CN109941984B - Preparation method of carbon micro-tube and carbon micro-tube - Google Patents
Preparation method of carbon micro-tube and carbon micro-tube Download PDFInfo
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- CN109941984B CN109941984B CN201910385662.8A CN201910385662A CN109941984B CN 109941984 B CN109941984 B CN 109941984B CN 201910385662 A CN201910385662 A CN 201910385662A CN 109941984 B CN109941984 B CN 109941984B
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Abstract
The application provides a preparation method of a carbon micron tube and the carbon micron tube, wherein the preparation method of the carbon micron tube comprises the following steps: and a calcining step, namely heating the corn stigma to a calcining temperature under protective gas, and keeping the temperature for the first time at the calcining temperature to obtain the carbon micron tube. This application adopts the corn silk that has the source extensively, easily collect, the huge quantity is as raw and other materials preparation carbon micron tube, low cost, easily scale production, and the carbon micron tube of preparation has the advantage in length, can reach twenty a few centimetres, be far away from the carbon micron tube of current preparation such as adoption catkin, poplar wadding, moss, in addition, in this application, soak the corn silk with the acidizing fluid before the calcination and reduced calcination temperature by a wide margin, can calcine at the temperature of 200 ℃ at minimum and obtain carbon micron tube, thereby further reduce cost and requirement to equipment.
Description
Technical Field
The application relates to the field of materials, in particular to a preparation method of a carbon micron tube and the carbon micron tube.
Background
The carbon nanotube has excellent properties of the carbon nanotube, such as high mechanical strength, good electric and heat conductivity, excellent chemical and high-temperature stability, unique micron-scale pipe diameter, and can be filled with guest molecules with larger size, so that the carbon nanotube has wide application prospect in the fields of catalyst carriers, hydrogen storage materials, electrode materials, wave-absorbing materials, drug sustained release and other pharmaceutical and chemical materials, which is incomparable with the carbon nanotube with extremely small pipe diameter. At present, the preparation method of the carbon micron tube mainly comprises a chemical vapor deposition method (CVD), a catalyst method, a template method, a self-assembly method, a spinning method, a biomass carbonization method and the like. The carbon nanotube prepared by high-temperature carbonization of the natural structure of the biomass has the characteristics of low cost, simple process, controllable appearance and large-scale preparation, and is suitable for amplification production. In the invention patent with the application number of 201010590224.4, poplar catkins and willow catkins are used as raw materials to prepare carbon micron tubes; in the invention patent with application number 201711362149.4, kapok is used as a raw material, and the hollow carbon microtube is obtained through pretreatment, crosslinking, carbonization, activation and aftertreatment; in the invention patent with application number 201710967784.9, moss is used as a raw material to prepare the carbon tube.
In the prior art, when catkin, poplar catkin and moss are used as biomass to prepare the carbon nanotube, the following problems exist: on one hand, the natural yield of the poplar catkin, the catkin and the moss is low, the poplar catkin, the catkin and the moss are not easy to recover, the large-scale production is not facilitated, and the production cost can be greatly increased if the poplar catkin, the catkin and the moss are produced in a special renting place. On the other hand, the size of poplar catkins, willow catkins and moss is small, and it is difficult to prepare carbon nanotubes having an axial length of more than 10 cm.
In addition, in the prior art, a high-temperature calcination process is often adopted when the carbon micron tube is prepared, the calcination temperature is at least 300 ℃, and the higher the calcination temperature is, the higher the energy consumption is, the higher the requirement on the safety of equipment is, so that the reduction of the calcination temperature can greatly reduce the energy consumption and the requirement on the equipment, thereby reducing the cost.
Disclosure of Invention
The present application provides a method for preparing a carbon nanotube and a carbon nanotube for solving the above problems.
In order to solve the above problems, as one aspect of the present application, there is provided a method of manufacturing a carbon nanotube, including:
and a calcining step, namely heating the corn stigma to a calcining temperature under protective gas, and keeping the temperature for the first time at the calcining temperature to obtain the carbon micron tube.
Optionally, in the calcination step, the calcination temperature is 300-1000 ℃, and the first time period is 1-10 h.
Optionally, before the calcining step, the method further comprises:
and a soaking step, soaking the corn stigma in an acid solution for a second time and then taking out.
Optionally, the acid solution is one of hydrochloric acid, nitric acid or sulfuric acid, or,
the acid solution is a mixed solution of a plurality of acids of hydrochloric acid, nitric acid and sulfuric acid.
