CN110581210B - Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film - Google Patents
Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film Download PDFInfo
- Publication number
- CN110581210B CN110581210B CN201910874159.9A CN201910874159A CN110581210B CN 110581210 B CN110581210 B CN 110581210B CN 201910874159 A CN201910874159 A CN 201910874159A CN 110581210 B CN110581210 B CN 110581210B
- Authority
- CN
- China
- Prior art keywords
- swcnts
- ppy
- thermoelectric film
- solution
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002109 single walled nanotube Substances 0.000 title claims abstract description 85
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002120 nanofilm Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000002019 doping agent Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 58
- 239000002131 composite material Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 38
- 229920000128 polypyrrole Polymers 0.000 description 34
- 239000000463 material Substances 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920000767 polyaniline Polymers 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- GIJBLZITFMMNNN-UHFFFAOYSA-N C1CCCCC1.N1C=CC=C1 Chemical compound C1CCCCC1.N1C=CC=C1 GIJBLZITFMMNNN-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to a preparation method of a PPy-SWCNTs nano composite thermoelectric film and the nano composite thermoelectric film, which comprises the following steps: 1) Dissolving a proper amount of oxidant and p-toluenesulfonic acid serving as a doping agent into water to obtain a solution A, and pre-cooling the solution A at 6-10 ℃ for 1-2 hours; 2) Taking pyrrole monomer and SWCNTs powder, and ultrasonically dispersing the pyrrole monomer and SWCNTs powder in a cyclohexane solution to obtain a solution B; 3) Dropwise adding the solution B into the solution A to form a clear interface; 4) Compared with the prior art, the invention effectively combines the high conductivity of the PPy nano film obtained by low-temperature interfacial polymerization and the high Seebeck coefficient of the SWCNTs, and the power factor at room temperature reaches 37.6 mu V/mK 2 In addition, the preparation method is simple, and the repeatability is high.
Description
Technical Field
The invention relates to the field of semiconductor energy materials, in particular to a preparation method of a PPy-SWCNTs nano composite thermoelectric film and the nano composite thermoelectric film.
Background
With the acceleration of global industrialization process and the rapid population growth, worldwide energy consumption is also increasing, however, energy sources on the earth are limited, some traditional non-renewable energy sources such as coal, petroleum, natural gas and the like are gradually exhausted, and the problem of energy shortage is increasingly prominent, so that the problem of non-neglect of each country is solved, and the long-term stable development of the whole society is severely restricted. In order to alleviate the contradiction between economic development and energy and environment, new renewable clean energy and new high-efficiency energy conversion and storage technologies have been forced to be in the eyebrow as alternatives to traditional fossil fuels. In such a background, thermoelectric energy conversion technology has received high attention as a novel technology for environment-coordinated energy conversion in many advanced countries of the world. Thermoelectric materials are functional materials that enable direct conversion between thermal and electrical energy through the transport of solid internal carriers (holes or electrons). The thermoelectric conversion technology has the unique advantages in the aspect of heat energy utilization due to the characteristics of small volume, no vibration, no noise, no pollution, no abrasion, no moving parts, no maintenance, no pollution and the like.
In the research and application fields of the current thermoelectric materials, the thermoelectric performance of the inorganic semiconductor materials is ideal, and the research is the most extensive. However, the existing inorganic thermoelectric materials are mostly suitable for high and medium temperature conditions, the low-temperature inorganic thermoelectric materials have fewer selectable types, and in addition, the industrial development and application of the inorganic thermoelectric materials are greatly limited due to the factors of high raw material price, complex processing technology, heavy metal pollution and the like.
