CN116119652A - n-type doped single-walled carbon nanotube, preparation and application thereof, n-type doped single-walled carbon nanotube thermoelectric film and preparation method thereof - Google Patents
n-type doped single-walled carbon nanotube, preparation and application thereof, n-type doped single-walled carbon nanotube thermoelectric film and preparation method thereof Download PDFInfo
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
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Abstract
The invention belongs to the technical field of thermoelectric materials, and particularly relates to an n-type doped single-walled carbon nanotube, a preparation method and an application thereof, an n-type doped single-walled carbon nanotube thermoelectric film and a preparation method thereof. The invention provides an n-type doped single-walled carbon nanotube, which comprises a polyvinylpyrrolidone covalent grafting modified single-walled carbon nanotube. According to the invention, polyvinylpyrrolidone with excellent physiological inertia and excellent biocompatibility is used as an electron donating reducer, and when the single-wall carbon nano tube is modified through covalent bond grafting, a C-N covalent bond can be formed with pi electrons dissociated from SWCNTs, and electrons are provided for the SWCNTs, so that the SWCNTs have N-type semiconductor characteristics. Meanwhile, PVP is adsorbed on the surface of SWCNTs through covalent bonds, and the PVP is used as a surfactant, so that the dispersibility of n-type doped SWCNTs can be improved, the n-type doped SWCNTs can be more uniformly dispersed with each other, and the preparation of the SWCNTs film with uniform morphology is facilitated.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to an n-type doped single-walled carbon nanotube, a preparation method and an application thereof, an n-type doped single-walled carbon nanotube thermoelectric film and a preparation method thereof.
Background
Thermoelectric devices are devices capable of realizing the mutual conversion of heat energy and electric energy, and mainly have two applications, namely thermoelectric generation; and secondly, thermoelectric refrigeration and heating. The thermoelectric material applied to the thermoelectric device is a novel energy material which is environment-friendly and has wide application prospect.
Adjacent carbon atoms of single-walled carbon nanotubes (SWCNTs) form a hexagonal array, each carbon atom being adjacent to three nearest atoms to form a covalent bond, the remaining one electron being referred to as pi-electron, which can move approximately freely within the carbon tube, and the conductivity of single-walled carbon nanotubes depends primarily on pi-electrons. SWCNTs, a typical one-dimensional material, have received great attention in the field of thermoelectric materials due to their excellent mechanical, electrical and thermal properties. Currently, SWCNTs have been successfully used in the field of thermoelectric materials. Because the SWCNTs composite thermoelectric material has the advantages of light weight, strong flexibility, low cost and the like, the SWCNTs composite thermoelectric material is more suitable for flexible, stretchable and wearable electronic devices and complex working environments with uneven surfaces.
A complete thermoelectric device typically requires that both p-type and n-type materials operate simultaneously. Currently, the p-type doping of SWCNTs is very simple and requires little additional operation, as SWCNTs absorb oxygen from the air and are oxidized by oxygen to cause them to exhibit p-type behavior.
However, the n-type doping of SWCNTs is more challenging than the p-type doping, at present, organic small molecules and polyethyleneimine are often used as electron donors to prepare the n-type SWCNTs, however, the film forming performance of the organic small molecules is poor, the mechanical performance of the prepared SWCNTs is lower, and the inherent amplification electrical insulation of the polyethyleneimine inevitably leads to the reduction of the conductivity of the SWCNTs.
Disclosure of Invention
The invention aims to provide an n-type doped single-walled carbon nanotube, a preparation method and an application thereof, and an n-type doped single-walled carbon nanotube thermoelectric film and a preparation method thereof. The preparation method provided by the invention is simple and safe, and the obtained n-type doped single-walled carbon nanotube has high conductivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an n-type doped single-walled carbon nanotube, which comprises a polyvinylpyrrolidone covalent grafting modified single-walled carbon nanotube.
Preferably, the mass ratio of the polyvinylpyrrolidone to the single-walled carbon nanotubes is (2-4): 1.
The invention provides a preparation method of the n-type doped single-walled carbon nanotube, which comprises the following steps:
mixing polyvinylpyrrolidone, single-walled carbon nanotubes and an alcohol solvent to obtain a suspension;
and heating the suspension in a protective gas atmosphere to perform grafting reaction to obtain the n-type doped single-walled carbon nanotube.