Optionally, the acid solution has a concentration of 0.1 to 2 mol/L, and/or the second period of time is 6 to 12 hours.
Optionally, the concentration of the acid solution is 0.1-2 mol/L, and the second time is 6-12 h;
in the calcination step, the calcination temperature is 250-1000 ℃, and the first time period is 1-10 h.
Optionally, the acid solution is sulfuric acid with the mass fraction of 30-70%, the second time is 10-12h, the mass ratio of the acid solution to the corn stigma is 1-10:1, and the calcining temperature is 200-.
Optionally, after the soaking step and before the calcining step, the method further comprises:
a cleaning step, namely washing the corn stigma to be neutral and drying;
optionally, the protective gas is nitrogen or argon.
The application also provides a carbon micron tube prepared by any one of the methods provided by the application, the carbon micron tube has the carbon content of 92 at% -94 at%, the oxygen content of 5 at% -7 at%, the nitrogen content of 1 at% -2 at%, the inner diameter of 11.5 mu m-47 mu m, the wall thickness of 5.2 mu m-21.1 mu m, and the apparent density of 0.16-0.18g/cm3。
The carbon micron tube is prepared by adopting corn silk with wide source, easy collection and huge quantity as a raw material, the cost is low, the large-scale production is easy, the prepared carbon micron tube has advantages in length and can reach twenty-few centimeters, and the length is far greater than that of the existing carbon micron tube prepared by adopting catkin, poplar catkin, moss and the like.
Drawings
FIG. 1 is a schematic diagram illustrating a method for manufacturing a carbon nanotube according to an embodiment of the present disclosure;
FIG. 2 is a schematic length diagram of the corn stigma and the prepared carbon nanotube in the present application;
FIG. 3 is a scanning electron microscope image of stigma Maydis in an example of the present application;
FIG. 4 is a scanning electron microscope photograph of a carbon nanotube prepared in example 3 of the present application;
FIG. 5 is a scanning electron microscope photograph of a carbon nanotube prepared in example 4 of the present application;
fig. 6 is a schematic length diagram of the corn stigma and the prepared carbon nanotube in example 9 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. 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 application.
It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the application described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or air conditioner that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or air conditioner.
Example 1
In the prior art, when the catkin, the catkin and the moss are used as biomass to prepare the carbon nanotube, the natural yield of the catkin, the catkin and the moss is low, so that the carbon nanotube can be produced only in a specific season and is not easy to recover, large-scale production is not facilitated, and the production cost can be greatly increased if the catkin, the catkin and the moss are produced in a special renting place.
Corn is a main food crop in China, the seeding area of the corn in China in 2017 is 3544.5 ten thousand hectares, the total yield is 2.16 hundred million tons, and the yield of the corn silk serving as a byproduct is about 1 million tons. However, most of the corn silk is not fully utilized and is discarded.
The application provides a preparation method of a carbon micron tube, which comprises the following steps:
and a calcining step, namely heating the corn stigma to a calcining temperature under protective gas, and keeping the temperature for the first time at the calcining temperature to obtain the carbon micron tube.
Specifically, the calcining temperature is 300-. One of the main inventions of the present application is to use corn silk as a raw material to prepare the carbon nanotube, and compared with the technical scheme of using poplar seed, willow seed and moss in the prior art, the yield of the corn silk is far greater than that of the poplar seed, the willow seed and the moss, and when harvesting corn, the corn silk is gathered together in a large amount as a byproduct, so that the corn silk is very easy to recover, the cost is far lower than that of the poplar seed, the willow seed and the moss, and the large-scale preparation of the carbon nanotube can be realized without the need of renting a place to produce the corn silk. The carbon micron tube is prepared by adopting the corn stigma as the raw material, so that the cost of large-scale production is greatly reduced.
On the other hand, after observing the carbon nanotube prepared by the method provided by the application by using a microscope, the fact that when the carbon nanotube is prepared by using the corn silk with the length not less than 30cm, the length of the prepared carbon nanotube is not less than 20cm at this time is found, compared with the carbon nanotube prepared by using the poplar seed, the willow seed and the moss as raw materials, the carbon nanotube prepared by using the poplar seed, the willow seed and the moss as raw materials has smaller sizes, and the poplar seed, the willow seed and the moss with the sizes larger than 10cm are rarely, the axial length of the prepared carbon nanotube is only a few centimeters, and the carbon nanotube prepared by using the method is longer in axial length because of the corn silk, so that the carbon nanotube with the length of more than 10 centimeters and even more than 20 centimeters can be easily prepared as long as the selected corn silk is ensured to have enough axial length.
