CN110951253A - High-performance polypyrrole-based ternary composite thermoelectric material and preparation method thereof - Google Patents
High-performance polypyrrole-based ternary composite thermoelectric material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance polypyrrole-based ternary composite thermoelectric material and a preparation method thereof. And then compounding the composite thermoelectric material with polyaniline to obtain the polypyrrole/graphene/polyaniline ternary composite thermoelectric material. The method and the material adopted by the invention can improve the dispersibility and compatibility of the composite material, so that a special conductive path is formed between the ternary composite materials, the thermoelectric property of the composite material is improved, the defects of low intrinsic conductivity of polypyrrole, high thermal conductivity of graphene and the like are overcome, and the polypyrrole, the graphene and the polyaniline are compounded, so that a novel preparation method of the polypyrrole-based high thermoelectric property composite material, which is simple to operate, green and environment-friendly and has good component dispersion uniformity, is provided.
Description
Technical Field
The invention belongs to the technical field of preparation of novel energy materials, relates to a composite electric heating material, and particularly relates to a preparation method of a high-performance polypyrrole-based ternary composite thermoelectric material and the high-performance polypyrrole-based ternary composite thermoelectric material prepared by the method.
Background
Energy is the material basis of human activities, and the development of the human society cannot keep away from the appearance of high-quality energy and the use of advanced energy technology. With the development of production and science and technology, environmental pollution and energy crisis phenomena are more and more serious. The thermoelectric material is an environment-friendly functional material, and can realize interconversion of thermal energy and electric energy by utilizing movement of carriers (holes or electrons) in a solid. The thermoelectric device prepared by using the thermoelectric material has the advantages of simple structure, no moving part, no noise, no pollution and the like. Therefore, the thermoelectric material has quite wide application prospect. The thermoelectric materials used at present are mainly inorganic thermoelectric materials, such as Bi-Te base alloy, Pb-Te base alloy and the like, but the preparation process is relatively complex, and the defects of heavy metal pollution and the like exist, so that the large-scale application of the inorganic thermoelectric materials is limited to a certain extent.
The performance index of thermoelectric material is generally expressed by dimensionless figure of merit ZT ═ S2σ T/κ, where S (μ V/K) is Zeebeck coefficient, σ (S/m) is conductivity, T (K) is absolute temperature of high temperature end and low temperature end, and P (S)2σ) represents a power factor (Powerfactor). As can be seen from the ZT expression, in order to improve the thermoelectric conversion efficiency of the material, a thermoelectric material having both a large electrical conductivity and a thermal conductivity as low as possible should be selected. In fact, however, at a certain temperature, the 3 factors determining the ZT value are all functions of the carrier concentration, are interrelated, and it is impossible to optimize them at the same time, which is a main reason that the performance of the thermoelectric material is prevented from being further improved at present. Because the conductive polymer has the characteristics of better conductivity and mechanical property, lower heat conductivity coefficient and the like, the conductive polymer can possibly replace the traditional materials such as semiconductors, metals, superconduction and the like through composite optimization in the near future to become the most excellent thermoelectric material and be applied to the power supply and other fields of micro-electromechanical systems or microelectronic devices.
In recent years, with the intensive research on conductive polymers, various inexpensive conductive polymer materials having a low specific gravity, stable performance and excellent conductive characteristics, such as polyaniline, polypyrrole, polythiophene, polyphenylene ethylene, polydiyne, poly (3, 4-ethylenedioxythiophene), and the like, have been developed. Compared with inorganic thermoelectric materials, conductive polymers are abundant in variety, easy to manufacture, low in cost and light in specific gravity. People predict that through reasonable design of polymer molecular structure, the electric, optical and mechanical properties of the polymer can be effectively controlled, and at present, many countries in the world compete with electronic companies to put conductive polymers into recent electronic material scientific research projects.
For developing Bi capable of replacing the traditional thermoelectric material2Te3The researchers in various countries around the world develop a series of research works for preparing novel organic composite thermoelectric materials by utilizing various conductive polymers. As 2011, Wang et al conducted research work on the preparation of organic composite thermoelectric materials using Polyaniline (PANi) and graphite powder. In 2013, the research work of preparing the organic composite thermoelectric material by mixing Polythiophene (PTH) and multi-walled carbon nanotubes (MWNTs) is carried out by the research work. Research shows that by mixing 50 weight percent of graphite powder in the doped PANI, the electric conductivity of the prepared polymer composite thermoelectric material can be increased by 2 orders of magnitude, and the thermal conductivity is not changed greatly. Under the condition of 393K of temperature, the thermoelectric figure of merit of the polymer composite thermoelectric material can reach 1.37 multiplied by 10-3The thermoelectric figure of merit is greatly improved compared with that of the pure PANi doping. And by mixing 30-80 wt% MWNTs in the PTh, the thermoelectric figure of merit of the PTh/MWNTs composite thermoelectric material can reach 8.71 multiplied by 10-4. However, the thermoelectric figure of merit of the material is relatively small, and thus has a small difference from the application requirements.