Preferably, the temperature of the grafting reaction is 270-280 ℃, and the heat preservation time of the grafting reaction is 15-24 hours.
Preferably, the grafting reaction directly obtains a grafting reaction liquid, and the grafting reaction liquid is subjected to alcohol precipitation, solid-liquid separation and washing in sequence to obtain the n-type doped single-walled carbon nanotube; the alcohol solvent for alcohol precipitation is isopropanol.
The invention provides the application of the n-type doped single-walled carbon nanotube prepared by the technical scheme or the preparation method of the technical scheme as a thermoelectric material.
The invention provides a preparation method of an n-doped single-walled carbon nanotube thermoelectric film, which comprises the following steps:
mixing the n-type doped single-walled carbon nanotubes, an organic binder and an organic solvent to obtain mixed slurry; the n-type doped single-walled carbon nanotube is the n-type doped single-walled carbon nanotube prepared by the technical scheme or the preparation method of the technical scheme;
forming a film from the mixed slurry to obtain a wet film;
and heating and curing the wet film to obtain the n-type doped single-walled carbon nanotube thermoelectric film.
Preferably, the organic binder comprises polyvinylidene fluoride, and the mass ratio of the n-type doped single-walled carbon nanotubes to the organic binder is (4-6): 1.
Preferably, the curing temperature is 75-80 ℃, and the curing heat preservation time is 1-3 h.
The invention provides the n-type doped single-walled carbon nanotube thermoelectric film prepared by the preparation method, which is a self-supporting flexible film.
The invention provides an n-type doped single-walled carbon nanotube, which comprises a polyvinylpyrrolidone covalent grafting modified single-walled carbon nanotube. According to the invention, polyvinylpyrrolidone (PVP) with excellent physiological inertia and excellent biocompatibility is used as an electron donating reducing agent, and when single-wall carbon nanotubes (SWCNTs) are modified through covalent bond grafting, a C-N covalent bond can be formed with pi electrons dissociated from the SWCNTs, and electrons are provided for the SWCNTs, so that the SWCNTs have N-type semiconductor characteristics. Meanwhile, PVP is adsorbed on the surface of SWCNTs through covalent bonds, and the PVP is used as a surfactant, so that the dispersibility of n-type doped SWCNTs can be improved, and the n-type doped SWCNTs can be more uniformly dispersed.
The invention provides a preparation method of the n-type doped single-walled carbon nanotube, which comprises the following steps: mixing polyvinylpyrrolidone, single-walled carbon nanotubes and an alcohol solvent to obtain a suspension; and heating the suspension in a protective gas atmosphere to perform grafting reaction to obtain the n-type doped single-walled carbon nanotube. In an alcohol solution, PVP is used as an electron donating reducer to carry out covalent grafting modification on SWCNTs, so that the n-type doped single-walled carbon nanotube is prepared. The preparation method provided by the invention is simple, low in cost and easy to implement, and is expected to be applied in a large scale.
The invention provides a preparation method of an n-type doped single-walled carbon nanotube thermoelectric film, which comprises the following steps: mixing the n-type doped single-walled carbon nanotubes, an organic binder and an organic solvent to obtain mixed slurry; the n-type doped single-walled carbon nanotube is the n-type doped single-walled carbon nanotube prepared by the technical scheme or the preparation method of the technical scheme; forming a film from the mixed slurry to obtain a wet film; and heating and curing the wet film to obtain the n-type doped single-walled carbon nanotube thermoelectric film. According to the preparation method provided by the invention, the n-type doped single-walled carbon nanotubes and the organic adhesive are mixed in the organic solvent, and as PVP is coated on the surface of SWCNTs, the dispersibility between the n-type doped single-walled carbon nanotubes and before the n-type doped single-walled carbon nanotubes and the organic adhesive is effectively improved, and the thermoelectric film obtained by curing and film forming has good flexibility and uniformity.
The invention provides the n-type doped single-walled carbon nanotube thermoelectric film prepared by the preparation method, which is a self-supporting flexible film. The n-type doped single-walled carbon nanotube thermoelectric film provided by the invention is a self-supporting flexible film, has good flexibility and uniformity, and is hopeful to be prepared into flexible thermoelectric equipment which can be worn by human body with the existing p-type thermoelectric film.