In recent years, conductive polymers have attracted more and more attention as an emerging thermoelectric material due to their abundant raw materials, light weight, low thermal conductivity, easy synthesis, easy processing, high electrical conductivity comparable to metals, and good environmental stability. The conductive polymer mainly comprises Polyaniline (PANi), polythiophene (PTh), poly 3, 4-ethylenedioxythiophene (PEDOT), polypyrrole (PPy), derivatives thereof and the like. The PEDOT and the PANi have the characteristics of higher conductivity, high solubility in treatment and the like, so that the research progress in the field of organic thermoelectric is great, and the thermoelectric figure of merit reported at present can reach 0.5. However, the conductivity of the PPy reported at present is relatively low, basically 10 1 About S/cm, 1-2 orders of magnitude lower than PEDOT, PANi, by zt=s 2 Sigma T/kappa shows that low electrical conductivity severely limits the thermoelectric properties of the material. The PPy self-supporting film obtained by interfacial polymerization has higher conductivity as reported by Qi et al (Journal of Materials Chemistry C, 2013, 1:7102-7110)) However, we tested that the Seebeck coefficient of the PPy film was low, at about 6-7. Mu.V/K, which limited its further thermoelectric applications.
Compounding with inorganic thermoelectric materials or nanocarbon materials having a high Seebeck coefficient is one common method of improving the performance of organic thermoelectric materials. Carbon Nanotubes (CNTs) are well suited as fillers for polymers to improve the thermoelectric properties of composites due to their good electrical conductivity, mechanical properties and thermal stability. The thermoelectric performance of the material can be remarkably improved by utilizing the synergistic effect and the energy filtering effect of the composite material through compounding with CNTs. The Meng et al (Advanced Materials, 2010, 22, 535-539) prepared PANi-MWCNTs composite material by an in-situ polymerization method, found that after the MWCNTs are compounded with polyaniline, the conductivity and Seebeck coefficient of the composite material are increased simultaneously, and the maximum power factor of the finally obtained composite material is 5.04 mu W/mK 2 The thermoelectric performance is improved by four orders of magnitude compared with that of pure PANi; yao et al (ACS Nano, 2010, 4:2445-2451) mixed SWCNTs powder with aniline monomer in hydrochloric acid solution, and polymerized in situ to obtain a composite material. The SWCNTs are added to improve the structural order of PANi molecular chains, the conductivity and Seebeck coefficient of the final composite material are synergistically increased, and the optimal thermoelectric power factor reaches 20 mu W/mK 2 . Thus, compounding highly conductive PPy films with SWCNTs having a high Seebeck coefficient can result in composites with excellent thermoelectric properties.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a PPy-SWCNTs nano composite thermoelectric film and the nano composite thermoelectric film.
The technical scheme of the invention is as follows:
a preparation method of a PPy-SWCNTs nano composite thermoelectric film comprises the following steps:
1) Dissolving a proper amount of oxidant and p-toluenesulfonic acid serving as a doping agent into water to obtain a solution A, and pre-cooling the solution A at 6-10 ℃ for 1-2 hours;
2) Taking pyrrole monomer and SWCNTs powder, and ultrasonically dispersing the pyrrole monomer and SWCNTs powder in a cyclohexane solution to obtain a solution B;
3) Dropwise adding the solution B into the solution A to form a clear interface;
4) After the reaction is fully carried out at the temperature of 6-10 ℃, the PPy-SWCNTs nano composite thermoelectric film is obtained after cleaning and drying.
The oxidant is FeCl 3 。
The concentration of the dopant is 0.2-0.4M, and the molar ratio of the oxidant to the dopant is 1 (1-5).
The pre-cooling temperature in step 1) was 8℃and the cooling time was 1 hour.
The concentration of pyrrole monomer in step 2) is 0.2-0.4M.
The SWCNTs were added in an amount of 0.1-5mg in step 2).
In the step 3), the ultrasonic time is 15-30min, the ultrasonic power is 100-200W, and the frequency is 40-60KHz.
In the step 4), the temperature in the step 4) is 8 ℃, the cleaning time is 5-60min, and the drying condition is vacuum drying at 60 ℃.
The nano composite thermoelectric film prepared by the preparation method based on the PPy-SWCNTs nano composite thermoelectric film is prepared by polymerizing SWCNTs with high Seebeck coefficient and a high-conductivity PPy nano film through a low-temperature interface.
The thickness of the nano composite thermoelectric film is 50-300nm, and the diameter of SWCNTs is less than 10nm.
The invention has the beneficial effects that:
(1) The PPy nano film is prepared by oxidizing and polymerizing pyrrole monomers at the water-cyclohexane interface at 8 ℃, and the preparation method is simple and has good repeatability.