Alternatively, as shown in fig. 1, the present application provides another method for preparing a carbon nanotube, comprising
Soaking, namely soaking the corn stigma in an acid solution for a second time and then taking out;
and a calcining step, namely heating the corn stigma to a calcining temperature under protective gas, and keeping the temperature for the first time at the calcining temperature to obtain the carbon micron tube.
Optionally, after the soaking step and before the calcining step, the method further comprises: a cleaning step, namely washing the corn stigma to be neutral and drying; the cleaning process is to remove the acid solution on the surface of the corn stigma to prevent pollution.
Optionally, the acid solution is one of hydrochloric acid, nitric acid and sulfuric acid, or the acid solution is a mixed solution of a plurality of acids of hydrochloric acid, nitric acid and sulfuric acid, the concentration of the acid solution is 0.1-2 mol/L, and optionally, the second time length of soaking in the acid solution is 6-12 hours.
In the present embodiment, the soaking treatment of the corn silk with the acid solution includes reducing the sintering temperature and removing stains, the acid solution itself can remove attachments on the surface of the corn silk, some alkaline substances contained in the corn silk are removed, organic substances are partially hydrolyzed, soluble metal ions are dissolved out, which is beneficial to improve the quality of the carbon nanotube, on the other hand, the acid solution has a certain dehydration effect, which can partially remove moisture in the cellulose on the surface of the corn silk, so that partial carbonization is achieved, and the water on the surface of the corn silk is removed, so that the cellulose in the middle of the corn silk is easily heated and dehydrated during the subsequent calcination process, thereby greatly reducing the temperature required for calcination.
The calcining step can be carried out in a tubular furnace, in the application, because the corn stigma is soaked in the acid liquor, the corn stigma can be calcined at a lower temperature, so that the energy consumption and the requirements on equipment are greatly reduced, and in the prior art, the calcining temperature during the preparation of the carbon nanotube is mostly higher than 300 ℃, a large amount of energy is needed, and the requirements on the equipment are higher. Optionally, the first time period for calcination is from 1 to 10 hours, preferably 2 and 4 hours.
Preferably, in the present application, when the acid solution is sulfuric acid with a mass fraction of 30-70%, the second time period is 10-12h, and the mass ratio of the corn stigma to the acid solution is 1-10:1, the calcination temperature can be 200-240 ℃. In the application, the lowest calcining temperature is 200 ℃, the shortest calcining time is 1h, and the rapid low-temperature preparation of the carbon micro-tube can be realized under the condition that the temperature and the time are far lower than those in the prior art. The sulfuric acid solution is used for soaking, so that the hydrolysis of lignin, cellulose, hemicellulose and other components is promoted; secondly, the corn stigma can be dehydrated and carbonized, and the carbonization temperature is finally reduced by the two effects. It is noted that the concentration of the sulfuric acid needs to be controlled to be 30-70% by mass, and the mass ratio of the sulfuric acid to the corn stigma is 1-10: 1. when the concentration of the sulfuric acid is too low, the hydrolysis and carbonization degrees of the surface of the corn stigma are incomplete, and the effect of obviously reducing the calcining temperature cannot be achieved; when the concentration of the sulfuric acid is too high, the corn stigma is completely carbonized, the corn stigma collapses, and the pore structure of the carbon tube is damaged.
Optionally, a pre-washing step is included to pre-wash the corn prior to the steeping step. The cleaning process can adopt the prior art, and can be cleaning by clear water or cleaning by clear water to be neutral after cleaning by alkaline solution.
Example 2
Selecting corn stigma with the length of 32cm, cleaning, drying, placing into a tube furnace, heating to 600 ℃ in nitrogen atmosphere, keeping for 3h, cooling, and taking out to obtain a carbon micron tube with the length of 21 cm.
The corn silk adopted in the embodiment and the length of the prepared carbon micron tube are shown in figure 2, the inner diameter of the carbon micron tube is 11.5 microns, the wall thickness is 5.2 microns, and the structure is that two ends are the sameThe crystal form of the hollow pipeline is an amorphous carbon structure, and the conductivity reaches 3.1 × 105S/m, as can be seen from the figure, the axial length of the carbon micron tube decreases after calcination, and the inventors of the present application have found through experiments that when the length of the selected corn silk is not less than 30cm, the length of the prepared carbon micron tube can be ensured to be more than 20cm, and thus the corn silk of more than 30cm is preferably used in the present application.
