CN114456607A - Room temperature base thermoelectric material containing infinite conjugated polymer and preparation method thereof - Google Patents
Room temperature base thermoelectric material containing infinite conjugated polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a room temperature base thermoelectric material containing infinite conjugated polymer and a preparation method thereof, wherein the preparation method comprises the following steps: an infinite conjugated polymer, p-type bismuth telluride Bi2‑ xSbxTe3Carrying out mixing ball milling to obtain composite material powder, wherein x is more than 0 and less than or equal to 2; carrying out hot-pressing discharge plasma sintering on the composite material powder at 240-450 ℃ to obtain a thermoelectric material; the infinite conjugated polymer is a metal-based infinite conjugated polymer synthesized by an organic ligand of the following structural formula (1) and a metal element; whereinR is amino or mercapto, R' is mercapto, hydroxyl, carboxyl or amino. By adopting the technical scheme of the invention, the carrier concentration and the lattice thermal conductivity of the thermoelectric material are synergistically regulated and controlled, the electrical and thermal properties of the thermoelectric material are improved, and a new idea is provided for obtaining the high-performance thermoelectric material.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a room temperature based thermoelectric material containing an infinite conjugated polymer and a preparation method thereof.
Background
The thermoelectric material is a green functional material which realizes direct interconversion of heat energy and electric energy by utilizing directional movement of carriers in a solid. The thermoelectric material can be used for converting waste heat in production and life into electric energy through thermoelectric power generation, so that the use efficiency of the traditional energy is improved, and the thermoelectric material can be electrified to realize solid-state refrigeration. The thermoelectric conversion device taking the thermoelectric material as the core has the characteristics of small volume, high reliability, wide use temperature range, environmental friendliness and the like, is applied to various fields of industry, agriculture, national defense and human life, can effectively relieve the problems of energy shortage and environmental pollution in China, and is one of the key topics of the current new energy research.
The advantages and disadvantages of the thermoelectric material are mainly based on the dimensionless thermoelectric figure of merit ZT ═ S introduced by German physicist E2σ · T/κ, where σ is the electrical conductivity, S is the Seebeck coefficient, κ is the thermal conductivity, and T is the absolute temperature. The zT value of the thermoelectric material directly reflects the thermoelectric performance of the material. As can be seen from the above formula, a thermoelectric material with excellent performance should have large σ and S coefficients, while having low κ at a specific temperature. However, three parameters (electrical conductivity, Seebeck coefficient and thermal conductivity) influencing the performance of the thermoelectric material are mutually coupled, and how to demodulate the electrical and thermal transport characteristics to the maximum extent is a key scientific problem for improving the thermoelectric performance.
(Bi,Sb)2(Te,Se)3The alloy is the most widely commercialized thermoelectric material so far as the earliest discovered compound semiconductor thermoelectric material, and can be used for further improving the thermoelectric performance of the material and effectively regulating the zT peak temperature zone of the material so as to obtain the thermoelectric material in the fields of medium-low temperature waste heat power generation, thermoelectric refrigeration and the likeMore widely used, is the main research target in recent years. Because the thermoelectric parameters are essentially determined by the transport mechanisms of electrons and phonons, and the mechanical properties can be improved by grain refinement, nano second-phase compounding, process regulation and the like, the electrical and thermal coupling effects and the multiple optimization effects of the thermoelectric and mechanical properties need to be cooperatively considered in the actual material research. Therefore, exploring a new research method for optimizing the thermoelectric properties of the material and obtaining the thermoelectric material with enhanced mechanical properties is of great significance for the application of thermoelectric devices. Since the fifties and sixties of the 20 th century, bismuth telluride alloy semiconductor thermoelectric materials have been reported with the highest zT values approaching 1.0. Subsequently, a large amount of research is carried out by scholars at home and abroad aiming at the aspects of electron and phonon decoupling, mechanical property strengthening, synthesis process regulation and control and the like in the bismuth telluride.
In more than ten years, nano-compounding is considered as a means for effectively optimizing the thermoelectric performance of inorganic materials, and the basic idea is to reduce the size of a microstructure in the materials to be tens of nanometers or below, so that the size reaches the order of magnitude equivalent to the wavelengths of electrons and phonons, thereby realizing the coordinated optimization of the transport of current carriers and phonons, and meanwhile, the nano second phase filling is expected to obtain the enhancement of the mechanical performance.