In 2011, c.a. hewitt et al prepared graphene/polyvinylidene fluoride (GNs/PVDF) organic composite thermoelectric materials, found that the characteristics of carbon-based thermoelectric materials are related to the intrinsic characteristics of the materials and the external environment, and under certain external conditions, in order to increase the thermoelectric figure of merit of the composite thermoelectric materials, the electrical conductivity of the composite materials must be increased while the thermal conductivity is kept unchanged, which can only be achieved by adding a conductive polymer.
In addition, in recent years, the results of the thermoelectric performance studies of composite materials prepared by using polypyrrole as a matrix are not satisfactory: for example, Wang et al, by in situ polymerization, form pyrrole monomer on the surface of GNs to form adsorption sites, and pyrrole grows along the GNs sheet to obtain PPy/GNs composite material. Due to the strong pi-pi interaction between GNs and PPy, PPy is uniformly coated on the surface of GNs, and finally the power factor of the composite material reaches 10.24 mu Wm-1K-2(RSC adv., 2014, 4, 46187-. Liang et al prepared a series of PPy/SWCNT composites with different SWCNT contents and found that at 40% SWCNT content, the composites had the largest power factor of (19.7 + -0.8) μ Wm-1K-2(J.Mater.chem.C., 2016, 4, 526-. Zhang et al use graphene oxide (rGO) as a template, and the maximum power factor of the prepared PPy/rGO compound is (8.56 +/-0.76) mu Wm-1K-2(J.Mater.chem.C., 2015, 3, 1649-1654). The power factor of the PPy/SWCNT composite material prepared by Liang and the like reaches (21.7 +/-0.8) mu Wm-1K-2(Compos.Sci.Technol.，2016，129，130-136)。
Based on the analysis, the polypyrrole-based high thermoelectric performance composite material which improves the dispersibility and compatibility of the composite material, overcomes the defects of low intrinsic conductivity of polypyrrole, high thermal conductivity of graphene and the like, is simple to operate, is green and environment-friendly, and has good component dispersion uniformity is urgently needed in the industry.
Disclosure of Invention
In view of the above disadvantages, the present invention aims to provide a method for preparing a polypyrrole-based ternary composite thermoelectric material, wherein the polypyrrole-based material in the prior art has low thermoelectric performance. Polypyrrole is introduced into the graphene nanosheets through in-situ polymerization, the advantages of low thermal conductivity of the polypyrrole and high electrical conductivity of the graphene are exerted, and meanwhile polyaniline is introduced into a material system through solution mixing, so that a special conductive network is formed in the composite material, the energy filtering effect is increased, the Zeebeck coefficient is improved, and the thermoelectric performance of the material system is improved. The method combining in-situ polymerization and solution mixing enables polypyrrole to be uniformly coated on the surface of a graphene nanosheet, meanwhile, polyaniline and polypyrrole are similar in structure and have a synergistic effect, the defects that polyaniline nanorods are agglomerated and are not easy to disperse are effectively overcome, the conductivity of the material is effectively improved, and the thermoelectric property of a polypyrrole-based ternary composite material system is enhanced.
The technical scheme of the invention is as follows:
a preparation method of a high-performance polypyrrole-based ternary composite thermoelectric material comprises the following steps:
(1) preparing polyaniline:
preparing polyaniline in situ by aniline, ammonium persulfate and concentrated hydrochloric acid;
(2) preparing a polypyrrole/graphene binary compound:
s1: adding 3-5 g of graphene into 30-50 ml of ethanol solution for ultrasonic dispersion to obtain graphene suspension
S2: maintaining the temperature of the S1 suspension at 0-5 ℃, dropwise adding 2-8 g of pyrrole monomer, and stirring for 30min to obtain a mixed solution;
s3: adding 8-16 g of oxidant into 30-50 mL of deionized water, stirring for dissolving, adding into the mixed solution obtained in the step S2, keeping the temperature at 0-5 ℃, and continuously stirring for reacting to obtain suspended matters;
s4: filtering the suspended substance obtained in the step S3 to obtain black solid precipitate, and then washing and drying the black solid precipitate to obtain a polypyrrole/graphene binary compound;
(3) preparation of polypyrrole/graphene/polyaniline ternary complex
And (3) compounding the polyaniline prepared in the step (1) and the polypyrrole/graphene prepared in the step (2) according to a certain proportion to form a uniform suspension, filtering and drying to obtain the high-performance polypyrrole/graphene/polyaniline ternary composite thermoelectric material.
