional electron and ion transport path, and can improve the transmission efficiency of electrons and ions, so that extensive research is carried out in the fields of electric power and electronics. The amorphous carbon nanotube has not only the advantage of one-dimensional structure, but also a great number of defects because the amorphous carbon nanotube has a unique structure formed by discontinuous graphene sheets and carbon clustersTrap sites, with good lithium storage capacity. It is known that the thinner the wall of the carbon nanotube, the better the conductivity and the better the electrolyte penetration. Therefore, the thin-wall amorphous carbon nano tube has wide application prospect as the lithium ion battery cathode material.
At present, a template method is generally adopted to synthesize the thin-wall amorphous carbon nano tube, specifically, silicon dioxide and aluminum oxide are used as templates, carbon sources are uniformly wrapped on the templates in a thickness-controlled manner by CVD, hydrothermal method and other methods, and then the templates are removed. The method has complex operation, needs special equipment and has high reagent cost, and the specific capacity and the cycling stability of the prepared thin-wall amorphous carbon nano tube are still to be improved.
Disclosure of Invention
The preparation method provided by the invention is simple to operate, no special device or expensive reagent is needed, and the prepared thin-wall amorphous carbon nanotube shows excellent electrochemical performance when being used as a lithium ion battery cathode material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a thin-wall amorphous carbon nano tube, which comprises the following steps:
providing sulfonated polymer nanotubes-SiO 2 Composite material, sulfonated polymer nanotube-SiO 2 SiO in composite materials 2 Embedded in the walls of the sulfonated polymer nanotubes;
the sulfonated polymer nano-tube-SiO 2 Calcining the composite material to obtain the carbon nano tube-SiO 2 A composite material;
the carbon nano tube-SiO is treated by hydrofluoric acid 2 And etching the composite material to obtain the thin-wall amorphous carbon nano tube.
Preferably, the sulfonated polymer nanotube-SiO 2 The preparation method of the composite material comprises the following steps:
mixing the sulfonated polymer nanotube, tetraethoxysilane and ethanol to obtain an tetraethoxysilane-sulfonated polymer nanotube composite material;
mixing the tetraethoxysilane-sulfonated polymer nanotube composite material with ethanol, ammonia water and water, and carrying out hydrolysis reaction to obtain wet gel;
drying the wet gel to obtain the sulfonated polymer nanotube-SiO 2 A composite material.
Preferably, the sulfonated polymer nanotubes, tetraethoxysilane and water are used in a ratio of 200 mg: (8-12) mL: (4-6) mL;
the temperature of the hydrolysis reaction is 15-60 ℃, and the time is 4.5-5.5 h.
Preferably, the calcining temperature is 850-950 ℃, and the heat preservation time is 2.5-3.5 h; the heating rate of heating to the temperature required by calcination is 4.5-5.5 ℃/min.
Preferably, the calcination is performed in a nitrogen-hydrogen mixed atmosphere or a nitrogen atmosphere.
Preferably, the mass concentration of the hydrofluoric acid is 20-40%.
Preferably, the etching temperature is 55-65 ℃ and the etching time is 6-8 h.
The invention provides the thin-wall amorphous carbon nano tube prepared by the preparation method in the technical scheme.
Preferably, the outer diameter of the thin-wall amorphous carbon nano tube is 100-120 nm, and the thickness of the tube wall is 5-10 nm.
The invention provides application of the thin-wall amorphous carbon nano tube in the technical scheme as a lithium ion battery cathode material.