Drawings
FIG. 1 is a Raman spectrum of an n-type doped SWCNTs film prepared in example 1 of the present invention;
FIG. 2 is a partial magnified view of the Raman spectrum of an n-type doped SWCNTs film prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of an n-type doped SWCNTs film prepared in example 2 of the present invention;
FIG. 4 is a Seebeck coefficient plot of n-type doped SWCNTs films prepared in examples 1, 2, and 3 of the present invention;
FIG. 5 is a graph of conductivity and power factor for n-doped SWCNTs films prepared according to examples 1, 2, and 3 of the present invention.
Detailed Description
The invention provides an n-type doped single-walled carbon nanotube, which comprises a polyvinylpyrrolidone covalent grafting modified single-walled carbon nanotube.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
In the invention, the mass ratio of the polyvinylpyrrolidone to the single-walled carbon nanotubes is (2-4): 1, and particularly preferably 2:1, 3:1 or 4:1.
The invention provides a preparation method of the n-type doped single-walled carbon nanotube, which comprises the following steps:
mixing polyvinylpyrrolidone, single-walled carbon nanotubes and an alcohol solvent to obtain a suspension;
and heating the suspension in a protective gas atmosphere to perform grafting reaction to obtain the n-type doped single-walled carbon nanotube.
In the present invention, polyvinylpyrrolidone, single-walled carbon nanotubes and an alcohol solvent are mixed (hereinafter referred to as a first mixture) to obtain a suspension.
In the present invention, the alcohol solvent is particularly preferably ethylene glycol.
In the invention, the mass ratio of the polyvinylpyrrolidone to the single-walled carbon nanotubes is (2-4): 1, and particularly preferably 2:1, 3:1 or 4:1.
The invention has no special requirement on the dosage of the glycol, and can ensure that the grafting reaction is carried out.
In the present invention, the first mixing is preferably performed under stirring, and the stirring speed is preferably 1100rad/min.
After the suspension is obtained, the n-type doped single-walled carbon nanotube is obtained by heating the suspension in a protective gas atmosphere to perform grafting reaction.
In the present invention, the protective gas atmosphere is particularly preferably an inert gas atmosphere.
In the present invention, the temperature of the grafting reaction is preferably 270 to 280℃and more preferably 275 ℃.
In the present invention, the holding time of the grafting reaction is preferably 15 to 24 hours, more preferably 20 hours.
In the present invention, the grafting reaction is preferably carried out under stirring, preferably at a speed of 1100rad/min. In a specific embodiment of the present invention, the stirring is particularly preferably magnetic stirring.
In the present invention, the grafting reaction is preferably carried out in a reactor with a magnetically heated stirrer.
In the invention, the grafting reaction directly obtains grafting reaction liquid, and after the grafting reaction, the invention preferably further comprises the steps of sequentially carrying out alcohol precipitation, solid-liquid separation and washing on the grafting reaction liquid to obtain the n-type doped single-walled carbon nanotube; the alcohol solvent for alcohol precipitation is isopropanol.
In the present invention, the alcohol precipitation is preferably performed by mixing the grafting reaction solution with an alcohol solvent for alcohol precipitation. In the present invention, the ratio of the volume of the alcohol solvent for alcohol precipitation to the volume of the grafting reaction liquid is preferably 1:1.
In the invention, the solid-liquid separation is preferably carried out on the alcohol precipitation reaction liquid obtained by alcohol precipitation, in the invention, the solid-liquid separation is preferably centrifugal, and the invention has no special requirement on the specific implementation process of the ions.
The solid product obtained by the solid-liquid separation is preferably washed, and in the present invention, the washing solvent is preferably ethanol, and in the present invention, the number of times of washing is preferably 3. The present invention preferably removes unreacted raw materials and ethylene glycol by the washing.
The invention provides the application of the n-type doped single-walled carbon nanotube prepared by the technical scheme or the preparation method of the technical scheme as a thermoelectric material.
The invention provides a preparation method of an n-doped single-walled carbon nanotube thermoelectric film, which comprises the following steps:
mixing the n-type doped single-walled carbon nanotubes, an organic binder and an organic solvent to obtain mixed slurry; the n-type doped single-walled carbon nanotube is the n-type doped single-walled carbon nanotube prepared by the technical scheme or the preparation method of the technical scheme;
forming a film from the mixed slurry to obtain a wet film;
and heating and curing the wet film to obtain the n-type doped single-walled carbon nanotube thermoelectric film.