Wherein the process of in-situ polymerizing polyaniline in step (1) can further adopt the following modes:
adding aniline into the first part of 100mL concentrated hydrochloric acid, and uniformly stirring to prepare an aniline hydrochloric acid solution A; and adding ammonium persulfate into the second part of 100mL concentrated hydrochloric acid, uniformly stirring to prepare a hydrochloric acid solution B of ammonium persulfate, mixing the solution A and the solution B, placing the mixture in a water bath for reaction, and then filtering, washing and drying to obtain polyaniline powder.
The preferred embodiments in step (1) further preferably may be:
carrying out reduced pressure distillation on the aniline monomer for 1-2 times;
the concentration of the concentrated hydrochloric acid of the first part and the second part is 0.8-2.0 mol/L;
the molar ratio of the ammonium persulfate to the aniline is 0.5-2: 1;
the temperature of the water bath is 30-60 ℃;
the reaction time is 8-12 h;
sequentially washing 0.5-1 mol/L HCl solution, absolute ethyl alcohol and deionized water used in the washing process until filtrate is colorless;
the drying time is 20-24 hours, and the drying temperature is 60-80 ℃.
In the step (2), the ethanol solution in the step S1 may be selected from water and absolute ethanol, and is preferably an ethanol solution in which the volume ratio of absolute ethanol to water is 1: 1.
In the step (2), in the step (S3), an oxidant ferric trichloride can be ammonium persulfate, ferric sulfate, potassium persulfate and the like, and is preferably ferric trichloride hexahydrate.
The reaction time of the step S3 in the step (2) is 20-24 h, preferably 24 h.
The washing process of step S4 in step (2) may use ethanol, deionized water, acetone, and diethyl ether, preferably ethanol and deionized water; the drying temperature was 60 ℃.
And (3) compounding polyaniline and polypyrrole/graphene to form a suspension, wherein the used dispersion system is an ethanol solution.
In the step (3), the mass ratio of the polyaniline to the polypyrrole/graphene is 1-1.6: 2.
The invention also discloses a high-performance polypyrrole-based ternary composite thermoelectric material prepared by any one of the preparation methods.
The invention has the beneficial effects that:
1. the method has the advantages of low cost, mild conditions and quick reaction, can maintain lower thermal conductivity while improving the electrical conductivity and the Zeebeck coefficient of the material, and is easy to realize the regular-modulus preparation of higher thermoelectric performance.
2. The novel preparation method of the polypyrrole/graphene/polyaniline ternary composite material is characterized in that the characteristics of low thermal conductivity of polypyrrole and high electrical conductivity of graphene are fully utilized, and the advantages of good compatibility between polypyrrole and polyaniline are organically compounded, so that the novel preparation method of the polypyrrole/graphene/polyaniline ternary composite material is green and environment-friendly, simple to operate, mild in reaction, good in component dispersion uniformity and high in thermoelectric property is provided.
Drawings
FIG. 1 is an SEM photograph of graphene used in example 2 of the present invention;
FIG. 2 is an SEM photograph of polyaniline nanorods of example 2 of the present invention;
FIG. 3 is an SEM photograph of polypyrrole/graphene of example 2 of the present invention;
FIG. 4 is an SEM photograph of polypyrrole/graphene/polyaniline in example 2 of the present invention;
fig. 5 is an SEM photograph of polyaniline/graphene of example 2 of the present invention.
Detailed Description
Example 1
Weighing 2mL of aniline subjected to twice reduced pressure distillation, adding the aniline into 100mL of concentrated hydrochloric acid with the concentration of 0.8mol/L, and uniformly stirring to prepare an aniline hydrochloric acid solution A; adding 5g of ammonium persulfate into 100mL of concentrated hydrochloric acid with the concentration of 0.8mol/L to prepare solution B; and mixing the solution A and the solution B, placing the mixture in a water bath at the temperature of 30 ℃, and stirring to react for 10 hours. Carrying out suction filtration on the suspension, and washing the suspension with 0.8mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water until the filtrate is colorless; and finally, drying the filter cake in a vacuum oven at 60 ℃ for 20 hours to obtain polyaniline powder.