In addition, conjugated polymer nanomaterials (ICPs) are a class of porous materials with periodic network structures formed by the interconnection of inorganic metal centers (metal ions or metal clusters) and bridged organic ligands by self-assembly. ICPs are an organic-inorganic hybrid material, also known as coordination polymer, which is different from inorganic porous materials and from general organic complexes. With the increasing variety of ICPs and the increasing emergence of composite materials, the ICPs have immeasurable application prospects. Therefore, the development of ICPs and composites with functional diversity and their application in different fields will greatly promote the development of the subject. ICPs materials are inherently low in conductivity (10)-13～10-1S cm-1) Making it difficult to apply it alone in the thermoelectric field.
However, the structure of metal sites and ligands in conjugated polymers is various, and the chemical properties are very different, and it is very important to explore a screening mechanism for infinite conjugated polymer materials which are effectively used for improving the thermoelectric properties of inorganic materials, and a research on how to fully utilize the diversity advantages of the material structures and chemical compositions of ICPs for optimizing the thermoelectric and mechanical properties of traditional inorganic materials has not been reported.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a room temperature based thermoelectric material containing an infinite conjugated polymer and a preparation method thereof.
In contrast, the technical scheme adopted by the invention is as follows:
a method for preparing a room temperature based thermoelectric material containing an infinite conjugated polymer comprises the following steps:
an infinite conjugated polymer, p-type bismuth telluride Bi2-xSbxTe3Carrying out mixing ball milling to obtain composite material powder, wherein x is more than 0 and less than or equal to 2;
carrying out hot-pressing discharge plasma sintering on the composite material powder at 250-450 ℃ to obtain a thermoelectric material;
the infinite conjugated polymer is a metal-based infinite conjugated polymer synthesized by an organic ligand of the following structural formula (1) and a metal element;
wherein R is amino or mercapto, and R' is mercapto, hydroxyl, carboxyl or amino.
Further, the p-type bismuth telluride Bi2-xSbxTe3Is prepared by a smelting method.
As a further improvement of the invention, the pressure when the hot-pressing discharge plasma sintering is carried out is 40-60 MPa.
As a further improvement of the invention, the metal elements are copper, nickel and zinc.
As a further improvement of the invention, the infinite conjugated polymer is a nano material of coordination of tetrahydroxy thiophenol and copper, a coordination product of copper and 1, 4-benzenedithiol, a coordination product of nickel and p-phenylenediamine or a coordination product of zinc and terephthalic acid.
The preparation method of the nano material of coordination of tetrahydroxy thiophenol and copper, namely CuHT, comprises the following steps:
0.882g (7.0mmol) of 4-hydroxythiophenol (hydroxythiophenol) is weighed into a 100ml round bottom flask with a condenser containing 50ml of absolute ethanol, 0.500g (3.5mmol) of cuprous oxide is added into the flask, after three times of degassing, nitrogen is introduced, the flask is put into a constant temperature oil bath at 85 ℃, and the reaction is carried out for 48 hours under continuous stirring. When the solution turns yellow, the solution is taken out, and the obtained sample is dried for 12 hours in a vacuum drying oven at 40 ℃ by 3X 10ml of ethanol, 3X 100ml of deionized water and 2X 10ml of diethyl ether to obtain CuHT.
Coordination product Cu of copper and 1, 4-benzenedithiol2The preparation method of the (1, 4-benzenedithiol) comprises the following steps: on the basis of the CuHT, 4-Hydroxythiophenol (HT) is replaced by 1, 4-benzenedithiol (1, 4-benzenedithiol), and the compound is prepared according to the method.
Nickel and p-phenylenediamine coordination product Ni2The preparation method of the (p-phenylenediamine) comprises the following steps: the preparation method is characterized in that 4-Hydroxythiophenol (HT) is replaced by p-Phenylenediamine, cuprous oxide is replaced by nickel nitrate hexahydrate, and the preparation method is adopted.
The coordination product MOF-5 of zinc and terephthalic acid is prepared from zinc nitrate hexahydrate and terephthalic acid in a stoichiometric ratio (molar ratio of Zn to terephthalic acid) of 1: and 1, reacting at 120 ℃ for 24 hours in a DMF solvent under the protection of nitrogen. And after the reaction is finished, filtering and cleaning the mixture by deionized water and ethanol, and drying the mixture in vacuum at 40 ℃ to obtain an MOF-5 powder sample.
