CN110676369A - One-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material and preparation method thereof - Google Patents
One-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material and preparation method thereof Download PDFInfo
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- CN110676369A CN110676369A CN201910989144.7A CN201910989144A CN110676369A CN 110676369 A CN110676369 A CN 110676369A CN 201910989144 A CN201910989144 A CN 201910989144A CN 110676369 A CN110676369 A CN 110676369A
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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- H10N10/856—Thermoelectric active materials comprising organic compositions
Abstract
The invention relates to a strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with a core-shell structure and a preparation method thereof, and belongs to the field of composite material preparation. The composite nano-fiber has the characteristics of good one-dimensional morphology structure, good flexibility and the like, and the power factor of the composite material at room temperature reaches 20.73 mu Wm‑1K‑2Is 30 times of pure polyaniline, and the composite material has good oxidation resistance and good oxidation resistanceThe method is an effective way for improving the thermoelectric performance of the polymer, and has the advantages of simplicity, practicability, low cost, convenience, rapidness, large-scale production and the like.
Description
Technical Field
The invention relates to the field of functional material preparation, in particular to a strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with a one-dimensional core-shell structure and a preparation method thereof.
Background
The thermoelectric material is a functional material capable of directly converting heat energy and electric energy, and the power generation or refrigeration device manufactured by utilizing the thermoelectric material has the advantages of reliable performance, no pollution, no noise during working, long service life and the like. The method is widely applied to thermoelectric power generation and electric refrigeration equipment. The performance of thermoelectric materials is mainly dependent on the dimensionless thermoelectric figure of merit (ZT value). Different materials can be classified into conductors, semiconductors, and insulators according to their electrical conductivity. Intrinsic coupling relationships between different types of material carrier concentrations and electrical conductivity, Seebeck coefficient, and thermal conductivity, and their respective thermoelectric conversion efficienciesZTThe value relationship.
Inorganic thermoelectric systems that have been developed to date include metal-based thermoelectric materials including near-room-temperature thermoelectric material Bi and oxide thermoelectric materials2Te3The research on the traditional inorganic thermoelectric material has obtained remarkable achievements, but the main components of the raw material of the traditional inorganic thermoelectric material are heavy or scarce in mass and toxic, the traditional inorganic thermoelectric material usually needs a complex preparation process, namely consumes a large amount of energy, and the prepared material is difficult to integrate into a thermoelectric device.
Disclosure of Invention
The invention provides a strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with a one-dimensional core-shell structure and a preparation method thereof.
The technical scheme for realizing the invention is as follows:
the composite nano thermoelectric material is a one-dimensional core-shell structure taking strontium titanate nanofiber as a core and zinc oxide and polyaniline as shells. The diameter of the core layer is 50-120 nm, the thickness of the zinc oxide shell layer is 20-80nm, and the thickness of the polyaniline shell layer is 20-100 nm.
Carrying out surface modification on the strontium titanate @ zinc oxide material, and then carrying out liquid phase polymerization on the strontium titanate @ zinc oxide material and an aniline solution to prepare the composite nano thermoelectric material.
The preparation method of the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the one-dimensional core-shell structure comprises the following steps:
(1) placing the strontium titanate @ zinc oxide nano-fiber in a polyvinyl alcohol aqueous solution, stirring for 2-5h at the temperature of 20-40 ℃, and then centrifuging and drying to obtain the strontium titanate @ zinc oxide nano-fiber subjected to surface polymer modification treatment;
(2) placing the strontium titanate @ zinc oxide nano-fiber modified in the step (1) in an alcohol solution of ferric chloride for uniform dispersion to obtain a dispersion liquid;
(3) and mixing the dispersion liquid with a carbon tetrachloride solution of aniline to form an interface, reacting, centrifuging and drying after polymerization to obtain the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure.
In the step (1), the concentration of the polyvinyl alcohol aqueous solution is 3-10%, and the mass ratio of the strontium titanate @ zinc oxide nano fiber to the polyvinyl alcohol aqueous solution is 1 (2 ~ 5).
The mass ratio of the ferric chloride, the modified strontium titanate @ zinc oxide nanofiber and the alcohol in the step (2) is 1 (1 ~ 10): 3 ~ 8.
The volume ratio of the dispersion liquid to the carbon tetrachloride solution of aniline in the step (3) is 1 (2 ~ 4).
The temperature of the interface reaction in the step (3) is 0 ~ 30 ℃, and the reaction time is 15 ~ 100 min.
The invention has the beneficial effects that: the invention adopts the electrostatic spinning method combined with the interfacial polymerization method to prepare the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material, the composite nano fiber has the characteristics of good one-dimensional morphology structure, good flexibility and the like, and the power factor of the composite material at room temperature reaches 20.73 mu Wm-1K-2The composite material has the advantages of 30 times of pure polyaniline, good oxidation resistance, direct use in the air, controllable shell thickness of the composite fiber and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a transmission electron microscopy ("TEM") spectrum of the nanocomposite fiber of example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure comprises the following steps:
(1) preparing strontium titanate @ zinc oxide nano-fibers by an electrostatic spinning method; placing the strontium titanate @ zinc oxide nano-fiber into a polyvinyl alcohol aqueous solution with the concentration of 3%, wherein the mass ratio of the strontium titanate @ zinc oxide nano-fiber to the polyvinyl alcohol aqueous solution is 1: stirring for 2h at 20 ℃, and then centrifuging and drying to obtain the strontium titanate @ zinc oxide nanofiber with the surface polymer modified and modified;
(2) adding 1g of ferric chloride into 3g of alcohol to form a uniform solution, placing 1g of modified strontium titanate @ zinc oxide nanofiber into the alcohol solution of ferric chloride, and dispersing the strontium titanate @ zinc oxide nanofiber into the uniform solution;
(3) dissolving aniline monomer into carbon tetrachloride (the mass ratio of aniline monomer to carbon tetrachloride is 1: 10), and mixing the dispersion liquid in the step (2) and the carbon tetrachloride solution of aniline in a volume ratio of 1: 2, mixing to form an interface, reacting at 0 ℃ for 100min, centrifuging and drying after polymerization to obtain the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure.