0.03mol of FeCl3·6H2O was dissolved in 30mL of distilled water for use. Adding 3g of graphene into 50mL of ethanol solution (vol ethanol: vol water: 1), stirring for 1h, carrying out ultrasonic treatment for 2h to obtain uniformly dispersed graphene suspension, dissolving 0.03mol of pyrrole monomer in 50mL of ethanol solution, carrying out magnetic stirring for 30min, and slowly stirringSlowly dripping the prepared oxidant solution, and stirring and reacting for 24 hours at the temperature of 5 ℃. And (3) carrying out suction filtration on the reaction liquid to obtain black powder, repeatedly washing the black powder with ethanol and distilled water until filtrate is clear, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the polypyrrole/graphene binary compound. 0.8g of PPy/GNs (polypyrrole/graphene) powder and 0.5g of polyaniline powder are mixed and placed in 100mL of absolute ethyl alcohol, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 2h, so as to obtain uniformly dispersed suspension. And carrying out suction filtration on the reaction suspension, and carrying out vacuum drying for 24h at the temperature of 60 ℃ to obtain the polypyrrole/graphene/polyaniline ternary compound.
Example 2
Weighing 2mL of aniline subjected to twice reduced pressure distillation, adding the aniline into 100mL of concentrated hydrochloric acid with the concentration of 1mol/L, and uniformly stirring to prepare an aniline hydrochloric acid solution A; adding 2.5g of ammonium persulfate into 100mL of concentrated hydrochloric acid with the concentration of 1mol/L to prepare solution B; and mixing the solution A and the solution B, placing the mixture in a water bath at 40 ℃, and stirring to react for 8 hours. Carrying out suction filtration on the suspension, and washing the suspension with 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water until the filtrate is colorless; and finally, drying the filter cake in a vacuum oven at 60 ℃ for 20 hours to obtain polyaniline powder, wherein fig. 2 is an SEM image of the polyaniline nanorod prepared in the embodiment.
0.04mol of FeCl3·6H2O was dissolved in 30mL of distilled water for use. Adding 5g of graphene (fig. 1 is an SEM photo of graphene nanoplatelets used in an example) into 50mL of ethanol solution (vol ethanol: vol water: 1), stirring for 1h, performing ultrasonic treatment for 2h to obtain a uniformly dispersed graphene suspension, dissolving 0.08mol of pyrrole monomer in 50mL of ethanol solution, magnetically stirring for 30min, slowly dropwise adding a prepared oxidant solution, and stirring and reacting for 24h at 5 ℃. And (3) carrying out suction filtration on the reaction solution to obtain black powder, repeatedly washing the black powder with ethanol and distilled water until filtrate is clear, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the polypyrrole/graphene binary compound, wherein an SEM image of the polypyrrole/graphene binary compound is shown in figure 3, and the polypyrrole is uniformly coated on the surface of the graphene sheet layer. And (3) the steps are repeated to synthesize the polypyrrole without adding graphene. Mixing 0.6g of PPy/GNs powder and 0.42g of polyaniline powder, placing the mixture in 100mL of absolute ethyl alcohol, magnetically stirring for 1h, and carrying out ultrasonic treatment for 2h to obtain a uniformly dispersed suspension. The reaction suspension is filtered off with suction and dried in vacuo at 60 ℃And drying for 24 hours to obtain the polypyrrole/graphene/polyaniline ternary compound. Fig. 4 is an SEM image of the polypyrrole/graphene/polyaniline ternary complex prepared in this example. For comparison, 0.6g of graphene powder and 0.42g of polyaniline powder are mixed and placed in 100mL of absolute ethyl alcohol, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 2h, so as to obtain the polyaniline/graphene binary compound. Fig. 5 is an SEM image of polyaniline/graphene, where the polyaniline and graphene nanoplatelets have poor dispersibility and serious polyaniline agglomeration, resulting in large areas of exposed graphene surface. According to the result of fig. 4, polyaniline is uniformly coated on the surface of polypyrrole/graphene, the nano rod-shaped structure of the polyaniline is clear and visible, and compared with the SEM image of polyaniline/graphene in fig. 5, the agglomeration phenomenon of polyaniline is obviously improved, and the structural advantages of the polypyrrole/graphene/polyaniline ternary complex are reflected. Table 1 shows thermoelectric properties of polypyrrole, polyaniline/graphene binary complex, polypyrrole/graphene binary complex, and polypyrrole/graphene/polyaniline ternary complex in this embodiment.