(2) The PPy nano film in the invention has higher conductivity and good film forming performance, and can be prepared into a film thermoelectric material with excellent performance by compounding with SWCNTs.
(3) The PPy-SWCNTs composite film material prepared by the invention can be used as an organic thermoelectric material with excellent performance;
(4) The PPy-SWCNTs composite film material prepared by the invention has good flexibility, can be bent and cut into any shape at will, and provides a foundation for the application of the PPy-SWCNTs composite film material as a flexible wearable electronic device;
(5) The PPy-SWCNTs composite film thermoelectric material combines the advantages of PPy and SWCNTs, and the synergistic effect of the PPy and the SWCNTs is utilized to improve the overall thermoelectric performance of the composite material.
Drawings
FIG. 1 is a photograph of a prepared PPy-SWCNTs composite thermoelectric thin film material immersed in ethanol.
Fig. 2 is a Field Emission Scanning Electron Microscope (FESEM) topography of the prepared PPy nano-film.
FIG. 3 is a Field Emission Scanning Electron Microscope (FESEM) photograph of PPyr-SWCNTs composite nano-film in example 1.
FIG. 4 shows the thermoelectric properties of PPy-SWCNTs composite nano-film materials with different SWCNTs content (A: PPy powder obtained by traditional oxidative polymerization; B: PPy nano-film obtained by low-temperature interfacial polymerization; C: PPy-SWCNTs (0.1 mg) composite nano-film obtained by low-temperature interfacial polymerization; D: PPy-SWCNTs (0.3 mg) composite nano-film obtained by low-temperature interfacial polymerization; E: PPy-SWCNTs (0.5 mg) composite nano-film obtained by low-temperature interfacial polymerization; F: PPy-SWCNTs (0.8 mg) composite nano-film obtained by low-temperature interfacial polymerization).
Detailed Description
Embodiments of the invention are further described below with reference to the accompanying drawings:
the invention prepares the PPy-SWCNTs nano composite thermoelectric film with high thermoelectric performance by a low-temperature interfacial polymerization method, and the method well solves the problems that the PPy obtained by traditional in-situ chemical oxidation polymerization and electrochemical polymerization is powdery and has low conductivity, and obtains higher thermoelectric performance by the synergistic effect and the energy filtering effect of the composite utilization with the SWCNTs.
In the preparation process, the low-temperature interfacial polymerization is adopted, and the reaction is oxidized and polymerized at the water-cyclohexane interface at 8 ℃ to obtain the PPy nano film. If the temperature is lower than 6 ℃, cyclohexane is solidified, which greatly reduces the reaction rate, whereas if the temperature is too high, the polymerization rate is too fast, and the conjugation length and order of PPy chains are affected, resulting in deterioration of the conductivity of the resulting PPy film. The polymerization rate is proper at the temperature of 6-10 ℃ which is a good reaction condition, so that PPy chains with good conjugation and more ordered structures can be obtained, and further, the PPy film with smooth and compact surface can be obtained. In the polymerization process, the dispersed SWCNTs in cyclohexane can be coated into the film along with the generation of a PPy film, one-dimensional SWCNTs are interwoven into a good conductive network structure in the film, and the PPy-SWCNTs nano composite film is obtained after cleaning and drying. The composite material combines the high conductivity of the PPy film polymerized at the low temperature interface and the high Seebeck coefficient of SWCNTs, and the synergistic effect and the energy filtering effect of the high conductivity of the PPy film polymerized at the low temperature interface are utilized to improve the overall thermoelectric performance of the composite material.
In the examples described below, SWCNTs were commercially available from Mitsui Chemie Inc. under the product model TNST.
Wherein the oxidant adopts FeCl 3 Or other ferric salts.
Example 1
A PPy-SWCNTs nano-composite film thermoelectric material with high thermoelectric performance is prepared through preparing aqueous solution of oxidant and dopant, pre-cooling at 8 deg.C, ultrasonic dispersing SWCNTs in pyrrole-cyclohexane solution, dropping SWCNTs-pyrrole-cyclohexane solution into aqueous solution of oxidant to form water-cyclohexane interface, oxidizing polymerization reaction at 8 deg.C, washing and drying to obtain PPy-SWCNTs nano-composite film. Wherein the oxidizing agent FeCl used for preparing PPy 3 And the molar ratio of the dopant to toluene sulfonic acid was 1:1, and the SWCNTs were added in an amount of 0.1mg.