The invention provides a preparation method of a thin-wall amorphous carbon nanotube, which comprises the following steps: providing sulfonated polymer nanotubes-SiO 2 Composite material, sulfonated polymer nanotube-SiO 2 SiO in composite materials 2 Embedded in the walls of the sulfonated polymer nanotubes; calcining the sulfonated polymer nanotube-SiO 2 composite material to obtain the carbon nanotube-SiO 2 A composite material; the carbon nano tube-SiO is treated by hydrofluoric acid 2 Etching the composite material to obtain a thin wallAmorphous carbon nanotubes. The invention uses sulfonated polymer nano-tube-SiO 2 The composite material is calcined, the polymer nano tube shrinks in the calcining process, and simultaneously SiO 2 The particles are formed and can generate physical extrusion effect on the polymer nano tube to obtain the carbon nano tube-SiO 2 Composite material, said polymer nano-tube-SiO 2 SiO in composite material 2 Will be embedded into the wall of the polymer nanotube, which is different from the traditional template method that the carbon source is wrapped in SiO 2 On the template; then removing SiO by hydrofluoric acid etching 2 Finally, the thin-wall amorphous carbon nano tube is prepared. The preparation method provided by the invention is simple to operate, a special device and an expensive reagent are not needed, and the prepared thin-wall amorphous carbon nanotube shows excellent electrochemical performance when being used as a lithium ion battery cathode material.
Drawings
FIG. 1 is a powder diffraction pattern of thin-walled amorphous carbon nanotubes prepared in example 1;
FIG. 2 shows the carbon nanotube-SiO prepared in example 1 2 Scanning electron microscope and transmission electron microscope images of the composite material and the thin-wall amorphous carbon nano tube;
fig. 3 is a cycle life diagram and a rate performance diagram of the thin-walled amorphous carbon nanotube prepared in example 1 under different current densities.
Detailed Description
The invention provides a preparation method of a thin-wall amorphous carbon nanotube, which comprises the following steps:
providing sulfonated polymer nanotubes-SiO 2 Composite material, sulfonated polymer nanotube-SiO 2 SiO in composite materials 2 Embedded in the walls of the sulfonated polymer nanotubes;
the sulfonated polymer nano-tube-SiO 2 Calcining the composite material to obtain the carbon nano tube-SiO 2 A composite material;
the carbon nano tube-SiO is treated by hydrofluoric acid 2 And etching the composite material to obtain the thin-wall amorphous carbon nano tube.
The present invention provides sulfonated polymer nanotubes-SiO 2 Composite material, sulfonated polymer nanotube-SiO 2 SiO in composite materials 2 Embedded within the walls of the sulfonated polymer nanotubes. In the present invention, the sulfonated polymer nanotube-SiO 2 The preparation method of the composite material preferably comprises the following steps:
mixing the sulfonated polymer nanotube, tetraethoxysilane and ethanol to obtain an tetraethoxysilane-sulfonated polymer nanotube composite material;
mixing the tetraethoxysilane-sulfonated polymer nanotube composite material with ethanol, ammonia water and water, and carrying out hydrolysis reaction to obtain wet gel;
drying the wet gel to obtain the sulfonated polymer nanotube-SiO 2 A composite material.
The sulfonated polymer nanotube, the tetraethoxysilane and the ethanol are mixed to obtain the tetraethoxysilane-sulfonated polymer nanotube composite material. The present invention preferably provides first sulfonated polymer nanotubes, preferably prepared from polymer nanotubes by sulfonation, preferably from divinylbenzene and vinylbenzyl chloride by polymerization. In the present invention, the method for preparing the sulfonated polymer nanotube preferably comprises the steps of:
mixing divinyl benzene, vinyl benzyl chloride, an initiator and an organic solvent, and then carrying out polymerization reaction to obtain a polymer nanotube;
mixing the polymer nanotube with concentrated sulfuric acid, and then carrying out sulfonation reaction to obtain a sulfonated polymer nanotube; the mass concentration of the concentrated sulfuric acid is 96-98%.
In the invention, the divinyl benzene, the vinyl benzyl chloride, the initiator and the organic solvent are preferably mixed and then subjected to polymerization reaction to obtain the polymer nanotube. In the present invention, the amount ratio of divinylbenzene, vinylbenzyl chloride, initiator and organic solvent is preferably 3 g: 1 g: (140-160) mg: (90-110) g, more preferably 3 g: 1 g: 150 mg: 100g of the total weight of the mixture; the initiator preferably comprises boron trifluoride etherate; the organic solvent preferably comprises n-heptane. In the present invention, the divinylbenzene, the vinylbenzyl chloride, the initiator and the organic solvent are preferably mixed, and then the initiator is added dropwise to the resulting mixture; the dropping rate of the initiator is not particularly limited in the invention, and the initiator can be added dropwise.