As a further improvement of the invention, the p-type bismuth telluride Bi2-xSbxTe3Ball milling is carried out for 3-5 hours, and then the mixture is mixed with infinite conjugated polymer for ball milling. Preferably, the p-type bismuth telluride Bi2-xSbxTe3Ball milling is carried out for 4 hours, and then the mixture is mixed with the infinite conjugated polymer for ball milling.
As a further improvement of the invention, x satisfies 0.3 ≦ 2x ≦ 1.5.
As a further improvement of the invention, the p-type bismuth telluride Bi2-xSbxTe3Is Bi0.5Sb1.5Te3、Bi0.3Sb1.7Te3Or Bi1.5Sb0.5Te3。
As a further improvement of the invention, the infinite conjugated polymer and the p-type Bi2-xSbxTe3The powder is loaded into a ball mill pot and ball milled for 2 to 12 minutes.
As a further improvement of the invention, the sintering temperature of the discharge plasma is 365-450 ℃.
As a further improvement of the invention, when the infinite conjugated polymer and the p-type bismuth telluride are mixed and ball-milled, the mass percentage of the infinite conjugated polymer is not more than 10%.
The invention also discloses a room temperature based thermoelectric material containing the infinite conjugated polymer, which is prepared by adopting the preparation method of the room temperature based thermoelectric material containing the infinite conjugated polymer.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention provides a new idea for optimizing the inorganic thermoelectric material, and the infinite conjugated polymer nano material and the inorganic thermoelectric material are compounded, so that the carrier concentration and the lattice thermal conductivity of the thermoelectric material are cooperatively regulated and controlled, and the electrical and thermal properties of the thermoelectric material are cooperatively optimized and improved. The composite thermoelectric material with greatly improved thermoelectric performance is obtained by fully utilizing the advantages of the porous structure and structural diversity of the infinite conjugated polymer material and regulating and controlling the processing technology. Compared with the prior art which utilizes compounding to reduce lattice thermal conductivity or doping to improve electrical property, the technical scheme of the invention adopts the infinite conjugated polymer, can comprehensively utilize the unique advantages of the material structure, realizes double optimization effects on the electrical property and the thermal property, enriches means for optimizing the inorganic thermoelectric material, and provides a new idea for obtaining the high-performance thermoelectric material.
Drawings
FIG. 1 is a reaction scheme of an infinite conjugated polymer of the present invention.
FIG. 2 is a thermogravimetric decomposition curve of a CuHT material of an embodiment of the present invention.
FIG. 3 shows thermoelectric materials Bi obtained at different SPS sintering temperatures according to an embodiment of the present invention0.5Sb1.5Te3/CuHT5And comparative example Cu0.02Bi0.5Sb1.5Te3The electrical properties of the alloy are compared with the change of sintering temperature; wherein (a) is conductivity, (b) is carrier concentration, (c) is carrier concentration, (d) is Seebeck coefficient, and (e) is power factor.
FIG. 4 shows a thermoelectric material Bi obtained at a sintering temperature of 365 ℃ in accordance with an embodiment of the present invention0.5Sb1.5Te3CuHT and Bi0.5Sb1.5Te3Scanning electron microscope images of the cross section; wherein (a) is Bi0.5Sb1.5Te3(b) and (c) are Bi with different magnification0.5Sb1.5Te3Sectional Scanning Electron Microscope (SEM) picture of/CuHT.
FIG. 5 shows a thermoelectric material Bi obtained at a sintering temperature of 365 ℃ in an example of the present invention0.5Sb1.5Te3/CuHT5Section of a 365 Block composite, Bi0.5Sb1.5Te3、Bi0.5Sb1.5Te3/CuHT5-EBSD map of a cross-section polished sample of 365; wherein (a) is Bi0.5Sb1.5Te3The insert shows the statistics of the pole figure and the average grain size, and (b) is Bi0.5Sb1.5Te3/CuHT5-scanning electron microscope image of a section of 365 bulk composite material, (c) being Bi0.5Sb1.5Te3/CuHT5EBSD map of section 365 polished sample.
FIG. 6 shows Bi obtained at different SPS sintering temperatures in example 1 of the present invention0.5Sb1.5Te3/CuHT5(BST/CuHT5The thermal behavior of X) as a function of the sintering temperature, where (a) is the thermal conductivity and (b) is the lattice heatThermal conductivity and (c) is a dimensionless thermoelectric figure of merit, zT.
FIG. 7 shows BST/CuHT obtained by the preparation of the present invention5-365 Electrical Performance comparison plot of Single-leg device, wherein (a) BST/CuHT5-experimental and theoretical output voltages (U) of 365 single-leg devices, (b) output power (P) and thermoelectric conversion efficiency (η) as a function of current; (c) the comparison curve of the theoretical and actual maximum testing thermoelectric conversion efficiency of the sample with the temperature difference before and after optimization; (d) the BST/CuPc single-leg thermoelectric device efficiency is compared with the conversion efficiency of commercial BST and partial BST-based composite thermoelectric materials under different temperature difference conditions.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Chemically synthesized infinite conjugated polymer and smelting process to prepare bismuth telluride, p-type Bi2-xSbxTe3(x is more than 0 and less than 2), performing high-energy ball milling for 4 hours, filling the mixture into a ball milling tank according to the metering ratio, and performing ball milling for 2 to 12 minutes to obtain the composite material powder. And putting the obtained composite material powder into a graphite mold, and carrying out hot pressing for 2-5 minutes in a discharge plasma sintering process at the temperature of 240-450 ℃ and under 50 MPa.
The infinite conjugated polymer is a metal-based infinite conjugated polymer synthesized by an organic ligand of the following structural formula (1) and a metal element, and the specific reaction formula is shown in figure 1.
Wherein R is amino or mercapto, and R' is mercapto, hydroxyl, carboxyl or amino.
The infinite conjugated polymer covered by the invention comprises two-dimensional infinite conjugated polymer nano materials formed by coordinating different functional groups with different metal elements, and the materials have similar chemical structures. Selecting representative CuHT (HT represents coordination of tetrahydroxy thiophenol and copper) nano material and p-type bismuth telluride Bi2-xSbxTe3The compounding is specifically described.
Example 1
Coordinating tetrahydroxy thiophenol and copper to obtain an infinite conjugated polymer CuHT, which comprises the following steps:
first, 0.882g (7.0mmol) of 4-hydroxythiophenol (hydroxythiophenol) was weighed into a 100ml round bottom flask with a condenser containing 50ml of absolute ethanol, 0.500g (3.5mmol) of cuprous oxide was added thereto, after three times of degassing, nitrogen was introduced, and the mixture was put into an oil bath at a constant temperature of 85 ℃ with continuous stirring and reacted for 48 hours. When the solution turns yellow, the solution is taken out and dried by 3X 10ml of ethanol, 3X 100ml of deionized water and 2X 10ml of ether in a vacuum drying oven at 40 ℃ for 12 hours to obtain CuHT.
Smelting method for preparing p-type Bi0.5Sb1.5Te3Performing high-energy ball milling for 4 hours to obtain infinite conjugated polymer CuHT and p-type Bi0.5Sb1.5Te3And (3) filling the two substances into a ball milling tank according to a metering ratio, wherein CuHT accounts for 5% of the total mass, and carrying out ball milling for 6 minutes to obtain the composite material powder. Putting the obtained composite material powder into a graphite die, and carrying out hot pressing for 6 minutes in a discharge plasma sintering process at the sintering temperature of 265 ℃ under 50MPa to obtain a thermoelectric material Bi0.5Sb1.5Te3/CuHT5Wherein 5 represents 5% of CuHT by mass.
Thermoelectric materials obtained by sintering at 290 ℃, 365 ℃ and 450 ℃ at different sintering temperatures according to the above steps were used as examples 2 to 4.
Comparative example 1
Bi sintered at 450 DEG C0.5Sb1.5Te3The thermoelectric material was used as comparative example 1.
Comparative example 2
On the basis of example 1, the obtained composite material powder is filled into a graphite die, and hot-pressed for 6 minutes in a discharge plasma sintering process at a sintering temperature of 240 ℃ and under 50MPa to obtain a thermoelectric material Bi0.5Sb1.5Te3/CuHT5As comparative example 2.