The invention mixes the n-type doped single-walled carbon nanotube, the organic binder and the organic solvent (hereinafter referred to as second mixing) to obtain mixed slurry; the n-type doped single-walled carbon nanotube is the n-type doped single-walled carbon nanotube prepared by the technical scheme or the preparation method.
In the present invention, the organic binder preferably includes polyvinylidene fluoride.
In the present invention, the organic solvent is particularly preferably N, N-Dimethylformamide (DMF).
In the present invention, the mass ratio of the n-type doped single-walled carbon nanotubes to the organic binder is preferably (4 to 6): 1, more preferably 5:1.
The invention has no special requirement on the dosage of the organic solvent, and can ensure that the n-type doped single-walled carbon nanotube and the organic adhesive are uniformly mixed.
In the present invention, the second mixing is preferably performed under ultrasonic conditions, and the power of the ultrasonic waves is preferably 360W; the frequency of the ultrasound is preferably 40HZ and the time of the ultrasound is preferably 1h.
After the mixed slurry is obtained, the mixed slurry is formed into a film to obtain a wet film.
In the present invention, the film formation is preferably: and coating the mixed slurry on the surface of a substrate to form a film.
In the present invention, the substrate is preferably made of glass.
In the present invention, the coating is particularly preferably spin coating.
In the present invention, the thickness of the wet film is preferably 60 μm.
After the wet film is obtained, the wet film is heated and solidified, and the n-type doped single-walled carbon nanotube thermoelectric film is obtained.
In the present invention, the curing temperature is preferably 75 to 80 ℃, more preferably 80 ℃.
In the present invention, the heat-retaining time for the curing is preferably 1 to 3 hours, more preferably 3 hours.
In the present invention, the n-type doped single-walled carbon nanotube thermoelectric thin film is preferably peeled from the substrate after the curing when the film is formed on the substrate surface.
The invention has no special requirements for the specific implementation process of the stripping.
In the present invention, the thickness of the n-type doped single-walled carbon nanotube thermoelectric thin film is preferably 30 μm.
The invention provides the n-type doped single-walled carbon nanotube thermoelectric film prepared by the preparation method, which is a self-supporting flexible film.
The n-type doped single-walled carbon nanotube thermoelectric film provided by the invention has uniform morphology, independent self-supporting performance, good flexibility and uniformity, and is expected to be prepared into flexible thermoelectric equipment which can be worn by human body with the existing p-type thermoelectric film.
The technical solutions provided by the present invention are described in detail below with reference to the drawings and examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
0.098232g PVP and 0.032744g SWCNTs are weighed and mixed with ethylene glycol to obtain a suspension;
transferring the suspension to a reaction kettle under the inert gas atmosphere condition, placing the suspension in a magnetic heating stirrer, stirring while heating, and reacting for 20 hours at 275 ℃ at the stirring speed of 1100 rad/min; obtaining grafting reaction liquid;
and cooling the grafting reaction liquid to room temperature, carrying out alcohol precipitation by using isopropanol with the volume ratio of the isopropanol to the grafting reaction liquid being 1:1, then carrying out centrifugal precipitation to obtain a solid product, and washing the solid product with ethanol for 3 times to remove unreacted raw materials and ethylene glycol, thereby obtaining the n-type doped single-walled carbon nanotube.
Mixing n-doped single-walled carbon nanotubes and 0.0109g PVDF in DMF at a mass ratio of 5:1 for 1h with an ultrasonic power of 360W and an ultrasonic frequency of 40HZ; obtaining mixed slurry;
coating the mixed slurry on glass to obtain a wet film with the thickness of 60 mu m;
and (3) solidifying the wet film at 80 ℃ for 3 hours, and then stripping the wet film from the glass to obtain the independently supportable n-type doped single-walled carbon nanotube thermoelectric film with the thickness of 30 mu m.
The structure and morphology of the n-type doped single-walled carbon nanotube thermoelectric film were analyzed by raman spectroscopy. Characteristic Raman peaks of SWCNTs include the D peak (-1341 cm) -1 ) And G peak (. About.1592 cm) -1 ) Resonance scattering and sp induced by defect, respectively 2 In-plane stretching vibrations of the hybridized carbon atoms. As can be seen from the Raman spectra of FIGS. 1-2, the n-type doped single-walled carbon nanotube thermoelectric film prepared in the embodiment is SWCNTs, and the spectrum shows that the G diffraction peak of the SWCNTs film (n-type doped single-walled carbon nanotube thermoelectric film) after covalent grafting modification PVP has blue shift compared with that of the original carbon tube, and the spectrum is 1592.48cm -1 To 1591.11cm -1 This indicates PVP and carbon nanotube SP 2 The hybridization bonds and electrons are transferred from PVP to SWCNTs, which is also consistent with the n-type Seebeck coefficient measured by PTM.