The preparation method of the composite film material with excellent thermoelectric performance comprises the following steps:
1) FeCl of 0.36 and 0.36M 3 Adding p-toluenesulfonic acid into 12ml of deionized water, stirring for 15min until the p-toluenesulfonic acid is completely dissolved to obtain a solution A, and then pre-cooling the solution A at 8 ℃ for 1h for later use;
2) Adding 0.036M pyrrole monomer into 12ml cyclohexane solution, stirring for 30min, adding 0.1mg SWCNTs powder, and then performing ultrasonic dispersion for 30min to obtain solution B;
3) Dropwise adding the solution B into the solution A, and then reacting for 15min at 8 ℃ to obtain a deep black composite film;
4) The obtained composite film was repeatedly washed with deionized water and ethanol three times, and then dried in a vacuum oven at 60℃for 12 hours to obtain a PPy-SWCNTs (0.1 mg) nanocomposite thermoelectric film.
FIG. 1 is a photograph of a prepared PPy-SWCNTs (0.1 mg) nanocomposite thermoelectric film immersed in ethanol, and it can be seen that the prepared film has good flexibility
Fig. 2 is a scanning electron microscope picture of a PPy nano film prepared by low-temperature interfacial polymerization, and it can be seen that the sample film has good compactness and smooth and flat surface.
FIG. 3 is a scanning electron microscope image of a PPy-SWCNTs nanocomposite film, showing that SWCNTs are coated with the PPy film and are randomly distributed and interwoven into a conductive network structure in the film.
FIG. 4 is a graph of thermoelectric performance of a composite material made in accordance with the present invention, wherein the electrical conductivity and Seebeck coefficient were measured using a thin film thermoelectric test system (Jia Jiu Tong, MRS-3).
As can be seen, the electrical conductivity of the powdery PPy obtained by the conventional polymerization method after tabletting was 10.3S/cm, the Seebeck coefficient was 6.8. Mu.V/K, and the power factor was 4.8X10 -2 μV/mK 2 The conductivity of the PPy nano film obtained by low-temperature interfacial polymerization is as high as 475.7S/cm, which is improved by nearly 40 times compared with that of PPy powder, and the Seebeck coefficient has small change, so that the thermoelectric performance of the PPy nano film is improved by nearly 50 times. After adding SWCNTs, the conductivity tends to decrease and the Seebeck coefficient tends to increase as the content of SWCNTs in the composite increases, mainly due to the lower conductivity of SWCNTs than the PPy nanofilm and the higher Seebeck coefficient. Because the power factor is in direct proportion to the square of the Seebeck coefficient, the power factor of the final composite material has a tendency of rising and then falling with the rising of the SWCNTs content, when the adding amount of the SWCNTs is 0.5mg, the conductivity is 341.6S/cm, the Seebeck coefficient is 33.2 mu V/K, and the power factor is 37.7 mu V/mK 2 The power factor of the purer PPy nano film is improved by nearly 20 times.
Example 2
A PPy-SWCNTs nano-composite film thermoelectric material with high thermoelectric performance is prepared through preparing aqueous solution of oxidant and dopant, pre-cooling at 8 deg.C, ultrasonic dispersing SWCNTs in pyrrole-cyclohexane solution, dropping SWCNTs-pyrrole-cyclohexane solution into aqueous solution of oxidant to form water-cyclohexane interface, oxidizing polymerization reaction at 8 deg.C, washing and drying to obtain PPy-SWCNTs nano-composite film. Wherein the oxidizing agent FeCl used for preparing PPy 3 And the molar ratio of the dopant to toluene sulfonic acid was 1:1, and the SWCNTs were added in an amount of 0.3mg.