TABLE 1
Example 3
Weighing 1.5mL of aniline subjected to vacuum distillation twice, adding the aniline into 100mL of concentrated hydrochloric acid with the concentration of 1.5mol/L, and uniformly stirring to prepare an aniline hydrochloric acid solution A; adding 3.4g of ammonium persulfate into 100mL of concentrated hydrochloric acid with the concentration of 1.5mol/L to prepare solution B; and mixing the solution A and the solution B, placing the mixture in a water bath at the temperature of 60 ℃, and stirring to react for 12 hours. Carrying out suction filtration on the suspension, and washing the suspension with 1.5mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water until the filtrate is colorless; and finally, drying the filter cake in a vacuum oven at 60 ℃ for 20 hours to obtain polyaniline powder.
0.06mol of FeCl3·6H2O was dissolved in 30mL of distilled water for use. 3g of graphene was added to 5Stirring for 1h in 0mL of ethanol solution (vol ethanol: vol water: 1), carrying out ultrasonic treatment for 2h to obtain uniformly dispersed graphene suspension, then dissolving 0.12mol of pyrrole monomer in 50mL of ethanol solution, carrying out magnetic stirring for 30min, slowly dropwise adding the prepared oxidant solution, and carrying out stirring reaction at 5 ℃ for 24 h. And (3) carrying out suction filtration on the reaction liquid to obtain black powder, repeatedly washing the black powder with ethanol and distilled water until filtrate is clear, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the polypyrrole/graphene binary compound. Mixing 2g of PPy/GNs powder and 1.5g of polyaniline powder, placing the mixture in 100mL of absolute ethyl alcohol, magnetically stirring for 1 hour, and carrying out ultrasonic treatment for 2 hours to obtain a uniformly dispersed suspension. And carrying out suction filtration on the reaction suspension, and carrying out vacuum drying for 24h at the temperature of 60 ℃ to obtain the polypyrrole/graphene/polyaniline ternary compound.
Example 4
Weighing 1.8mL of aniline subjected to twice reduced pressure distillation, adding the aniline into 100mL of concentrated hydrochloric acid with the concentration of 1mol/L, and uniformly stirring to prepare an aniline hydrochloric acid solution A; adding 4.1g of ammonium persulfate into 100mL of concentrated hydrochloric acid with the concentration of 1mol/L to prepare solution B; and mixing the solution A and the solution B, placing the mixture in a water bath at 40 ℃, and stirring to react for 10 hours. Carrying out suction filtration on the suspension, and washing the suspension with 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water until the filtrate is colorless; and finally, drying the filter cake in a vacuum oven at 60 ℃ for 24 hours to obtain polyaniline powder.
0.06mol of FeCl3·6H2O was dissolved in 30mL of distilled water for use. Adding 5g of graphene into 50mL of ethanol solution (vol ethanol: vol water: 1), stirring for 1h, carrying out ultrasonic treatment for 2h to obtain uniformly dispersed graphene suspension, dissolving 0.03mol of pyrrole monomer in 50mL of ethanol solution, carrying out magnetic stirring for 30min, slowly dropwise adding the prepared oxidant solution, and carrying out stirring reaction at 5 ℃ for 24 h. And (3) carrying out suction filtration on the reaction liquid to obtain black powder, repeatedly washing the black powder with ethanol and distilled water until filtrate is clear, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the polypyrrole/graphene binary compound. 0.87g of PPy/GNs powder and 0.7g of polyaniline powder are mixed and placed in 100mL of absolute ethyl alcohol, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 2h, so as to obtain evenly dispersed suspension. And carrying out suction filtration on the reaction suspension, and carrying out vacuum drying for 24h at the temperature of 60 ℃ to obtain the polypyrrole/graphene/polyaniline ternary compound.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are merely preferred embodiments of the present invention, the present invention is not limited thereto, and those skilled in the art will be able to devise many other modifications and embodiments which fall within the spirit and scope of the principles disclosed herein.