In the present invention, the temperature of the polymerization reaction is preferably room temperature, i.e., no additional heating or cooling is required; the time of the polymerization reaction is preferably 10-20 min, more preferably 15min, and the time of the polymerization reaction is counted from the completion of the dropping of the initiator. In the present invention, the polymerization reaction is preferably carried out under ultrasonic conditions; the conditions of the ultrasound in the present invention are not particularly limited, and the ultrasound conditions known to those skilled in the art may be used. In the invention, preferably, divinylbenzene, vinylbenzyl chloride, an initiator and an organic solvent are mixed, and the polymerization reaction is carried out under the conditions of sealing and ultrasound; during the polymerization reaction, a large amount of reddish brown precipitate is generated in the system.
After the polymerization reaction is finished, preferably adding ethanol into the system to terminate the polymerization reaction, and filtering the obtained system to obtain a solid material, namely the polymer nanotube; the amount of ethanol added in the present invention is not particularly limited, and the polymerization reaction can be terminated.
After the polymer nano tube is obtained, the polymer nano tube is preferably crushed and then mixed with concentrated sulfuric acid for sulfonation reaction to obtain a sulfonated polymer nano tube; the mass concentration of the concentrated sulfuric acid is 96-98%. The invention has no special limitation on the pulverization, and the subsequent sulfonation reaction is ensured to be smoothly carried out. In the present invention, the ratio of the amount of the polymer nanotubes to the amount of the concentrated sulfuric acid is preferably 1 g: (25-35) mL, more preferably 1 g: 30 mL; the temperature of the sulfonation reaction is preferably 45-55 ℃, and more preferably 50 ℃; the sulfonation reaction time is preferably 10-15 h, and more preferably 12 h.
After the sulfonation reaction is finished, the system is preferably cooled to room temperature, then diluted by distilled water, filtered, washed to be neutral, and dried to obtain a yellow brown or brown loose substance, namely the sulfonated polymer nanotube. The amount of the distilled water, and the specific operation conditions of washing and drying are not particularly limited in the present invention, and a technical scheme well known to those skilled in the art can be adopted.
After the sulfonated polymer nanotube is obtained, the sulfonated polymer nanotube, the tetraethoxysilane and the ethanol are mixed to obtain the tetraethoxysilane-sulfonated polymer nanotube composite material. In the present invention, the sulfonated polymer nanotubes, tetraethoxysilane and ethanol are preferably used in a ratio of 200 mg: (8-12) mL: (15-25) mL, more preferably 200 mg: 10mL of: 20 mL. In the present invention, the ethanol is preferably anhydrous ethanol. In the invention, the sulfonated polymer nanotube, ethyl orthosilicate and ethanol are preferably mixed, after uniform ultrasonic dispersion, the ethanol dispersion liquid of the sulfonated polymer nanotube and the ethanol solution of ethyl orthosilicate are stirred and mixed for 7-9 h, so that ethyl orthosilicate is absorbed and permeated into the sulfonated polymer nanotube to form the ethyl orthosilicate-sulfonated polymer nanotube composite material.
In the invention, after the mixing is finished, preferably, the obtained system is subjected to solid-liquid separation, and the obtained solid material is the tetraethoxysilane-sulfonated polymer nanotube composite material. The solid-liquid separation method is not particularly limited, and a method known to those skilled in the art, such as filtration, may be used.