The preparation method of the composite film material with excellent thermoelectric performance comprises the following steps:
1) FeCl of 0.36 and 0.36M 3 Adding p-toluenesulfonic acid into 12ml of deionized water, stirring for 15min until the p-toluenesulfonic acid is completely dissolved to obtain a solution A, and then pre-cooling the solution A at 8 ℃ for 1h for later use;
2) Adding 0.036M pyrrole monomer into 12ml cyclohexane solution, stirring for 30min, adding 0.3mg SWCNTs powder, and then performing ultrasonic dispersion for 30min to obtain solution B;
3) Dropwise adding the solution B into the solution A, and then reacting for 15min at 8 ℃ to obtain a deep black composite film;
4) The obtained composite film was repeatedly washed with deionized water and ethanol three times, and then dried in a vacuum oven at 60℃for 12 hours to obtain a PPy-SWCNTs (0.3 mg) nanocomposite thermoelectric film.
The prepared composite electrode material has the conductivity of 389.3S/cm, the Seebeck coefficient of 27.6 mu V/K and the power factor of 29.7 mu V/mK at room temperature 2 。
Example 3
A PPy-SWCNTs nano-composite film thermoelectric material with high thermoelectric performance is prepared through preparing the aqueous solution of oxidant and dopant, pre-cooling at 8 deg.C, ultrasonic dispersing SWCNTs in pyrrole-cyclohexane solution, dropping SWCNTs-pyrrole-cyclohexane solution into the aqueous solution of oxidant to form water-cyclohexane interface, and interfacial at 8 deg.CAnd (3) performing oxidation polymerization reaction on the surface, and after the reaction is complete, cleaning and drying the film to obtain the PPy-SWCNTs nano composite film. Wherein the oxidizing agent FeCl used for preparing PPy 3 And the molar ratio of the dopant to toluene sulfonic acid was 1:1, and the SWCNTs were added in an amount of 0.5mg.
The preparation method of the composite film material with excellent thermoelectric performance comprises the following steps:
1) FeCl of 0.36 and 0.36M 3 Adding p-toluenesulfonic acid into 12ml of deionized water, stirring for 15min until the p-toluenesulfonic acid is completely dissolved to obtain a solution A, and then pre-cooling the solution A at 8 ℃ for 1h for later use;
2) Adding 0.036M pyrrole monomer into 12ml cyclohexane solution, stirring for 30min, adding 0.5mg SWCNTs powder, and then performing ultrasonic dispersion for 30min to obtain solution B;
3) Dropwise adding the solution B into the solution A, and then reacting for 15min at 8 ℃ to obtain a deep black composite film;
4) The obtained composite film was repeatedly washed with deionized water and ethanol three times, and then dried in a vacuum oven at 60℃for 12 hours to obtain a PPy-SWCNTs (0.5 mg) nanocomposite thermoelectric film.
The conductivity of the prepared composite electrode material at room temperature is 341.6S/cm, the Seebeck coefficient is 33.2 mu V/K, and the power factor is 37.7 mu V/mK 2 。
Example 4
A PPy-SWCNTs nano composite film thermoelectric material with high thermoelectric performance is prepared by the following steps:
1) FeCl of 0.36 and 0.36M 3 Adding p-toluenesulfonic acid into 12ml of deionized water, stirring for 15min until the p-toluenesulfonic acid is completely dissolved to obtain a solution A, and then pre-cooling the solution A at 8 ℃ for 1h for later use;
2) Adding 0.036M pyrrole monomer into 12ml cyclohexane solution, stirring for 30min, adding 0.8mg SWCNTs powder, and then performing ultrasonic dispersion for 30min to obtain solution B;
3) Dropwise adding the solution B into the solution A, and then reacting for 15min at 8 ℃ to obtain a deep black composite film;
4) The obtained composite film was repeatedly washed with deionized water and ethanol three times, and then dried in a vacuum oven at 60℃for 12 hours to obtain a PPy-SWCNTs (0.8 mg) nanocomposite thermoelectric film.