Claims (10)
1. A preparation method of a high-performance polypyrrole-based ternary composite thermoelectric material is characterized by comprising the following steps:
(1) preparing polyaniline:
preparing polyaniline powder in situ by aniline, ammonium persulfate and concentrated hydrochloric acid for later use;
(2) preparing a polypyrrole/graphene binary compound:
s1: adding 3-5 g of graphene into 30-50 ml of ethanol solution, and performing ultrasonic dispersion to obtain graphene suspension;
s2: maintaining the temperature of the S1 suspension at 0-5 ℃, dropwise adding 2-8 g of pyrrole monomer, and stirring for 30min to obtain a mixed solution;
s3: adding 8-16 g of oxidant into 30-50 mL of deionized water, stirring for dissolving, adding into the mixed solution obtained in the step S2, keeping the temperature at 0-5 ℃, and continuously stirring for reacting to obtain suspended matters;
s4: filtering the suspended substance obtained in the step S3 to obtain black solid precipitate, and then washing and drying the black solid precipitate to obtain a polypyrrole/graphene binary compound;
(3) preparing a polypyrrole/graphene/polyaniline ternary compound:
and (3) compounding the polyaniline prepared in the step (1) and the polypyrrole/graphene binary compound prepared in the step (2) in proportion to form uniform suspension, filtering and drying to obtain the high-performance polypyrrole-based ternary composite thermoelectric material.
2. The method according to claim 1, wherein the in-situ preparation of polyaniline in step (1) comprises the following steps:
adding aniline monomer into the first part of 100mL concentrated hydrochloric acid, and uniformly stirring to prepare an aniline hydrochloric acid solution A; and adding ammonium persulfate into the second part of 100mL concentrated hydrochloric acid, uniformly stirring to prepare a hydrochloric acid solution B of ammonium persulfate, mixing the solution A and the solution B, placing the mixture in a water bath for reaction, and then filtering, washing and drying to obtain polyaniline powder.
3. The preparation method according to claim 2, wherein the aniline monomer is subjected to reduced pressure distillation for 1-2 times; the concentration of the concentrated hydrochloric acid of the first part and the second part is 0.8-2.0 mol/L; the molar ratio of the ammonium persulfate to the aniline is 0.5-2: 1; the water bath reaction temperature is 30-60 ℃, and the time is 8-12 h; sequentially washing 0.5-1 mol/L HCl solution, absolute ethyl alcohol and deionized water used in the washing process until filtrate is colorless; the drying time is 20-24 hours, and the drying temperature is 60-80 ℃.
4. The method according to claim 1, wherein the ethanol solution in step (2) at S1 is a mixture of anhydrous ethanol and water in equal volume.
5. The preparation method according to claim 1, wherein in the step (2), the oxidant S3 is selected from any one of ferric trichloride, ammonium persulfate, ferric sulfate and potassium persulfate, and is preferably ferric trichloride hexahydrate.
6. The preparation method according to claim 1, wherein the reaction time of S3 in step (2) is 20-24 h, preferably 24 h.
7. The preparation method according to claim 1, wherein the washing in step (2) S4 is selected from any one of ethanol, deionized water, acetone, and diethyl ether, preferably ethanol and deionized water; the drying temperature was 60 ℃.
8. The method according to claim 1, wherein the dispersion used for forming the suspension in the step (3) is an ethanol solution.
9. The preparation method according to claim 1, wherein the mass ratio of the polyaniline to the polypyrrole/graphene in the step (3) is 1-1.6: 2.
10. A high-performance polypyrrole-based ternary composite thermoelectric material prepared by the preparation method according to any one of claims 1 to 9.
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| CN113372767A (en) * | 2021-07-19 | 2021-09-10 | 东莞理工学院 | Thermoelectric-based flame-retardant coating with temperature sensing function and multiple heterogeneous interface structures, and preparation method and application thereof |
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| CN108841173A (en) * | 2018-05-21 | 2018-11-20 | 南昌航空大学 | A kind of synthetic method of material and its application in microorganism fuel cell cathode material |
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| CN108841173A (en) * | 2018-05-21 | 2018-11-20 | 南昌航空大学 | A kind of synthetic method of material and its application in microorganism fuel cell cathode material |
Non-Patent Citations (1)
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| YIHAN WANG ET AL.,: "Polypyrrole/Graphene/Polyaniline Ternary Nanocomposite with High Thermoelectric Power Factor", 《ACS APPL. MATER. INTERFACES》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372767A (en) * | 2021-07-19 | 2021-09-10 | 东莞理工学院 | Thermoelectric-based flame-retardant coating with temperature sensing function and multiple heterogeneous interface structures, and preparation method and application thereof |
| CN113372767B (en) * | 2021-07-19 | 2022-03-04 | 东莞理工学院 | Thermoelectric-based flame-retardant coating with temperature sensing function and multiple heterogeneous interface structures, and preparation method and application thereof |
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