After the tetraethoxysilane-sulfonated polymer nanotube composite material is obtained, the tetraethoxysilane-sulfonated polymer nanotube composite material is mixed with ethanol, ammonia water and water for hydrolysis reaction to obtain wet gel. In the invention, the preferred mixing of the tetraethoxysilane-sulfonated polymer nanotube composite material with ethanol, ammonia water and water is to mix the tetraethoxysilane-sulfonated polymer nanotube composite material with ethanol, adjust the pH value of the obtained system to 9-10 by using ammonia water (the mass concentration is preferably 25-28%), stir and mix for 50-70 min, and then mix the obtained system with water. In the present invention, the addition amounts of ethanol and water in this step are preferably determined based on the sulfonated polymer nanotubes, and specifically, the ratio of the sulfonated polymer nanotubes to ethanol to water is preferably 200 mg: (8-12) mL: (4-6) mL, more preferably 200 mg: 10mL of: 5 mL. In the invention, the temperature of the hydrolysis reaction is preferably 15-60 ℃, more preferably 20-40 ℃, and specifically, the hydrolysis reaction can be carried out at room temperature, i.e. no additional heating or cooling is needed; the time of the hydrolysis reaction is preferably 4.5-5.5 h, and more preferably 5 h; the hydrolysis reaction is preferably carried out under stirring.
After the hydrolysis reaction is completed, the obtained system is preferably subjected to centrifugal separation, and the obtained solid material is washed for 4-5 times by using ethanol to obtain wet gel.
After the wet gel is obtained, the invention dries the wet gel to obtain the sulfonated polymer nanotube-SiO 2 A composite material. In the invention, the drying temperature is preferably 75-85 ℃, and more preferably 80 ℃; the drying time is not specially limited, and the sulfonated polymer nanotube-SiO with constant weight can be obtained 2 And (3) preparing the composite material.
To obtain sulfonated polymer nanotube-SiO 2 After the composite material is prepared, the invention uses the sulfonated polymer nanotube-SiO 2 Calcining the composite material to obtain the carbon nano tube-SiO 2 A composite material. In the invention, the calcining temperature is preferably 850-950 ℃, and more preferably 900 ℃; the heat preservation time is preferably 2.5-3.5 h, and more preferably 3 h; the heating rate for heating to the temperature required by calcination is preferably 4.5-5.5 ℃/min, and more preferably 5 ℃/min; the calcination is carried out in a nitrogen-hydrogen mixed atmosphere or a nitrogen atmosphere, wherein the volume fraction of hydrogen in the nitrogen-hydrogen mixed atmosphere is preferably not more than 5%. In the present invention, the calcination can carbonize and shrink the polymer nanotubes to SiO 2 Particle-formed, SiO embedded in the wall of a polymer nanotube 2 The particles produce physical extrusion effect on the polymer nano-tube, which is beneficial to the formation of the thin-wall amorphous carbon nano-tube.
Obtaining the carbon nano tube-SiO 2 After the composite material is prepared, the invention utilizes hydrofluoric acid to treat the carbon nano tube-SiO 2 Etching the composite material to obtain the thin-wall amorphous materialA shaped carbon nanotube. In the invention, the mass concentration of the hydrofluoric acid is preferably 20-40%, and more preferably 20%; the dosage of the hydrofluoric acid is not particularly limited, and the polymer nanotube-SiO can be immersed 2 And (3) preparing the composite material. In the invention, the etching temperature is preferably 55-65 ℃, and more preferably 60 ℃; the time is preferably 6-8 h, and more preferably 7 h. In the present invention, the etching is capable of etching SiO 2 The occupied space volume is released, and the thin-wall amorphous carbon nano tube is ensured to be finally obtained.
After the etching is finished, the obtained system is preferably subjected to suction filtration and washing, and then the obtained solid material is dried to obtain the thin-wall amorphous carbon nano tube. The suction filtration washing and drying are not particularly limited in the present invention, and the technical scheme well known to those skilled in the art can be adopted.
The invention provides the thin-wall amorphous carbon nano tube prepared by the preparation method in the technical scheme. In the invention, the outer diameter of the thin-wall amorphous carbon nano tube is preferably 100-120 nm, and the thickness of the tube wall is preferably 5-10 nm.