Example 3
Weighing 10 g of corn silk with the length of 22cm, wherein the scanning electron microscope picture of the corn silk is shown in figure 3, the wall thickness of the corn silk is about 16 microns, cleaning the corn silk, soaking the corn silk in 0.1 mol/L nitric acid solution, washing the corn silk with deionized water to be neutral after 12 hours, drying, putting the dried sample into a tube furnace, heating to 600 ℃ under the nitrogen atmosphere, keeping the temperature for 3 hours, cooling and taking out the sample to prepare the carbon micron tube, wherein the length of the carbon micron tube is 16cm, figure 4 is the scanning electron microscope picture of the prepared carbon micron tube, the inner diameter of the prepared carbon micron tube is 40.1 microns, the wall thickness is 12.3 microns, the structure is a hollow pipeline with the same two ends, the crystal form is an amorphous carbon structure, and the electric conductivity reaches 3.2 × 105S/m, the prepared carbon micron tube is subjected to atom content determination, and test results show that the carbon content in the carbon micron tube is 93.3 at%, the oxygen content is 5.23 at%, and the nitrogen content is 1.47 at%, the preparation raw material selected by the application is natural biomass corn silk, the corn silk has a natural hollow pipeline structure, is very suitable for preparing the carbon micron tube, has high carbon content and contains nitrogen elements, the prepared carbon micron tube has natural nitrogen doping performance, the nitrogen doping causes local charge density change, contributes to the formation of an electric double layer, can improve the electrochemical activity of the material, improve the wettability of electrolyte in the material and increase the specific capacitance, and avoids morphological defects and structural damage of the carbon micron tube caused by artificial nitrogen doping.
Example 4 weighing 10 g of corn silk, washing, immersing in 2 mol/L nitric acid solution, washing with deionized water to neutral after 12 hours, drying, placing the dried sample in a tube furnace, heating to 800 ℃ under nitrogen atmosphere, keeping for 1 hour, cooling, and taking out to obtain the carbon micron tube, wherein the carbon micron tube is shown in figure 5As can be seen from FIGS. 3 and 5, the wall thickness of the carbon nanotube in this example was about 5 μm, which is much less than the wall thickness of the corn silk by 16 μm. the atomic content measurement of the prepared carbon nanotube revealed that the carbon nanotube had a carbon content of 93.86 at%, an oxygen content of 4.83 at%, a nitrogen content of 1.31 at%, and an electrical conductivity of 3.2 × 105S/m。
Example 5 weighing 10 g of corn silk, cleaning, soaking in 2 mol/L sulfuric acid solution, washing with deionized water to neutrality after 12 hours, drying, placing the dried sample in a tube furnace, heating to 260 ℃ under nitrogen atmosphere, keeping for 3 hours, cooling, and taking out to obtain the carbon micron tube.
Example 6, the corn silk is weighed, cleaned, soaked in 1.5 mol/L sulfuric acid solution, soaked for 12 hours, washed to neutrality with deionized water, dried, put the dried corn silk sample into a tube furnace, heated to 290 ℃ under nitrogen atmosphere, kept for 3 hours, cooled and taken out to obtain the carbon micron tube.
Example 7 weighing 10 g of corn silk, cleaning, soaking in L mass percent sulfuric acid solution with the mass ratio of sulfuric acid to corn silk being 5:1 for 12 hours, washing the corn silk with deionized water to be neutral, drying, placing the dried corn silk sample in a tube furnace, heating to 240 ℃ under nitrogen atmosphere, keeping for 3 hours, cooling, and taking out to obtain the carbon micron tube.
Example 8: weighing 10 g of corn silk, cleaning, soaking in a sulfuric acid solution with the mass fraction of 50%, wherein the mass ratio of sulfuric acid to corn silk is 5:1, soaking for 12 hours, washing the corn silk to be neutral by using deionized water, and drying. And (3) putting the dried corn stigma sample into a tube furnace, heating to 220 ℃ in a nitrogen atmosphere, keeping for 3h, cooling and taking out to obtain the carbon micron tube.
Example 9: weighing 10 g of corn silk with the length of 20cm, cleaning the corn silk, soaking the corn silk in a sulfuric acid solution with the mass fraction of 50%, wherein the mass ratio of the sulfuric acid to the corn silk is 10:1, soaking the corn silk for 12 hours, washing the corn silk with deionized water to be neutral, and drying. And (3) putting the dried corn stigma sample into a tube furnace, heating to 200 ℃ in a nitrogen atmosphere, keeping for 3h, cooling, and taking out to obtain a 16cm carbon micron tube with the tube diameter of 40 microns and the wall thickness of 7.47 microns.
Example 10: weighing 10 g of corn silk, cleaning, soaking in a sulfuric acid solution with the mass fraction of 70%, wherein the mass ratio of sulfuric acid to corn silk is 5:1, soaking for 12 hours, washing the corn silk to be neutral by using deionized water, and drying. And (3) putting the dried sample into a tube furnace, heating to 200 ℃ in nitrogen atmosphere, keeping for 3h, cooling and taking out to obtain the carbon micron tube.
Example 11: weighing 10 g of corn silk, cleaning, soaking in a sulfuric acid solution with the mass fraction of 70%, wherein the mass ratio of sulfuric acid to corn silk is 10:1, washing with deionized water to be neutral after 12 hours, and drying. And (3) putting the dried sample into a tubular furnace, heating to 200 ℃ in a nitrogen atmosphere, keeping for 1h, cooling and taking out to obtain the carbon micron tube.
The application also provides a carbon micron tube which is prepared by adopting any one of the methods provided by the application, wherein the carbon content of the carbon micron tube is 92at percent to 94at percent, the oxygen content is 5at percent to 7at percent, the nitrogen content is 1at percent to 2at percent, the inner diameter is 11.5 mu m to 47 mu m, and the wall thickness is 5.2 mu m to 21.1 mu m. The prepared carbon micron tube has a length up to twenty centimeters, is flat and straight as a whole, has wrinkles on the surface, and has an apparent density of 0.16-0.18g/cm3Compared with the carbon microtubes prepared by catkin or moss, the carbon microtubes prepared by the method are longer, straight and thicker in pipe wall, are easy to operate, can be easily selected without an optical microscope, are good in machinability and are convenient for operation of a micro-processing technology. The prepared carbon micron tube has large length-diameter ratio, and provides excellent storage capacity. The prepared carbon micron tube leads electrons out of the whole continuous carbon tube, thereby having excellent conductivity. The prepared carbon micron tube has an inner diameter of 11.5-47 microns and can meet the requirements of the fields of biological medicine delivery, biochips, microelectronics, microfluid devices and the like on large-size pipelines as a load channel. The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present applicationAre intended to be included within the scope of the present application.
Claims (9)
1. A method for preparing a carbon nanotube is characterized by comprising the following steps:
a calcining step, namely heating the corn stigma to a calcining temperature under protective gas, and keeping the temperature for a first time at the calcining temperature to obtain a carbon micron tube;
in the calcination step, the calcination temperature is 300-1000 ℃, and the first time period is 1-10 h.
2. The method of claim 1, further comprising, prior to the calcining step:
and a soaking step, soaking the corn stigma in an acid solution for a second time and then taking out.
3. The method for producing a carbon nanotube according to claim 2,
the acid solution is one of hydrochloric acid, nitric acid or sulfuric acid, or,
the acid solution is a mixed solution of a plurality of acids in hydrochloric acid, nitric acid and sulfuric acid.
4. The method for producing a carbon nanotube according to claim 2 or 3,
the concentration of the acid solution is 0.1-2 mol/L, and/or the second time length is 6-12 h.
5. The method for producing a carbon nanotube according to claim 4,
the concentration of the acid solution is 0.1-2 mol/L, and the second time length is 6-12 h;
in the calcination step, the calcination temperature is 250-1000 ℃, and the first time period is 1-10 h.
6. The method for producing a carbon nanotube according to claim 3,
the acid solution is sulfuric acid with the mass fraction of 30-70%, the second time is 10-12h, the mass ratio of the acid solution to the corn stigma is 1-10:1, and the calcination temperature is 200-240 ℃.
7. The method of manufacturing a carbon nanotube according to any one of claims 2, 3, 5, or 6, further comprising, after the soaking step and before the calcining step:
and a cleaning step, namely washing the corn stigma to be neutral and drying.
8. The method for producing a carbon nanotube according to any one of claims 1 to 3, 5 or 6,
the protective gas is nitrogen or argon.
9. A carbon nanotube produced by the method according to any one of claims 1 to 8;
the carbon microtube has carbon content of 92 at% -94 at%, oxygen content of 5 at% -7 at%, nitrogen content of 1 at% -2 at%, inner diameter of 11.5 μm-47 μm, wall thickness of 5.2 μm-21.1 μm, and apparent density of 0.16-0.18g/cm3。
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