CN110676369B - 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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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 ‑1 K ‑2 The 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.
Description
Technical Field
The invention relates to the field of preparation of functional materials, 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, insulators according to their electrical conductivity. Internal coupling relations between different kinds of material carrier concentrations and electric conductivity, Seebeck coefficient and thermal conductivity and respective thermoelectric conversion efficiencies thereofZTThe 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 materials 2 Te 3 And its alloy, thermoelectric material PbTe and its alloy in medium temperature region (400-700K), and thermoelectric material SiGe and its alloy in high temperature region (400-700K). The research on the traditional inorganic thermoelectric materials has achieved remarkable success, but the main components of the raw materials are heavy or scarce in mass, toxic, and they often require complicated preparation processes, i.e. consume a large amount of energy, and the prepared materials are difficult to integrate into thermoelectric devices. The oxide thermoelectric material has the characteristics of high-temperature chemical stability, environmental friendliness, low cost and the like, and gradually becomes a hot spot for thermoelectric material research. At present, research mainly focuses on cobalt-based oxide semiconductors and perovskite-type oxide semiconductors, and the main problem existing in the development of oxide thermoelectric materials is that thermoelectric figure of merit ZT is low and needs to be further improved.
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 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).
In the step (2), the mass ratio of ferric chloride to the modified strontium titanate @ zinc oxide nanofiber to the alcohol is 1: (1-10): (3-8).
The volume ratio of the dispersion liquid to the aniline carbon tetrachloride solution 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 shape structure, good flexibility and the like, and the power factor of the composite material at room temperature reaches 20.73 mu Wm -1 K -2 30 times of pure polyaniline, the composite material has good oxidation resistance, and can be directly used in airThe method is an effective way for improving the thermoelectric performance of the polymer, and has the advantages of simplicity, easiness in operation, low cost, convenience, rapidness, large-scale production and the like.
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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 TEM image 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 nanofibers by adopting an electrostatic spinning method; placing the strontium titanate @ zinc oxide nano-fiber in 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 alcohol 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: 20), and mixing the dispersion liquid in the step (2) and the carbon tetrachloride solution of aniline in a volume ratio of 1: 3, forming 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 nanofiber with the surface polymer modified and modified;
(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 at 20 ℃ for 70min, and 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 should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (7)
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; 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 aniline solution to prepare the composite nano thermoelectric material.
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 according to claim 2, 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) into an alcohol solution of ferric chloride for uniform dispersion to obtain a dispersion liquid;
(3) 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.
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 in that: 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).
5. 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 in that: in the step (2), the mass ratio of ferric chloride to the modified strontium titanate @ zinc oxide nanofiber to the alcohol is 1: (1-10): (3-8).
6. The preparation method of the one-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material according to claim 3, characterized in that: the volume ratio of the dispersion liquid to the aniline carbon tetrachloride solution in the step (3) is 1: (2-4).
7. The preparation method of the one-dimensional core-shell structured strontium titanate @ zinc oxide @ polyaniline composite nano thermoelectric material according to claim 3, characterized in that: 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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| JP2012061735A (en) * | 2010-09-16 | 2012-03-29 | Nippon Shokubai Co Ltd | Composite and method of manufacturing the same |
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