FIG. 1 is a Transmission Electron Microscope (TEM) micrograph of the composite material of example 1. It can be seen that the composite has a good core-shell structure.
Example 2
The preparation method of the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure comprises the following steps:
(1) preparing strontium titanate @ zinc oxide nano-fibers by an electrostatic spinning method; placing the strontium titanate @ zinc oxide nano-fiber into a polyvinyl alcohol aqueous solution with the concentration of 10%, wherein the mass ratio of the strontium titanate @ zinc oxide nano-fiber to the polyvinyl alcohol aqueous solution is 1: stirring for 5 hours at the temperature of 40 ℃, and then centrifuging and drying to obtain the strontium titanate @ zinc oxide nano fiber subjected to surface polymer modification treatment;
(2) adding 1g of ferric chloride into 8g of alcohol to form a uniform solution, placing 10g of modified nanofiber into the ferric chloride alcohol solution, and dispersing the strontium titanate @ zinc oxide nanofiber into the uniform solution;
(3) dissolving aniline monomer in carbon tetrachloride (the mass ratio of aniline monomer to carbon tetrachloride is 1: 20), and mixing the dispersion liquid in the step (2) and the carbon tetrachloride solution of aniline in a volume ratio of 1: 3, mixing to form an interface, reacting for 15min at 30 ℃, centrifuging and drying after polymerization to obtain the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure.
Example 3
The preparation method of the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure comprises the following steps:
(1) preparing strontium titanate @ zinc oxide nano-fibers by an electrostatic spinning method; placing the strontium titanate @ zinc oxide nano-fiber in a polyvinyl alcohol aqueous solution with the concentration of 7%, wherein the mass ratio of the strontium titanate @ zinc oxide nano-fiber to the polyvinyl alcohol aqueous solution is 1: 5, stirring for 4 hours at 30 ℃, and then centrifuging and drying to obtain the strontium titanate @ zinc oxide nano fiber subjected to surface polymer modification treatment;
(2) adding 1g of ferric chloride into 7g of alcohol to form a uniform solution, placing 5g of modified nanofiber into the alcoholic solution of ferric chloride, and dispersing the strontium titanate @ zinc oxide nanofiber into the uniform solution;
(3) dissolving aniline monomer in carbon tetrachloride (the mass ratio of aniline monomer to carbon tetrachloride is 1: 15), and mixing the dispersion liquid in the step (2) and the carbon tetrachloride solution of aniline in a volume ratio of 1: 4, mixing to form an interface, reacting for 70min at 20 ℃, centrifuging and drying after polymerization to obtain the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The one-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material is characterized in that: the composite nano thermoelectric material is a one-dimensional core-shell structure taking strontium titanate nanofiber as a core and zinc oxide and polyaniline as shells.
2. The one-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material according to claim 1, characterized in that: the diameter of the core layer is 50-120 nm, the thickness of the zinc oxide shell layer is 20-80nm, and the thickness of the polyaniline shell layer is 20-100 nm.
3. The preparation method of the one-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material as described in claim 1 or 2, characterized in that: carrying out surface modification on the strontium titanate @ zinc oxide material, and then carrying out liquid phase polymerization on the strontium titanate @ zinc oxide material and an aniline solution to prepare the composite nano thermoelectric material.
4. The preparation method of the one-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material according to claim 3, which is characterized by comprising the following steps:
(1) placing the strontium titanate @ zinc oxide nano-fiber in a polyvinyl alcohol aqueous solution, stirring for 2-5h at the temperature of 20-40 ℃, and then centrifuging and drying to obtain the strontium titanate @ zinc oxide nano-fiber subjected to surface polymer modification treatment;
(2) placing the strontium titanate @ zinc oxide nano-fiber modified in the step (1) in an alcohol solution of ferric chloride for uniform dispersion to obtain a dispersion liquid;
(3) and mixing the dispersion liquid with a carbon tetrachloride solution of aniline to form an interface, reacting, centrifuging and drying after polymerization to obtain the strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material with the core-shell structure.
5. The preparation method of the one-dimensional core-shell structure strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material according to claim 4, wherein the concentration of the polyvinyl alcohol aqueous solution in the step (1) is 3-10%, and the mass ratio of the strontium titanate @ zinc oxide nanofibers to the polyvinyl alcohol aqueous solution is 1 (2 ~ 5).
6. The preparation method of the one-dimensional core-shell strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material of claim 4 is characterized in that the mass ratio of the ferric chloride, the modified strontium titanate @ zinc oxide nano fiber and the alcohol in the step (2) is 1 (1 ~ 10): 3 ~ 8.
7. The preparation method of the one-dimensional core-shell structure strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material as claimed in claim 4, wherein the volume ratio of the dispersion liquid to the carbon tetrachloride solution of aniline in the step (3) is 1 (2 ~ 4).
8. The preparation method of the one-dimensional core-shell strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material of claim 4, wherein the temperature of the interface reaction in the step (3) is 0 ~ 30 ℃, and the reaction time is 15 ~ 100 min.
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| CN112820818A (en) * | 2020-12-31 | 2021-05-18 | 东华大学 | Flexible strontium titanate nanofiber-based composite thermoelectric film and preparation method thereof |
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