The invention provides application of the thin-wall amorphous carbon nano tube in the technical scheme as a lithium ion battery cathode material. The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding 3g of divinylbenzene and 1g of vinylbenzyl chloride into 100g of n-heptane, adding 150mg (10 drops) of boron trifluoride diethyl etherate complex serving as an initiator, sealing, and carrying out polymerization reaction for 15min under the conditions of ultrasound and room temperature to generate a large amount of reddish brown precipitates in the system; after the polymerization reaction is finished, adding ethanol into the system to terminate the polymerization reaction, and filtering to obtain a white cotton bulk substance, namely the polymer nanotube;
4g of the polymer nanotubes were pulverized with a stirrer and placed in 120mL of concentrated sulfuric acid (H) 2 SO 4 98 percent of mass concentration), and carrying out sulfonation reaction for 12 hours at 50 ℃; cooling to room temperature after the sulfonation reaction is finished, then diluting with distilled water, washing the obtained solid material to be neutral after suction filtration, and then drying to obtain a brown loose substance, namely the sulfonated polymer nanotube;
(2) adding 200mg of the sulfonated polymer nanotube into 15mL of absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding 15mL of ethyl orthosilicate ethanol solution (formed by mixing 5mL of absolute ethyl alcohol and 10mL of ethyl orthosilicate) into the mixture, stirring and mixing for 8 hours, centrifuging to remove supernatant, dissolving the obtained solid material into 10mL of absolute ethyl alcohol, adjusting the pH value to 9 by using ammonia water, stirring and mixing for 1 hour, adding 5mL of water, and carrying out hydrolysis reaction for 5 hours under the conditions of stirring and room temperature; after the hydrolysis reaction is finished, carrying out centrifugal separation on the obtained system, and washing the obtained solid material for 5 times by adopting ethanol to obtain wet gel;
drying the wet gel at the temperature of 80 ℃ to obtain the sulfonated polymer nanotube-SiO 2 A composite material; subjecting the sulfonated polymer nanotube-SiO 2 Placing the composite material in a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, keeping the temperature, calcining for 3 hours, and naturally cooling to room temperature to obtain the carbon nano tube-SiO 2 A composite material;
the carbon nano tube-SiO 2 Immersing the composite material in hydrofluoric acid (the mass concentration is 20%) at 60 ℃, etching for 7h, carrying out suction filtration and washing on the obtained system, and drying the obtained solid material to obtain the thin-wall amorphous carbon nano tube.
Characterization and Performance testing
FIG. 1 is a powder diffraction pattern of thin-walled amorphous carbon nanotubes prepared in example 1; as can be seen from fig. 1, the material prepared in example 1 is an amorphous carbon material.
FIG. 2 shows the carbon nanotube-SiO prepared in example 1 2 Scanning electron microscope and transmission electron microscope images of the composite material and the thin-wall amorphous carbon nano tube, wherein a is carbon nano tube-SiO 2 Scanning electron microscope image of the composite material, b is carbon nano tube-SiO 2 The transmission electron microscope image of the composite material, c is the scanning electron microscope image of the thin-wall amorphous carbon nano tube, and d is the transmission electron microscope image of the thin-wall amorphous carbon nano tube. As can be seen from FIG. 2, the carbon nanotube-SiO 2 SiO in composite material 2 Embedded in the tube wall of the carbon nano tube, which is different from the traditional template method that the carbon source is wrapped in SiO 2 On the template; meanwhile, as can be seen from FIG. 2, the carbon nanotube-SiO 2 The thickness of the tube wall of the carbon nano tube in the composite material is 30-40 nm, and the thickness of the tube wall of the thin-wall amorphous carbon nano tube is 5-10 nm.