Example 2
0.130976g PVP and 0.032744g SWCNTs are weighed and mixed with ethylene glycol to obtain a suspension;
transferring the suspension to a reaction kettle under the inert gas atmosphere condition, placing the suspension in a magnetic heating stirrer, stirring while heating, and reacting for 20 hours at 275 ℃ at the stirring speed of 1100 rad/min; obtaining grafting reaction liquid;
and cooling the grafting reaction liquid to room temperature, carrying out alcohol precipitation by using isopropanol with the volume ratio of the isopropanol to the grafting reaction liquid being 1:1, then carrying out centrifugal precipitation to obtain a solid product, and washing the solid product with ethanol for 3 times to remove unreacted raw materials and ethylene glycol, thereby obtaining the n-type doped single-walled carbon nanotube.
Mixing n-doped single-walled carbon nanotubes and 0.0109g PVDF in DMF at a mass ratio of 5:1 for 1h with an ultrasonic power of 360W and an ultrasonic frequency of 40HZ; obtaining mixed slurry;
coating the mixed slurry on glass to obtain a wet film with the thickness of 60 mu m;
and (3) solidifying the wet film at 80 ℃ for 3 hours, and then stripping the wet film from the glass to obtain the independently supportable n-type doped single-walled carbon nanotube thermoelectric film with the thickness of 30 mu m.
The surface morphology of the n-type doped single-walled carbon nanotube thermoelectric film sample prepared in this example was observed by using a scanning electron microscope, and SWCNTs in the n-type doped single-walled carbon nanotube thermoelectric film prepared in this example were well dispersed and the film surface was uniform, as shown in fig. 3. And the SWCNTs are subjected to covalent grafting modification by PVP, and compared with SWCNTs without PVP, the SWCNTs with PVP are clear in root and uniformly dispersed. The PVP adsorbed on the carbon tubes can be used as a surfactant and a dispersing agent, so that agglomeration of the carbon tubes is reduced, the carbon tubes are fully and uniformly dispersed, and the PVP can fully coat SWCNTs while being heated in the preparation process, so that the agglomeration among the carbon tubes is reduced.
Example 3
0.065488g PVP and 0.032744g SWCNTs are weighed and mixed with an ethylene glycol solution to obtain a suspension;
transferring the suspension to a reaction kettle under the inert gas atmosphere condition, placing the suspension in a magnetic heating stirrer, stirring while heating, and reacting for 20 hours at 275 ℃ at the stirring speed of 1100 rad/min; obtaining grafting reaction liquid;
and cooling the grafting reaction liquid to room temperature, carrying out alcohol precipitation by using isopropanol with the volume ratio of the isopropanol to the grafting reaction liquid being 1:1, then carrying out centrifugal precipitation to obtain a solid product, and washing the solid product with ethanol for 3 times to remove unreacted raw materials and ethylene glycol, thereby obtaining the n-type doped single-walled carbon nanotube.
Mixing n-doped single-walled carbon nanotubes and 0.0109g PVDF in DMF at a mass ratio of 5:1 for 1h with an ultrasonic power of 360W and an ultrasonic frequency of 40HZ; obtaining mixed slurry;
coating the mixed slurry on glass to obtain a wet film with the thickness of 60 mu m;
and (3) solidifying the wet film at 80 ℃ for 3 hours, and then stripping the wet film from the glass to obtain the independently supportable n-type doped single-walled carbon nanotube thermoelectric film with the thickness of 30 mu m.
The variation of Seebeck coefficient with PVP content of the n-type doped single-walled carbon nanotube thermoelectric film samples prepared in examples 1 to 3 was tested by using a room temperature thermoelectric property evaluation device PTM, as shown in FIG. 4. The Seebeck coefficients of the n-type doped single-walled carbon nanotube thermoelectric films prepared by the embodiment of the invention are all negative numbers, which indicates that the n-type doped single-walled carbon nanotube thermoelectric films prepared by the embodiment of the invention are all n-type semiconductors. And as PVP content increases, seebeck coefficient of the SWCNTs film increases, and the Seebeck coefficient of the n-type doped single-walled carbon nanotube thermoelectric film prepared when the mass ratio PVP is SWCNTs=4:1 is the largest, which is-53 mu V.K -1 The method shows that the covalent bond interaction between PVP and SWCNTs can be further enhanced by a solvothermal method, and PVP provides electrons for the SWCNTs, so that the SWCNTs film shows n-type conduction behavior.