Comparative example 3
Preparation of Cu by smelting process0.02Bi0.5Sb1.5Te3The experimental procedure was as follows: high-purity Bi powder (99.999%), Te powder (99.999%), Sb powder (99.999%) and Cu (particles, 99.99%, Alfa-Aesar) are mixed according to a certain stoichiometric ratio, and then the mixture is filled into a quartz tube with the diameter of 14mm for vacuum sealing. Putting the quartz glass tube into a box furnace, and smelting at the high temperature of 800 ℃ for 10 hours at the heating speed of 10 ℃/min. Cu obtained by smelting0.02Bi0.5Sb1.5Te3The ingot was pulverized for 4 hours using a high energy ball mill (SPEX 8000M) to obtain Cu0.02Bi0.5Sb1.5Te3And (3) powder. For bulk material preparation, the obtained powder was loaded into a graphite mold with a diameter of 12.7mm, and Cu was prepared by Spark Plasma Sintering (SPS) under 753K vacuum at a pressure of 50MPa for 5 minutes0.02Bi0.5Sb1.5Te3。
Comparative example 4
On the basis of comparative example 2, in this comparative example, CuHT accounts for 3% of the total mass, and the rest is the same as in comparative example 2.
The thermogravimetric decomposition curve of the CuHT material used in the present example is shown in FIG. 2, and the thermogravimetric decomposition curves of the CuHT material obtained at different sintering temperatures are BST/CuHT5X is distinguished, wherein X represents sintering temperature, a comparison graph of the thermoelectric materials obtained in examples 1-4 and the electrical properties of comparative examples 1-4 along with the change of the sintering temperature is shown in figure 3, and specific properties are shown in table 1.
For Bi0.5Sb1.5Te3(hereinafter, BST) and Bi0.5Sb1.5Te3/CuHT5(hereinafter, BST/CuHT)5) Cross-section Scanning Electron Microscope (SEM) testing of the sample perpendicular to the SPS hot pressing direction. From fig. 4(a) and 4(b) it can be seen that BST exhibits a layered crystal structure, but without a distinct preferred orientation, the presence of CuHT nanoplatelets can be observed in the composite, as in fig. 4 (c). This result indicates that even after the 365 ℃ high temperature SPS sintering process, some of the CuHT remains in its crystalline structure, which is beneficial for the growth scattering effect of the composite. The sample obtained by SPS sintering at 365 ℃ is named BST/CuHT5-365。
Further, Electron Back Scattering Diffraction (EBSD) characterization was performed on the samples before and after the recombination, and the results are shown in fig. 5(a) and 5 (b). Pure BST was found to exhibit a large lamellar structure with an average grain size of about 1.5 μm. The average grain size did not significantly decrease after the addition of CuHT, but as can be seen from the size distribution plot, the samples after compositing CuHT exhibited nanomaterials with sizes less than 500 nanometers (CuHT), and the elemental distribution of the composite is shown in fig. 5. FIG. 5(c) shows BST/CuHT5EBSD image of polished surface of-365 sample, CuHT (grey in the figure) is mainly distributed on grain boundary of BST (black in the figure), which is advantageous for enhancing interface phonon scattering.
Thermal conductivity (κ) and lattice thermal conductivity (κ) of thermoelectric materials of examples 1 to 4 and comparative examples 1 to 3Lat) Fig. 6 shows a graph of the dimensionless thermoelectric figure of merit zT as a function of temperature. BST/CuHT from example 15The 365 thermoelectric material is made into a single-leg device, and the performance of electrical property detection is performed on the device, as shown in fig. 7, it can be seen that by adopting the technical scheme of the embodiment, the dual optimization effects of electrical property and thermal property of the composite thermoelectric material can be greatly improved.
Comparative example 4
The same procedure as in example 1 was repeated except that the content of the infinite conjugated polymer was changed to 3% by mass of CuHT and that the sintering temperature was 240 ℃.
Example 5
The content of the infinite conjugated polymer was changed on the basis of example 1, wherein CuHT was 10% of the total mass, the sintering temperature was 450 ℃, and the other examples were the same as example 1.
Comparative example 5
The same procedure as in example 1 was repeated except that the content of the infinite conjugated polymer was changed to 3% by mass of CuHT and that the sintering temperature was 450 ℃.
The thermoelectric performance results of examples 1 to 5 and comparative examples 1 to 5 are shown in table 1, and it can be seen from the comparison between examples 1 to 5 and comparative examples 1 to 5 that the room temperature-based thermoelectric material containing an infinite conjugated polymer obtained by sintering at a temperature higher than 240 ℃ has a better performance (higher zT value than that obtained by sintering at 240 ℃), and the thermoelectric material obtained by sintering at 365 ℃ and 450 ℃ has the best performance.
For the amount of the infinite conjugated polymer, when the mass percent of the infinite conjugated polymer exceeds 3%, preferably 5-10%, the performance is good, the zT value is high, and the performance is good.
TABLE 1
Note: HT is tetrahydroxy thiophenol, and MOF-5 is a polymer formed by coordination of zinc (Zn) and terephthalic acid.
Example 6
Based on example 1, in this example, p-type Bi is prepared by a smelting method0.3Sb1.7Te3Performing high-energy ball milling for 4 hours to obtain infinite conjugated polymer CuHT and p-type Bi0.3Sb1.7Te3And (3) filling the two substances into a ball milling tank according to a metering ratio, wherein CuHT accounts for 5% of the total mass, and carrying out ball milling for 6 minutes to obtain the composite material powder. Putting the obtained composite material powder into a graphite die, and carrying out hot pressing for 6 minutes in a discharge plasma sintering process at the sintering temperature of 450 ℃ and under the pressure of 50MPa to obtain a thermoelectric material Bi0.3Sb1.7Te3/CuHT5Wherein 5 represents 5% of CuHT by mass.
Comparative example 6
With Bi0.3Sb1.7Te3As comparative example 6, it was prepared by a melting method of the prior art.
The thermoelectric properties of the materials obtained in example 6 and comparative example 6 are shown in table 1, and the zT value of example 6 is higher, so that the thermoelectric properties of the thermoelectric material obtained by the embodiment of the present invention are improved.
Example 7
Based on example 1, in this example, p-type Bi is prepared by a smelting method1.5Sb0.5Te3Performing high-energy ball milling for 4 hours to obtain infinite conjugated polymer CuHT and p-type Bi1.5Sb0.5Te3And (3) filling the two substances into a ball milling tank according to a metering ratio, wherein CuHT accounts for 5% of the total mass, and carrying out ball milling for 6 minutes to obtain the composite material powder. Putting the obtained composite material powder into a graphite die, and carrying out hot pressing for 6 minutes in a discharge plasma sintering process at the sintering temperature of 450 ℃ and under the pressure of 50MPa to obtain a thermoelectric material Bi1.5Sb0.5Te3/CuHT5Wherein 5 represents 5% of CuHT by mass.
Comparative example 7
With Bi1.5Sb0.5Te3As comparative example 7, it was prepared by a melting method of the prior art.
The thermoelectric properties of the materials obtained in example 7 and comparative example 7 are shown in table 1, and the zT value of example 7 is higher, so that the thermoelectric properties of the thermoelectric material obtained by the embodiment of the present invention are improved.
Example 8
In addition to example 1, Cu was used as an infinite conjugated polymer2(1,4 benzenedithiol)5Copper with 1, 4-benzenedithiol2The preparation method of the (1, 4-benzenedithiol) comprises the following steps: prepared by replacing 4-Hydroxythiophenol (HT) with 1, 4-benzenedithiol (1, 4-benzenedithiol) on the basis of the above CuHT, and then by the method of example 1.
An infinite conjugated polymer Cu2(1,4 benzenedithiol)5And p-type Bi0.5Sb1.5Te3The two materials are filled into a ball milling tank according to a metering ratio, Cu2(1,4 benzenedithiol)5Accounting for 5 percent of the total mass, and ball-milling for 6 minutes to obtain the composite material powder. The obtained composite material powder is put into a graphite die, and is hot-pressed for 6 minutes in a discharge plasma sintering process at the sintering temperature of 450 ℃ and under the pressure of 50 MPa. The obtained thermoelectric material had excellent thermoelectric properties, as shown in table 1, and had a zT value of 1.2.
Example 9
Nickel and p-phenylenediamine coordination product Ni2The preparation method of the (p-phenylenediamine) comprises the following steps: is 4-Hydroxythiophenol (HT) instead ofp-Phenylenediamine (p-Phenylenediamine) was substituted, and cuprous oxide was substituted with nickel nitrate hexahydrate, followed by preparation in accordance with example 1.
An infinite conjugated polymer Ni2(p-phenylenediamine) and p-type Bi0.5Sb1.5Te3The two materials are filled into a ball milling tank according to a certain proportion, Ni2The (p-phenylenediamine) accounts for 5 percent of the total mass, and the composite material powder is obtained after ball milling for 6 minutes. The obtained composite material powder is put into a graphite die, and is hot-pressed for 6 minutes in a discharge plasma sintering process at the sintering temperature of 450 ℃ and under the pressure of 50 MPa. The properties of the obtained thermoelectric material are shown in table 1. Therefore, the thermoelectric material has better thermoelectric performance.
