CN111223982A - Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance - Google Patents
Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance Download PDFInfo
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Abstract
A preparation method of an n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance comprises the steps of adding an n-type dopant into an organic solvent, and performing ultrasonic dispersion to obtain a solution of the n-type dopant; soaking the multi-wall carbon nanotube film in a solution of an n-type dopant for 1.5 to 3 hours; and then taking out the multiwalled carbon nanotube film obtained after soaking, washing and drying to obtain the n-type multiwalled carbon nanotube thermoelectric material. A series of related characterization of the performance and the stability of the doped carbon nanotube film shows that the multi-walled carbon nanotube film after being doped by the N-DMBI is successfully converted from a p type to an N type, and the conductivity and the Seebeck coefficient of the multi-walled carbon nanotube film are improved. The invention not only has convenient operation process, and the processed n-type multi-walled carbon nanotube film has higher power factor and stability of long-time performance in air, but also greatly improves the application prospect of the n-type multi-walled carbon nanotube film as a thermoelectric material.
Description
Technical Field
The invention relates to a preparation method of an n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance.
Background
The thermoelectric material can directly convert heat energy into electric energy, and the waste heat is utilized to recover energy, so that the energy utilization efficiency is improved. The environment-friendly clean energy material is more and more concerned due to abundant waste heat resources, and has great recycling potential. Compared with traditional brittle and rigid thermoelectric materials, the flexible thermoelectric material can be in close contact with a heat source of any geometric shape, thereby significantly improving conversion efficiency by reducing thermal energy loss. In addition, the flexible individual thermoelectric materials can achieve an optimal device shape, thereby further improving energy conversion efficiency by minimizing heat loss. Therefore, the flexible thermoelectric material, especially the independent self-supporting thin film, which is the next-generation thermoelectric material, is highly regarded for practical use.
Compared with single-wall carbon nanotube film and double-wall carbon nanotube film, the multi-wall carbon nanotube film has the advantages of large-scale production, high purity and low cost. They are promising flexible materials due to their unique electronic properties and flexibility. Since the pristine carbon nanotubes are very sensitive to oxygen, they generally exhibit p-type properties in air due to the doping of oxygen. The n-type carbon nanotube film is generally obtained by treating a p-type carbon nanotube film with a reducing agent, an electron-rich organic molecule, or an encapsulating metal atom/organic donor molecule in the carbon nanotube film. These methods are more commonly used to make n-type single-walled carbon nanotube films and double-walled carbon nanotube films. The Seebeck coefficient of the single-walled carbon nanotube film can reach-80 μ V/K [ ZHou, et al., nat. Commun.,8,14886(2017) ] after being doped by Polyethyleneimine (PEI). However, n-type multiwall carbon nanotube films have been reported less often and generally exhibit lower Seebeck coefficients of the "metallic" type around-10 μ V/K [ Baxendale, et al, physical ReviewB,61,12705(2000) ]. One reason for the low Seebeck coefficient of multi-walled carbon nanotube films is the low n-type doping level of multi-walled carbon nanotube films, due to their co-axial structure, which inhibits the approach of dopants to the inner carbon tubes. The n-type Seebeck coefficient of the multi-walled carbon nanotube is lower due to the competitive action of the inner wall of the p-type undoped multi-walled carbon nanotube and the outer wall of the n-type doped multi-walled carbon nanotube. The second reason may be the reduced surface area due to the large diameter of the multi-walled carbon nanotubes. The dopable surface area of multi-walled carbon nanotubes is much smaller than the dopable surface area of single-walled/double-walled carbon nanotubes. Thus, the surface of the multi-walled carbon nanotube absorbs less dopant species, resulting in a relatively low doping level. Theories and experiments prove that the seebeck coefficient is increased by increasing the doping amount of the n-type dopant during the process of converting the carbon nanotube from the p-type to the n-type. A third reason for the low Seebeck coefficient of multi-walled carbon nanotube films is that multi-walled carbon nanotube films are generally considered to be more "metallized" than single-walled/double-walled carbon nanotubes. Thus, the coaxial structure, associated low surface area, more "metallic" behavior, and larger diameter result in a low seebeck coefficient for n-type multiwall carbon nanotube films.
On the basis of ensuring the conversion from the p-type carbon nanotube film to the n-type film, the electrical conductivity is maintained at a high level and a high Seebeck coefficient, and the n-type carbon nanotube film which is stable in the air is a great challenge.
Disclosure of Invention
The invention aims to provide a preparation method of an n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing an n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance comprises the following steps:
(1) adding an n-type dopant into an organic solvent, and performing ultrasonic dispersion to obtain a solution of the n-type dopant;
(2) soaking the multi-wall carbon nanotube film in a solution of an n-type dopant for 1.5 to 3 hours; and then taking out the multiwalled carbon nanotube film obtained after soaking, washing and drying to obtain the n-type multiwalled carbon nanotube thermoelectric material.
The invention further improves the method that in the step (1), the mass ratio of the n-type dopant to the organic solvent is (2-8): 100.
In a further development of the invention, in step (1), the N-type dopant is N-DMBI or PEI.
In a further improvement of the invention, in the step (1), the organic solvent is dimethyl sulfoxide, ethanol or methanol.
The further improvement of the invention is that the ultrasonic dispersion in the step (1) is specifically as follows: ultrasonic dispersion is carried out for 0.5-1.5h under 400W.
The invention has the further improvement that in the step (2), the mass percentage of the iron in the multi-wall carbon nano tube film is 1 percent, 5 percent or 10 percent.
In the further improvement of the invention, in the step (2), the multi-wall carbon nano tube film is prepared by a chemical vapor deposition method.
The invention is further improved in that in the step (2), deionized water, absolute ethyl alcohol or methanol is adopted for cleaning.
The further improvement of the invention is that in the step (2), the drying is carried out in a vacuum drying oven, the drying temperature is 50-70 ℃, and the drying time is 1-3 h.
Compared with the prior art, the invention has the following beneficial effects: the multi-walled carbon nanotube film with the n-type thermoelectric material characteristic is prepared by taking the multi-walled carbon nanotube film as a matrix and adopting an n-type dopant for transformation. A series of related characterization of the performance and the stability of the doped carbon nanotube film shows that the multi-walled carbon nanotube film after being doped by the N-DMBI is successfully converted from a p type to an N type, and the conductivity and the Seebeck coefficient of the multi-walled carbon nanotube film are improved. Therefore, the synthesis method of the n-type multi-walled carbon nanotube film thermoelectric material has significant importance, and provides an important reference method for simply and efficiently preparing a wearable electronic device in a large area in the future. The invention not only has convenient operation process, and the processed n-type multi-walled carbon nanotube film has higher power factor and stability of long-time performance in air, but also greatly improves the application prospect of the n-type multi-walled carbon nanotube film as a thermoelectric material.
Furthermore, the invention utilizes the P-type multi-walled carbon nanotube film which is prepared at low cost as a substrate for transformation, optimizes the content of catalyst ferrocene in the process of preparing the multi-walled carbon nanotube film by a chemical vapor deposition method, and distributes partial iron catalyst particles in the carbon nanotube to form a carbon-coated iron structure after pyrolysis.
Drawings
FIG. 1 is a graph of conductivity versus temperature for N-DMBI doped multi-walled carbon nanotube films prepared in example 1.
FIG. 2 is a graph of Seebeck coefficient versus temperature for the N-DMBI doped multi-walled carbon nanotube film prepared in example 1.
FIG. 3 is a graph of power factor versus temperature for the N-DMBI doped multi-walled carbon nanotube film prepared in example 1.
FIG. 4 is a graph of conductivity and Seebeck coefficient of N-DMBI doped multi-walled carbon nanotube films prepared in example 1 after complete exposure to air as a function of time of sample exposure to air.
FIG. 5 is a graph showing the change of conductivity with temperature of the PEI-doped multi-walled carbon nanotube film prepared in example 2.
FIG. 6 is a graph showing the Seebeck coefficient as a function of temperature for the PEI-doped multi-walled carbon nanotube film prepared in example 2.
FIG. 7 is a graph showing the power factor as a function of temperature for the PEI doped multi-walled carbon nanotube film prepared in example 2.
FIG. 8 is a graph of the electrical conductivity and Seebeck coefficient of a PEI doped multi-walled carbon nanotube film prepared in example 2 tested after complete exposure to air as a function of time of the sample exposure to air.
FIG. 9 is a transmission electron microscope image of multi-walled carbon nanotube films prepared by chemical vapor deposition as used in examples 1 and 2.
FIG. 10 is a comparison of the Seebeck coefficients of the original multiwall carbon nanotube films of example 1, example 6 and example 7 with different iron contents and the multiwall carbon nanotube films after 6% Wt N-DMBI doping.
FIG. 11 is an X-ray photoelectron spectrum of a multi-walled carbon nanotube film containing 5% by mass of iron in example 1. Wherein, (a) is a Fe2p3/2 peak spectrum, (b) is a C1s peak spectrum, and (C) is an O1s peak spectrum.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention uses N-DMBI as a doping agent, and takes multi-walled carbon nanotube films with different titanium contents and carbon-coated iron structures prepared by chemical vapor deposition as a matrix, thereby preparing the multi-walled carbon nanotube film with N-type thermoelectric material characteristics and stability in air. The method specifically comprises the following steps:
(1) preparing a solution from an n-type dopant and an organic solvent according to the mass ratio of (2-8) to 100, and placing the prepared solution into an ultrasonic instrument for 400W ultrasonic dispersion for 0.5-1.5hmin to obtain a solution of the n-type dopant;
(2) cutting the multi-walled carbon nanotube film obtained by chemical vapor deposition into rectangular strips with the length and width of 25mm and 6mm respectively; the structure of the multi-walled carbon nanotube film obtained by chemical vapor deposition is shown in fig. 9, the iron content is 1%, 5% or 10%, the X-ray photoelectron spectrum diagram is shown in fig. 11, because the catalyst ferrocene used in the process of preparing the multi-walled carbon nanotube film by the chemical vapor deposition method has a carbon-coated iron structure formed by distributing partial iron catalyst particles in the carbon nanotube after high-temperature cracking, just because of the structure of the carbon-coated iron, the iron existing in the tube exists in the form of iron simple substance and has strong reducibility, so that the multi-walled carbon nanotube film is easily transformed into a thermoelectric material with n-type characteristics compared with the traditional multi-walled carbon nanotube.
(3) Soaking the cut multi-wall carbon nano tube film in a fully dispersed solution of an n-type dopant for 1.5 to 3 hours;
(4) clamping the multi-walled carbon nanotube film obtained after soaking in the step (3) by using tweezers, and cleaning the multi-walled carbon nanotube film for three times by using deionized water to remove organic matters remained on the surface of the film;
(5) and (5) placing the film obtained in the step (4) on clean pumping filter paper, clamping the film by using a glass sheet, and drying the film for 2 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the n-type multi-walled carbon nanotube film material.
Wherein the N-type dopant is N-DMBI (1, 3-dimethyl-2-phenyl-2, 3-dihydro-1H-benzimidazole), which may also be PEI chosen as the N-type dopant, preferably N-DMBI.
The mixture ratio of the N-DMBI to the organic solvent in the step (1) is (2-8):100, it may also be 6: 100. 2:100, 4:100 or 8:100, preferably 6:100, mass ratio. The organic solvent is dimethyl sulfoxide, ethanol or methanol.
The ultrasonic treatment time for the solution in the step (1) is 0.5-1.5h, and can be 30min, 1h or 1.5h, and preferably 30 min.
The soaking time of the multi-wall carbon nanotube film in the step (3) is 1.5h-3h, and the soaking time can be 1.5h, 2h or 3h, preferably 2 h.
Deionized water is used for cleaning the film in the step (4), and the deionized water can be replaced by absolute ethyl alcohol or methanol for cleaning the film, preferably deionized water.
In the step (5), the film obtained in the step (4) is dried for 1-3h at 50-70 ℃ in a vacuum drying oven, wherein the vacuum drying temperature can be 50 ℃, 60 ℃ and 70 ℃, and the vacuum drying time can be 1h, 2h and 3h, preferably 60 ℃ for 2 h.
Preferably, the preparation method of the N-type nanocomposite thermoelectric material compounded by N-DMBI (1, 3-dimethyl-2-phenyl-2, 3-dihydro-1H-benzimidazole) and the multi-wall carbon nanotube film containing the carbon-coated iron structure has the advantages that the multi-wall carbon nanotube after being doped by an N-type dopant N-DMBI shows high stability and good thermoelectric performance in air.
The following are specific examples.
Example 1
(1) Preparing N-DMBI and dimethyl sulfoxide into a solution according to the mass ratio of 6:100, and placing the prepared solution in an ultrasonic instrument for ultrasonic dispersion at 400W for 30 min;
(2) cutting a multi-wall carbon nanotube film (the iron mass is 5%) obtained by chemical vapor deposition into rectangular strips with the length and the width of 25mm and 6mm respectively;
(3) soaking the cut multi-wall carbon nano tube film in a fully dispersed solution for 2 hours;
(4) clamping the carbon film obtained in the step (3) out by using tweezers, and cleaning the carbon film for three times by using deionized water to remove organic matters remained on the surface of the film;
(5) and (5) placing the film obtained in the step (4) on clean pumping filter paper, clamping the film by using a glass sheet, and drying the film for 2 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the n-type multi-walled carbon nanotube film material.
The function curve of the conductivity of the n-type multi-walled carbon nanotube film prepared in the embodiment along with the change of temperature is shown in fig. 1, the function curve of the Seebeck coefficient along with the change of temperature is shown in fig. 2, the function curve of the power factor along with the change of temperature is shown in fig. 3, and as can be seen from the above fig. 1, 2 and 3, the conductivity decreases along with the increase of temperature and shows the metal characteristics; as the Seebeck coefficient is negative in the whole temperature range of the temperature change test, the multi-walled carbon nanotube film prepared by the embodiment has n-type characteristics, and the absolute value of the Seebeck coefficient shows an increasing trend along with the increase of the temperature; the power factor obtained by calculation has small change amplitude along with the increase of the temperature in the whole temperature-changing test interval; the power factor of the sample prepared in the embodiment can reach 121.8 mu Wm at the temperature of 95 DEG C-1K-2。
The change curve of the conductivity and the Seebeck coefficient of the N-type multi-walled carbon nanotube film obtained by the test in the embodiment after the N-type multi-walled carbon nanotube film is completely exposed in the air without any encapsulation along with the time of the sample exposed in the air is shown in fig. 4, and as can be seen from fig. 4, the conductivity has a small reduction after the N-type multi-walled carbon nanotube film is completely exposed in the air for 60 days, and the Seebeck coefficient has no obvious change and only a small reduction in the whole test period, so that the multi-walled carbon nanotube film doped with N-DMBI has good thermoelectric property stability.
Example 2
According to the steps and the method described in the example 1, the n-type dopant in the step (1) is replaced by PEI, and the PEI and a dimethyl sulfoxide solution (DMSO) are prepared into a solution according to the mass ratio of 5:100, so that the PEI-doped n-type multi-walled carbon nanotube film is prepared.
The function curve of the conductivity of the n-type multi-walled carbon nanotube film prepared by the embodiment along with the temperature change is shown in fig. 5, the function curve of the Seebeck coefficient along with the temperature change is shown in fig. 6, and the power factor isThe graph of the function of the daughter versus temperature is shown in fig. 7, and it can be seen from fig. 5, 6 and 7 that the conductivity decreases with the increase of the temperature, showing the metal characteristic; similarly, as the Seebeck coefficient is a negative value in the whole temperature range of the temperature change test, the multi-walled carbon nanotube film prepared by the embodiment shows an n-type characteristic, and the absolute value of the Seebeck coefficient shows an increasing trend along with the increase of the temperature; the power factor obtained by calculation is increased with the temperature in the whole temperature-changing test interval in a small amplitude; the power factor of the sample prepared in the embodiment can reach 65.7 mu Wm at 65 DEG C-1K-2。
The change curves of the conductivity and the Seebeck coefficient of the n-type multi-walled carbon nanotube film prepared in the embodiment, which are measured by completely exposing the film in the air without any encapsulation, along with the time of exposing the sample in the air are shown in FIG. 8, and it can be seen from FIG. 8 that the conductivity is greatly reduced after completely exposing the film in the air for 60 days, and simultaneously, the Seebeck coefficient is changed from-52.3 mu VK-1Sharp change to-11.2 μ VK-1Therefore, the multi-walled carbon nanotube film doped with PEI has unstable thermoelectric performance.
Example 3
(1) Preparing N-DMBI and dimethyl sulfoxide into a solution according to the mass ratio of 2:100, placing the prepared solution in an ultrasonic instrument, and performing ultrasonic dispersion for 30min at 400W;
(2) cutting the multi-walled carbon nanotube film obtained by chemical vapor deposition into rectangular strips with the length and width of 25mm and 6mm respectively;
(3) soaking the cut multi-wall carbon nano tube film in a fully dispersed solution for 2 hours;
(4) clamping the carbon film obtained in the step (3) out by using tweezers, and cleaning the carbon film for three times by using absolute ethyl alcohol to remove organic matters remained on the surface of the film;
(5) and (5) placing the film obtained in the step (4) on clean pumping filter paper, clamping the film by using a glass sheet, and drying the film for 2 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the n-type multi-walled carbon nanotube film material.
Example 4
(1) Preparing N-DMBI and ethanol into a solution according to a mass ratio of 4:100, and placing the prepared solution in an ultrasonic instrument under 400W for ultrasonic dispersion for 1 h;
(2) cutting a multi-wall carbon nanotube film (the mass percentage of iron is 1%) obtained by chemical vapor deposition into rectangular strips with the length and the width of 25mm and 6mm respectively;
(3) soaking the cut multi-wall carbon nano tube film in a fully dispersed solution for 1.5 h;
(4) clamping the carbon film obtained in the step (3) out by using tweezers, and cleaning the carbon film for three times by using absolute ethyl alcohol to remove organic matters remained on the surface of the film;
(5) and (3) placing the film obtained in the step (4) on clean pumping filter paper, clamping the film by using a glass sheet, and drying the film for 3 hours in a vacuum drying oven at the temperature of 50 ℃ to obtain the n-type multi-walled carbon nanotube film material.
Example 5
(1) Preparing a solution from N-DMBI and methanol according to a mass ratio of 8:100, and placing the prepared solution in a 400W ultrasonic instrument for ultrasonic dispersion for 1.5h at 400W;
(2) cutting a multi-wall carbon nano tube film obtained by chemical vapor deposition (the mass percentage of iron is 10%) into rectangular strips with the length and the width of 25mm and 6mm respectively;
(3) soaking the cut multi-wall carbon nano tube film in a fully dispersed solution for 3 hours;
(4) clamping the carbon film obtained in the step (3) out by using tweezers, and cleaning for three times by using methanol to remove organic matters remained on the surface of the film;
(5) and (5) placing the film obtained in the step (4) on clean pumping filter paper, clamping the film by using a glass sheet, and drying the film for 1h in a vacuum drying oven at 70 ℃ to obtain the n-type multi-walled carbon nanotube film material.
Example 6
Unlike example 1, the amount of iron in the multiwall carbon nanotube film was 1% by mass.
Example 7
Unlike example 1, the amount of iron in the multiwall carbon nanotube film was 10% by mass.
As can be seen from fig. 10, the n-type multi-walled carbon nanotube film material of the present invention has better performance than the multi-walled carbon nanotube film without n-type dopant, and the n-type multi-walled carbon nanotube film material prepared in example 5 has the best performance.
According to the invention, the multiwall carbon nanotube film is embedded with different iron contents, so that the multiwall carbon nanotube film has a carbon-coated iron structure and is converted into a high-performance N-type multiwall carbon nanotube film which stably exists in the air, specifically, a p-type multiwall carbon nanotube film which is cheap and can be prepared in a large area is selected as a conversion object, a plurality of rows of multiwall carbon nanotube films with different iron contents are designed, a plurality of N-type dopants are screened, and finally, N-DMBI is determined to be used as an N-type dopant, and a series of related characterization of performance and stability of the carbon nanotube film after being doped with N-DMBI shows that the multiwall carbon nanotube film after being doped with N-DMBI is successfully converted from p type to N type, and the conductivity and the Seebeck. Therefore, the synthesis method of the thermoelectric material has significant importance, and provides an important reference method for realizing simple, high-efficiency and large-area preparation of wearable electronic devices in the future.
Claims (9)
1. A preparation method of an n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance is characterized by comprising the following steps:
(1) adding an n-type dopant into an organic solvent, and performing ultrasonic dispersion to obtain a solution of the n-type dopant;
(2) soaking the multi-wall carbon nanotube film in a solution of an n-type dopant for 1.5 to 3 hours; and then taking out the multiwalled carbon nanotube film obtained after soaking, washing and drying to obtain the n-type multiwalled carbon nanotube thermoelectric material.
2. The method for preparing an air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein the n-type dopant is added to the organic solvent at a mass ratio of (2-8):100 in step (1).
3. The method of claim 1, wherein in step (1), the N-type dopant is N-DMBI or PEI.
4. The method for preparing an air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein in the step (1), the organic solvent is dimethyl sulfoxide, ethanol or methanol.
5. The method for preparing the air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein the ultrasonic dispersion in the step (1) is specifically as follows: ultrasonic dispersion is carried out for 0.5-1.5h under 400W.
6. The method for preparing an air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein in the step (2), the multi-walled carbon nanotube film is prepared by chemical vapor deposition.
7. The method for preparing an air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein the mass percentage of iron in the multi-walled carbon nanotube film in step (2) is 1%, 5% or 10%.
8. The method for preparing an air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein in the step (2), deionized water, absolute ethyl alcohol or methanol is used for cleaning.
9. The method for preparing an air-stable and high-performance n-type multi-walled carbon nanotube thermoelectric material as claimed in claim 1, wherein the drying in step (2) is performed in a vacuum drying oven at a temperature of 50-70 ℃ for 1-3 h.
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| CN114920965A (en) * | 2022-05-06 | 2022-08-19 | 武汉工程大学 | Metal ion modified polyethyleneimine carbon nanotube composite film and preparation method and application thereof |
| CN115260761A (en) * | 2022-07-01 | 2022-11-01 | 武汉工程大学 | Polyethyleneimine modified carbon nanotube composite film and preparation method and application thereof |
| CN116119652A (en) * | 2022-10-26 | 2023-05-16 | 中国科学院电工研究所 | n-type doped single-walled carbon nanotube, preparation and application thereof, n-type doped single-walled carbon nanotube thermoelectric film and preparation method thereof |
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