The change of the conductivity of the n-type doped single-walled carbon nanotube thermoelectric film samples prepared in examples 1 to 3 with the PVP content was tested by using a room temperature thermoelectric property evaluation device PTM, and the change of the power factor with the PVP content was obtained, as shown in FIG. 5. By comparison, the conductivity of the n-type doped single-walled carbon nanotube thermoelectric films prepared in examples 1-3 was reduced with increasing PVP content, contrary to the trend of Seebeck coefficient variation. Power factor pf=s 2 Sigma, where S refers to Seebeck coefficientSigma refers to the electrical conductivity of the material. Therefore, the n-doped single-walled carbon nanotube thermoelectric film prepared when the final mass ratio PVP and SWCNTs=3:1 shows the optimal power factor of-72.59 mu W.m -1 ·K -2 。
In summary, compared with the traditional inorganic thermoelectric material, the n-type doped single-walled carbon nanotube thermoelectric film provided by the invention has high Seebeck coefficient, conductivity and power factor, good flexibility and mechanical strength performance, and is expected to be combined with the traditional high-performance p-type thermoelectric film material and applied to flexible wearable thermoelectric equipment. Compared with other thermoelectric film material preparation methods, the n-type doped single-walled carbon nanotube thermoelectric film preparation method provided by the invention is simple, low in cost and easy to realize, and is expected to be applied in a large scale.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. An n-type doped single-walled carbon nanotube is characterized by comprising a polyvinylpyrrolidone covalent grafting modified single-walled carbon nanotube.
2. The n-doped single-walled carbon nanotube according to claim 1, wherein the mass ratio of polyvinylpyrrolidone to single-walled carbon nanotube is (2-4): 1.
3. The method for preparing the n-type doped single-walled carbon nanotube as claimed in claim 1 or 2, comprising the steps of:
mixing polyvinylpyrrolidone, single-walled carbon nanotubes and an alcohol solvent to obtain a suspension;
and heating the suspension in a protective gas atmosphere to perform grafting reaction to obtain the n-type doped single-walled carbon nanotube.
4. The method according to claim 3, wherein the temperature of the grafting reaction is 270-280 ℃, and the heat-preserving time of the grafting reaction is 15-24 hours.
5. The method according to claim 3, wherein the grafting reaction directly obtains a grafting reaction liquid, and the grafting reaction liquid is subjected to alcohol precipitation, solid-liquid separation and washing in sequence to obtain the n-type doped single-walled carbon nanotube; the alcohol solvent for alcohol precipitation is isopropanol.
6. Use of the n-type doped single-walled carbon nanotube of claim 1 or 2 or the n-type doped single-walled carbon nanotube prepared by the preparation method of any of claims 3 to 5 as a thermoelectric material.
7. The preparation method of the n-type doped single-walled carbon nanotube thermoelectric film is characterized by comprising the following steps of:
mixing the n-type doped single-walled carbon nanotubes, an organic binder and an organic solvent to obtain mixed slurry; the n-type doped single-walled carbon nanotube is the n-type doped single-walled carbon nanotube of claim 1 or 2 or the n-type doped single-walled carbon nanotube prepared by the preparation method of any one of claims 3 to 5;
forming a film from the mixed slurry to obtain a wet film;
and heating and curing the wet film to obtain the n-type doped single-walled carbon nanotube thermoelectric film.
8. The method according to claim 7, wherein the organic binder comprises polyvinylidene fluoride, and the mass ratio of the n-type doped single-walled carbon nanotubes to the organic binder is (4-6): 1.
9. The method according to claim 7, wherein the curing temperature is 75 to 80 ℃ and the curing holding time is 1 to 3 hours.
10. The n-type doped single-walled carbon nanotube thermoelectric film prepared by the preparation method of any one of claims 7 to 9, wherein the n-type doped single-walled carbon nanotube thermoelectric film is a self-supporting flexible film.
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