Example 10
The coordination product MOF-5 of zinc and terephthalic acid is prepared from zinc nitrate hexahydrate and terephthalic acid in a stoichiometric ratio (molar ratio of Zn to terephthalic acid) of 1: and 1, reacting at 120 ℃ for 24 hours in a DMF solvent under the protection of nitrogen. And after the reaction is finished, filtering and cleaning the mixture by deionized water and ethanol, and drying the mixture in vacuum at 40 ℃ to obtain an MOF-5 powder sample.
An infinite conjugated polymer MOF-5 and p-type Bi0.5Sb1.5Te3And (3) filling the two substances into a ball milling tank according to the metering ratio, and carrying out ball milling for 6 minutes to obtain composite material powder, wherein the weight of the two substances is 5% of the total weight of the MOF-5. The obtained composite material powder is put into a graphite die, and is hot-pressed for 6 minutes in a discharge plasma sintering process at the sintering temperature of 450 ℃ and under the pressure of 50 MPa. The properties of the obtained thermoelectric material are shown in table 1. Therefore, the thermoelectric material has better thermoelectric performance.
As can be seen from comparison between the examples and the comparative examples in Table 1, the technical scheme of the invention improves the zT value of the thermoelectric material and the performance of the thermoelectric material.
In the above embodiment, a series of bismuth telluride-based composite thermoelectric materials are prepared by first utilizing the combination of ball milling and discharge plasma sintering processes, with the aim of preparing a high-performance bismuth telluride/wireless conjugated polymer composite thermoelectric material from the synthesis of an infinite wireless conjugated polymer. The carrier concentration and the lattice thermal conductivity of the composite material are regulated and controlled by regulating the type, the proportion and the processing technological parameters of the wireless conjugated polymer in the composite material, so that the bismuth telluride-based composite thermoelectric material with optimized electrical property and thermal property is finally obtained, and the thermoelectric efficiency of the material is improved.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (8)
1. A method for preparing room temperature based thermoelectric material containing infinite conjugated polymer is characterized in that: which comprises the following steps:
an infinite conjugated polymer, p-type bismuth telluride Bi2-xSbxTe3Carrying out mixing ball milling to obtain composite material powder, wherein x is more than 0 and less than or equal to 2;
carrying out hot-pressing discharge plasma sintering on the composite material powder at 250-450 ℃ to obtain a thermoelectric material;
the infinite conjugated polymer is a metal-based infinite conjugated polymer synthesized by an organic ligand of the following structural formula (1) and a metal element;
wherein R is amino or sulfydryl, and R' is sulfydryl, hydroxyl, carboxyl or amino.
2. The method of claim 1, wherein the step of preparing room temperature-based thermoelectric materials comprises: the pressure when the hot-pressing discharge plasma sintering is carried out is 40-60 MPa.
3. The method of claim 1, wherein the step of preparing room temperature-based thermoelectric materials comprises: the metal elements are copper, nickel and zinc.
4. The method of claim 3, wherein the room temperature thermoelectric material comprises an infinite conjugated polymer, and wherein: the infinite conjugated polymer is a nano material of coordination of tetrahydroxy thiophenol and copper, a coordination product of copper and 1, 4-benzenedithiol, a coordination product of nickel and p-phenylenediamine or a coordination product of zinc and terephthalic acid.
5. The method of claim 1, wherein the step of preparing room temperature-based thermoelectric materials comprises: the p-type bismuth telluride Bi2-xSbxTe3Ball milling is carried out for 3-5 hours, and then the mixture is mixed with infinite conjugated polymer for ball milling.
6. The method of claim 1, wherein the step of preparing room temperature-based thermoelectric materials comprises: the infinite conjugated polymer and p-type Bi2-xSbxTe3The powder is loaded into a ball mill pot and ball milled for 2 to 12 minutes.
7. The method for producing a room-temperature-based thermoelectric material comprising an infinite conjugated polymer according to any one of claims 1 to 6, wherein: when the infinite conjugated polymer and the p-type bismuth telluride are mixed and ball-milled, the mass percentage of the infinite conjugated polymer is not more than 10%.
8. A room-temperature-based thermoelectric material comprising an infinite conjugated polymer, wherein: the thermoelectric material is prepared by the method for preparing the room-temperature-based thermoelectric material containing the infinite conjugated polymer according to any one of claims 1 to 7.
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