The thin-wall amorphous carbon nanotube prepared in the embodiment is used as a negative electrode material of a lithium ion battery and assembled into a button 2032 battery, and the button 2032 battery is subjected to electrochemical performance test at normal temperature within a voltage range of 0.01-3V. The results are shown in FIG. 3, where a is the cycle performance of the thin-walled amorphous carbon nanotube at current densities of 2A/g, 5A/g and 10A/g, and b is the rate performance of the thin-walled amorphous carbon nanotube. As can be seen from a in FIG. 3, the discharge capacity after 200 cycles can reach 400.6mAh/g under the condition of 2A/g current density, and the discharge capacity after 200 cycles can reach 265.1mAh/g and 210.3mAh/g respectively under the conditions of 5A/g and 10A/g ultrahigh current density; as can be seen from b in fig. 3, the thin-walled amorphous carbon nanotube still has good capacity retention rate under the condition of large-rate switching. The thin-wall amorphous carbon nano tube provided by the invention has excellent rate capability and cycle stability, and is a lithium ion battery cathode material with great application potential.
From the above embodiments, the thin-wall amorphous carbon nanotube with excellent electrochemical properties prepared by the method provided by the invention has the following advantages compared with the existing amorphous carbon cathode material: the thin-wall amorphous carbon nanotube provided by the invention has the kinetic advantage of a one-dimensional material, the thin-wall tubular structure is favorable for improving the conductivity of amorphous carbon and fully permeating electrolyte, and the thin-wall amorphous carbon nanotube is used as a lithium ion battery cathode material to show quite high reversible capacity and still has excellent capacity and cycle stability under the condition of ultrahigh current density.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a thin-wall amorphous carbon nanotube is characterized by comprising the following steps:
providing sulfonated polymer nanotubes-SiO 2 Composite material of sulfonated polymer nanotube-SiO 2 SiO in composite materials 2 Embedded in the walls of the sulfonated polymer nanotubes;
the sulfonated polymer nano-tube-SiO 2 Calcining the composite material to obtain the carbon nano tube-SiO 2 A composite material;
the carbon nano tube-SiO is treated by hydrofluoric acid 2 Etching the composite material to obtain a thin-wall amorphous carbon nanotube;
the sulfonated polymer nanotube-SiO 2 The preparation method of the composite material comprises the following steps:
mixing the sulfonated polymer nanotube, tetraethoxysilane and ethanol to obtain an tetraethoxysilane-sulfonated polymer nanotube composite material;
mixing the tetraethoxysilane-sulfonated polymer nanotube composite material with ethanol, ammonia water and water, and carrying out hydrolysis reaction to obtain wet gel;
drying the wet gel to obtain the sulfonated polymer nanotube-SiO 2 A composite material;
the dosage ratio of the sulfonated polymer nanotube, the tetraethoxysilane and the water is 200 mg: (8-12) mL: (4-6) mL;
the calcining temperature is 850-950 ℃, and the heat preservation time is 2.5-3.5 h.
2. The preparation method according to claim 1, wherein the temperature of the hydrolysis reaction is 15-60 ℃ and the time is 4.5-5.5 h.
3. The production method according to claim 1, wherein a temperature increase rate of increasing the temperature to the temperature required for the calcination is 4.5 to 5.5 ℃/min.
4. The production method according to claim 3, characterized in that the calcination is performed in a nitrogen-hydrogen mixed atmosphere or a nitrogen atmosphere.
5. The method according to claim 1, wherein the hydrofluoric acid has a concentration of 20 to 40% by mass.
6. The method according to any one of claims 1 and 3 to 5, wherein the etching temperature is 55 to 65 ℃ and the etching time is 6 to 8 hours.
7. The thin-walled amorphous carbon nanotube prepared by the preparation method according to any one of claims 1 to 6.
8. The thin-walled amorphous carbon nanotube according to claim 7, wherein the thin-walled amorphous carbon nanotube has an outer diameter of 100 to 120nm and a wall thickness of 5 to 10 nm.
9. Use of the thin-walled amorphous carbon nanotubes of claim 7 or 8 as a negative electrode material for lithium ion batteries.
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| CN1944535A (en) * | 2006-09-28 | 2007-04-11 | 同济大学 | Medium temperature proton conductive mateiral basedon hydrophilic carbon nano tube and its preparing method |
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| CN1944535A (en) * | 2006-09-28 | 2007-04-11 | 同济大学 | Medium temperature proton conductive mateiral basedon hydrophilic carbon nano tube and its preparing method |
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