The conductivity of the prepared composite electrode material at room temperature is 229.4S/cm, the Seebeck coefficient is 37.1 mu V/K, and the power factor is 31.6 mu V/mK 2 。
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (10)
1. A preparation method of a PPy-SWCNTs nano composite thermoelectric film is characterized in that: which comprises the following steps:
1) Dissolving a proper amount of oxidant and p-toluenesulfonic acid serving as a doping agent into water to obtain a solution A, and pre-cooling the solution A at 6-10 ℃ for 1-2 hours;
2) Taking pyrrole monomer and SWCNTs powder, and ultrasonically dispersing the pyrrole monomer and SWCNTs powder in a cyclohexane solution to obtain a solution B;
3) Dropwise adding the solution B into the solution A to form a clear interface;
4) After the reaction is fully carried out at the temperature of 6-10 ℃, the PPy-SWCNTs nano composite thermoelectric film is obtained after cleaning and drying.
2. The method for preparing the PPy-SWCNTs nanocomposite thermoelectric film according to claim 1, which is characterized in that: the oxidant is FeCl 3 。
3. The method for preparing the PPy-SWCNTs nano composite thermoelectric film according to claim 1 or 2, wherein the method comprises the following steps: the concentration of the dopant is 0.2-0.4M, and the molar ratio of the oxidant to the dopant is 1 (1-5).
4. The method for preparing the PPy-SWCNTs nanocomposite thermoelectric film according to claim 1, which is characterized in that: the pre-cooling temperature in step 1) was 8℃and the cooling time was 1 hour.
5. The method for preparing the PPy-SWCNTs nanocomposite thermoelectric film according to claim 1, which is characterized in that: the concentration of pyrrole monomer in step 2) is 0.2-0.4M.
6. The method for preparing the PPy-SWCNTs nanocomposite thermoelectric film according to claim 1, which is characterized in that: the SWCNTs were added in an amount of 0.1-5mg in step 2).
7. The method for preparing the PPy-SWCNTs nanocomposite thermoelectric film according to claim 1, which is characterized in that: in the step 3), the ultrasonic time is 15-30min, the ultrasonic power is 100-200W, and the frequency is 40-60KHz.
8. The method for preparing the PPy-SWCNTs nanocomposite thermoelectric film according to claim 1, which is characterized in that: in the step 4), the temperature in the step 4) is 8 ℃, the cleaning time is 5-60min, and the drying condition is vacuum drying at 60 ℃.
9. A nanocomposite thermoelectric film prepared by the method for preparing a PPy-SWCNTs nanocomposite thermoelectric film according to any one of claims 1, 2, 3,4, 5, 6, 7 or 8, characterized in that: the nano composite thermoelectric film is prepared by polymerizing SWCNTs with high Seebeck coefficient and a high-conductivity PPy nano film through a low-temperature interface.
10. The nanocomposite thermoelectric film according to claim 9, wherein: the thickness of the nano composite thermoelectric film is 50-300nm, and the diameter of SWCNTs is less than 10nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910874159.9A CN110581210B (en) | 2019-09-17 | 2019-09-17 | Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910874159.9A CN110581210B (en) | 2019-09-17 | 2019-09-17 | Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110581210A CN110581210A (en) | 2019-12-17 |
CN110581210B true CN110581210B (en) | 2023-06-23 |
Family
ID=68813072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910874159.9A Active CN110581210B (en) | 2019-09-17 | 2019-09-17 | Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110581210B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111440390A (en) * | 2020-03-11 | 2020-07-24 | 广州大学 | Thermoelectric polymer film and preparation method thereof |
CN112735860B (en) * | 2021-02-03 | 2022-06-14 | 东北师范大学 | High-crystallinity high-conductivity polypyrrole graphene composite structure and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102250324A (en) * | 2011-05-20 | 2011-11-23 | 中国科学院理化技术研究所 | Preparation method of composite material of poly (3, 4-dioxyethyl) thiophene coated carbon nanotube |
CN103840074A (en) * | 2014-02-12 | 2014-06-04 | 中国科学院化学研究所 | Method for preparing composite thermoelectric material of PPY cladding carbon nano tube |
CN106229403A (en) * | 2016-08-08 | 2016-12-14 | 中国科学院化学研究所 | N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof |
CN107146842A (en) * | 2017-06-13 | 2017-09-08 | 同济大学 | Self-supporting flexibility PEDOT nanofibers/SWCNTs composite thermoelectric material films and preparation method thereof |
WO2018055404A1 (en) * | 2016-09-23 | 2018-03-29 | Imperial Innovations Limited | Composite material |
-
2019
- 2019-09-17 CN CN201910874159.9A patent/CN110581210B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102250324A (en) * | 2011-05-20 | 2011-11-23 | 中国科学院理化技术研究所 | Preparation method of composite material of poly (3, 4-dioxyethyl) thiophene coated carbon nanotube |
CN103840074A (en) * | 2014-02-12 | 2014-06-04 | 中国科学院化学研究所 | Method for preparing composite thermoelectric material of PPY cladding carbon nano tube |
CN106229403A (en) * | 2016-08-08 | 2016-12-14 | 中国科学院化学研究所 | N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof |
WO2018055404A1 (en) * | 2016-09-23 | 2018-03-29 | Imperial Innovations Limited | Composite material |
CN107146842A (en) * | 2017-06-13 | 2017-09-08 | 同济大学 | Self-supporting flexibility PEDOT nanofibers/SWCNTs composite thermoelectric material films and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110581210A (en) | 2019-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Xie et al. | Nanostructured conjugated polymers for energy‐related applications beyond solar cells | |
Soleimani et al. | A review on recent developments of thermoelectric materials for room-temperature applications | |
Reddy et al. | Synthesis of MWCNTs‐core/thiophene polymer‐sheath composite nanocables by a cationic surfactant‐assisted chemical oxidative polymerization and their structural properties | |
CN102219997B (en) | Method for preparing polypyrrole coated bacterial cellulose nanometer electric-conduction composite material by utilizing bacterial cellulose as template | |
CN103840074A (en) | Method for preparing composite thermoelectric material of PPY cladding carbon nano tube | |
CN108539217B (en) | Preparation method and application of nitrogen-sulfur co-doped carbon nanotube | |
CN110581210B (en) | Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film | |
Oseni et al. | Bimetallic nanocomposites and the performance of inverted organic solar cell | |
CN106784288B (en) | Preparation method for enhancing performance of composite thermoelectric material | |
Purty et al. | Potentially enlarged supercapacitive values for CdS-PPY decorated rGO nanocomposites as electrode materials | |
Wang et al. | High-performance lithium ion batteries combining submicron silicon and thiophene–terephthalic acid-conjugated polymer binders | |
Wang et al. | A study of the thermoelectric properties of benzo [1, 2-b: 4, 5-b′] dithiophene–based donor–acceptor conjugated polymers | |
CN109251337B (en) | Preparation method of polyaniline carbon tube flexible composite thermoelectric thin film material | |
Folorunso et al. | Conductive polymers’ electronic structure modification for multifunctional applications | |
Ugraskan et al. | Enhanced thermoelectric properties of highly conductive poly (3, 4-ethylenedioxy thiophene)/exfoliated graphitic carbon nitride composites | |
Baruah et al. | Electrocatalytic acitivity of RGO/PEDOT: PSS nanocomposite towards methanol oxidation in alkaline media | |
CN109301060B (en) | Preparation method of composite aerogel thermoelectric material | |
CN105789423A (en) | Preparation method for thermoelectric composite material of polyaniline in-situ polymerization clad PEDOT modified nano-carbon | |
CN112300387A (en) | Preparation method of conductive polymer reinforced flexible carbon aerogel | |
CN108831749B (en) | Electrochemical energy storage composite material and preparation method thereof | |
CN110289176B (en) | Preparation method of polyaniline grafted reduced graphene oxide/multi-walled carbon nanotube composite material for electrochemical energy storage | |
Zhang et al. | Construction of a hierarchical multiscale conducting network for enhanced thermoelectric response in organic PEDOT: PSS based nanocomposites | |
CN103227054B (en) | The antimony trisulfide of DSSC is to electrode and preparation method thereof | |
Ji et al. | Improving the performance of ternary bulk heterojunction polymer cell by regioregular poly (3-hexylthiophene)-grafted oxide graphene on in situ doping of CdS | |
CN1598971A (en) | Conducting polymer carbon nanotube nano cable and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |