CN114639770A - Room temperature base thermoelectric material containing metal organic polymer and preparation method thereof - Google Patents

Room temperature base thermoelectric material containing metal organic polymer and preparation method thereof Download PDF

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CN114639770A
CN114639770A CN202210157806.6A CN202210157806A CN114639770A CN 114639770 A CN114639770 A CN 114639770A CN 202210157806 A CN202210157806 A CN 202210157806A CN 114639770 A CN114639770 A CN 114639770A
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organic polymer
metal organic
metal
thermoelectric material
room temperature
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张倩
王晓东
何伙伦
曹峰
毛俊
刘兴军
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Shenzhen Graduate School Harbin Institute of Technology
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Shenzhen Graduate School Harbin Institute of Technology
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    • 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
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • 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

Abstract

The invention provides a room temperature based thermoelectric material containing metal organic polymer and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a metal organic polymer and 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 400-500 ℃ to obtain a thermoelectric material; wherein the metal organic polymer is metal phthalocyanine or metal phthalocyanine derivative. According to the technical scheme, the representative micromolecular phthalocyanine or derivative material thereof in the metal organic polymer is compounded with the inorganic thermoelectric material, the advantages of the porous structure and structural diversity of the metal organic polymer material are utilized, the electrical and thermal properties of the inorganic material are cooperatively optimized, and the inorganic thermoelectric material is enrichedAnd a new idea is provided for obtaining the high-performance thermoelectric material.

Description

Room temperature base thermoelectric material containing metal organic polymer and preparation method thereof
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a room temperature base thermoelectric material containing a metal organic polymer and a preparation method thereof.
Background
Thermoelectric materials (TE) are an environment-friendly "green" energy conversion material, and can directly realize interconversion between thermal energy and electric energy. Thermoelectric conversion devices using thermoelectric materials as cores have been widely used in refrigeration equipment, generators, thermal sensors, etc. by utilizing the Seebeck effect and Peltier effect of semiconductors, and cover the fields of military, aviation, instruments, biology, medical treatment, industry, commerce, etc.
The performance of thermoelectric materials is mainly characterized by a dimensionless thermoelectric figure of merit, zT ═ S2σ · 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 ideal thermoelectric material should have high Seebeck coefficient, high electrical conductivity and low thermal conductivity at the same time. The larger the zT value, the higher the thermoelectric conversion efficiency of the material. The thermoelectric device is firstly applied to some special fields such as space exploration and the like. The zT value of the thermoelectric material directly reflects the thermoelectric performance of the material. As can be seen from the formula, a thermoelectric material with excellent performance should have large σ and S coefficients and 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.
The bismuth telluride alloy is the most widely commercialized thermoelectric material as the earliest discovered compound semiconductor thermoelectric material, and is a main research target in recent years for further improving the thermoelectric performance of the material and effectively regulating and controlling the zT peak temperature region of the material, so that the bismuth telluride alloy can be widely applied in the fields of medium-low temperature waste heat power generation, thermoelectric refrigeration and the like. In the actual material research, the electrical and thermal coupling effects need to be considered cooperatively. Therefore, the search for new research methods for optimizing the thermoelectric properties of the material and simultaneously obtaining the thermoelectric material with enhanced mechanical properties are 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. In recent years, nano-composite is considered as a means for effectively optimizing the thermoelectric performance of inorganic materials, the basic idea is to reduce the size of a microstructure in the materials to the order of tens of nanometers or below, and the order of magnitude is equivalent to the wavelength of electrons and phonons, so that the coordinated optimization of the transport of carriers and phonons is realized, and meanwhile, the nano second phase filling is expected to obtain the enhancement of the mechanical performance.
Metal Organic Polymers (MOPs) are a class of porous materials with a periodic network structure formed by the interconnection of inorganic Metal centers (Metal ions or Metal clusters) and bridging Organic ligands by self-assembly. With the increasing variety of MOPs and the increasing emergence of composite materials, the MOPs have immeasurable application prospect. Therefore, development of MOPs and composite materials with functional diversity and application thereof in different fields will greatly promote the development of the disciplines. However, MOPs materials have inherently low electrical conductivity (10)-13～10-1S cm-1) Making it difficult to apply it alone in the thermoelectric field. Another major problem limiting the application of MOPs materials in the thermoelectric field is that most of MOPs have low thermal stability (decomposition temperature is less than 300 ℃), while most of the conventional inorganic thermoelectric materials are subjected to a high-temperature sintering process (greater than 400 ℃), and how to effectively combine the two materials is a difficult problem from the viewpoint of processing technology.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a room temperature based thermoelectric material containing a metal organic polymer and a preparation method thereof, which synergistically optimize the electrical and thermal properties of an inorganic material and improve the properties of the thermoelectric material.
In contrast, the technical scheme adopted by the invention is as follows:
a method of making a room temperature-based thermoelectric material comprising a metal-organic polymer, comprising:
mixing a metal organic polymer and 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 400-500 ℃ to obtain a thermoelectric material;
wherein the metal organic polymer is metal phthalocyanine or metal phthalocyanine derivative.
By adopting the technical scheme of the invention, the nano material composite technology is applied, the performance of the inorganic material thermoelectric material is optimized by utilizing the metal organic polymer, the material carrier concentration and the lattice thermal conductivity are synergistically regulated and controlled through the effective composite material processing technology, and the thermoelectric performance is improved.
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 the metal organic polymer for ball milling.
As a further improvement of the invention, the pressure when the hot-pressing discharge plasma sintering is carried out is 40-60 MPa. Further preferably 50 MPa.
As a further improvement of the invention, the ball milling time is from 2 to 12 minutes.
As a further improvement of the invention, the sintering temperature of the discharge plasma is 450-500 ℃. More preferably 450 ℃.
As a further improvement of the present invention, x satisfies: x is more than or equal to 0.3 and less than or equal to 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 coordination metal in the metal phthalocyanine is at least one of Cu, Pb, Mg, Zn and Co.
As a further improvement of the present invention, the metal organic polymer is copper phthalocyanine, lead phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine or copper phthalocyanine.
As a further improvement of the invention, the coordination metal of the metal-organic polymer is Cu, and the metal-organic polymer and the p-type bismuth telluride Bi2-xSbxTe3When the ball milling is carried out, the mass percentage of the metal organic polymer is 1-5%.
As a further improvement of the invention, the coordination metal of the metal organic polymer is Pb, and the metal organic polymer and the p-type bismuth telluride Bi are mixed2-xSbxTe3When the ball milling is carried out, the mass percentage of the metal organic polymer is 0.5-5%.
The invention also discloses a room temperature based thermoelectric material containing the metal organic polymer, which is prepared by adopting the preparation method of the room temperature based thermoelectric material containing the metal organic polymer.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention provides a novel strategy for optimizing an inorganic thermoelectric material, and the electric and thermal properties of the inorganic material are synergistically optimized by compounding a representative micromolecular phthalocyanine or derivative material thereof in a metal organic polymer and the inorganic thermoelectric material and utilizing the advantages of the porous structure and structural diversity of the metal organic polymer material. Compared with the prior art that the lattice thermal conductivity is reduced compositely or the electrical property is improved by doping, the metal organic polymer adopted by the technical scheme of the invention can comprehensively utilize the unique advantages of the material structure, realize the double optimization effects of the electrical property and the thermal property, enrich the means for optimizing the inorganic thermoelectric material and provide a new idea for obtaining the high-performance thermoelectric material.
Drawings
FIG. 1 shows different Bi in the examples of the present invention0.5Sb1.5Te3(BST) thermoelectric property profile with temperature of a base composite; (a) electrical conductivity (σ), (b) carrier concentration (n)H) (c) Seebeck coefficient (S) and (d) Power Factor (PF) versus temperature.
FIG. 2 shows different Bi in the examples of the present invention0.5Sb1.5Te3(BST) radicalThe composite material comprises BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02-the thermal conductivity of BST) and the profile of the amorphous lattice thermal conductivity as a function of temperature; (a) thermal conductivity (κ) and (b) non-lattice thermal conductivity (κ)Latt+κB) (c) lattice thermal conductivity (κ)Latt) (d) Bipolar diffusion thermal conductivity (κ)B)。
FIG. 3 shows Bi according to an embodiment of the present invention05Sb15Te3CuP bulk sample, BST/CuPc5Electron microscopy of the bulk composite; (a) is Bi0.5Sb1.5Te3(ii) a scanning electron microscope image of a cross section of the CuP bulk sample, and (c) Bi0.5Sb1.5Te3Wherein the inset shows the pole figure and the statistical data of the average grain size; (d) is BST/CuPc5Scanning electron microscope images of sections of the bulk composite, (e) is an enlarged image of the square frame part in (d), and (f) is BST/CuPc5Wherein the inset shows the pole figure and the statistical data of the average grain size; (g) BST/CuPc5EBSD images of polished surfaces of bulk materials, (h) shows a schematic representation of multiple scattering centers in BST-based composites.
FIG. 4 shows Bi according to an embodiment of the present invention0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02-BST) thermal performance versus temperature curve; (a) thermal diffusivity (D), specific heat capacity (C)p)。
FIG. 5 shows Bi according to an embodiment of the present invention0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02μ of-BST)w/κLattThe curve and the histogram of the change with the temperature are shown in (a) and (b).
FIG. 6 shows Bi according to an embodiment of the present invention0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02-BST) thermoelectric figure of merit (zT) versus temperature.
FIG. 7 shows Bi according to an embodiment of the present invention0.5Sb1.5Te3Average thermoelectric figure of merit (zT) for (BST) -based composites and BSTavg) Compare the figures.
FIG. 8 shows BST/CuPc according to an embodiment of the present invention5A thermoelectric performance map of a single-leg device; (a) is BST/CuPc5The output voltage (U) (left) output power (P) (right) of the single-leg device is in a change relation with the current; (b) is BST/CuPc5Experimental and theoretical thermoelectric conversion efficiencies (η) for single-leg devices; (c) the method comprises the following steps of optimizing a comparison curve of theoretical and actual maximum test thermoelectric conversion efficiency of a sample with temperature difference; (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.
FIG. 9 shows Bi according to an embodiment of the present invention0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1, and 5), BST/PbPcx(x ═ 1 and 5) thermoelectric properties as a function of temperature; (a) electrical conductivity (σ), (b) Seebeck coefficient (S), (c) Power Factor (PF), (d) Carrier concentration (n)H) (e) thermal conductivity (κ), (f) thermoelectric figure of merit (zT).
FIG. 10 TGA decomposition curves for Pc, CuPc and PbPc samples of examples of the present invention.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
P-type bismuth telluride Bi prepared by adopting chemically synthesized metal organic polymer and smelting method2-xSbxTe3(x is more than 0 and less than or equal to 2) is filled into a ball milling tank according to the metering ratio, and the ball milling is carried out for 2 to 12 minutes to obtain composite material powder; wherein, the p-type bismuth telluride Bi2-xSbxTe3High-energy ball milling is carried out for 4 hours. Then the obtained composite material powder is put into a graphite die at 450-500 DEG CAnd hot pressing for 2-5 minutes in the discharge plasma sintering process under 50 MPa.
The specific implementation mode of the invention selects micromolecular phthalocyanine and derivatives thereof as research objects, aims to prepare the high-performance bismuth telluride/metal organic polymer composite thermoelectric material, and combines ball milling and discharge plasma sintering processes to prepare a series of bismuth telluride-based composite thermoelectric materials. The carrier concentration and the lattice thermal conductivity of the composite material are regulated and controlled by regulating the type and the proportion of the wireless conjugated polymer in the composite material and processing technological parameters.
The following description will be given with reference to specific examples.
Example 1
Copper (II) phthalocyanine (CuPc) is a typical metal-organic polymer, featuring a metallic and organic porous framework. Single crystal CuPc is reported to exhibit high carrier mobility (-40 cm)2 V-1 s-1) And a high seebeck coefficient (-900 mu V K)-1). The CuPc particles have an ultra-low thermal conductivity of about 0.15W m-1 K-1. The research for optimizing the thermoelectric performance of the traditional inorganic material by fully utilizing the diversity advantages of the structure and the chemical composition of the CuPc material has not been reported.
In this example, copper (II) phthalocyanine (CuPc) and a smelting method are used to prepare a p-type bismuth telluride Bi0.5Sb1.5Te3Filling the mixture into a ball milling tank according to the metering ratio, and performing ball milling for 6 minutes to obtain composite material powder; wherein, the p-type bismuth telluride Bi0.5Sb1.5Te3High-energy ball milling is carried out for 4 hours. Then the obtained composite material powder is put into a graphite die and is hot-pressed for 5 minutes in a discharge plasma sintering process at the temperature of 450 ℃ and under the pressure of 50 MPa.
In this example, the mass percentage of CuPc is 1%, and the thermoelectric material obtained in this example is referred to as BST/CuPc1。
Example 2
The mass percentage of CuPc in example 1 was 3%, and the rest was the same as in example 1. The thermoelectric material obtained in this example was designated as BST/CuPc3。
Example 3
The mass percentage of CuPc in example 1 was 5%, and the rest was the same as in example 1. The thermoelectric material obtained in this example was designated as BST/CuPc5。
Comparative example 1
This comparative example is conventional Bi0.5Sb1.5Te3。
Comparative example 2
In the comparative example, the mass percentage of CuPc is 0.5% based on the example 1, and the rest is the same as the example 1. The thermoelectric material obtained in this example was designated as BST/CuPc0.5。
Comparative example 3
In the comparative example, the mass percentage of CuPc is 10% based on the example 1, and the rest is the same as the example 1. The thermoelectric material obtained in this example was designated as BST/CuPc10。
Comparative example 4
With Cu0.02Bi0.5Sb1.5Te3(Cu0.02BST) comparative example 4.
The method comprises the following steps: high-purity Bi powder (99.999 percent), Te powder (99.999 percent), Sb powder (99.999 percent) and Cu (particles, 99.99 percent and Alfa-Aesar) are mixed according to a certain stoichiometric ratio and then are 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. Thermoelectric properties of examples 1 to 3 and comparative examples 1 to 4 were compared, and Bi0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10, where x ═ 0 represents a group containing noCuPc, i.e. BST only, the same applies below), BST/Pc5、Cu0.02Bi0.5Sb1.5Te3(Cu0.02-BST), conductivity (σ), carrier concentration (n)H) The curves of the Seebeck coefficient (S) and the Power Factor (PF) with the temperature are shown in FIG. 1, and the curves of the thermoelectric performance with the temperature are shown in FIG. 2.
TABLE 1
Figure BDA0003512923660000061
Bi0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02-density (p), thermal diffusion coefficient (D) and specific heat capacity (C) of BST)p) The temperature profile is shown in FIG. 4, and the comparative performance table is shown in Table 1.
As can be seen from the comparison of the data in fig. 1, fig. 2, fig. 4 and table 1, the embodiment using the technical solution of the present invention has better thermoelectric performance and better thermal performance.
For Bi0.5Sb1.5Te3CuPc bulk sample, BST/CuPc5As a result of observing the microstructure of the bulk composite material, as shown in fig. 3, the morphology was observed from the fracture surface shown in fig. 3(a) and (b). BST exhibits a layered crystal structure but no apparent preferred orientation, whereas CuPc exhibits a two-dimensional sheet structure. Fig. 3(d) shows a low power SEM image of a composite BST bulk from 5 wt.% CuPc, where the observed BST particles are significantly smaller than the original BST particles shown in fig. 3(a), indicating that the introduction of CuPc may lead to a reduction in the grain size of BST. FIG. 3(e) shows BST/CuPc5High power SEM images of the composite material, in which the layered structure of BST and the elongated structure of CuPc are clearly visible. These results indicate that CuPc has high thermal stability.
To clearly reveal the effect of CuPc on BST grain growth, electron back-scattered diffraction (EBSD) characterization was also performed on the samples before and after compounding, junctionAs shown in fig. 3(c) and (f). Pure BST was found to exhibit a large lamellar structure with an average grain size of about 1.5 μm. The average grain size was significantly reduced to about 0.8 μm after the addition of CuPc. FIG. 3(g) shows BST/CuPc5EBSD image of the polished surface of the sample. CuPc (black) is mainly distributed on the grain boundary of BST (gray), which is beneficial to inhibiting the grain growth of BST and enhancing interface phonon scattering. Fig. 3(h) shows an optimization mechanism of CuPc for BST thermoelectric performance, that is, CuPc can introduce a multi-scale scattering center to enhance phonon scattering effect, and Cu can diffuse and dope to optimize electrical properties of the composite material.
Bi0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02μ of-BST)w/κLattThe curves and histograms of the variation with temperature are shown in figure 5. As can be seen from the comparison of the results in FIG. 5, due to the substantial reduction of the lattice thermal conductivity in the BST/CuPc composite, the thermal conductivity is favorable for μw/κLattIs increased. As the content of CuPc increases, μw/κLattThe average value in the full temperature range is increased and then decreased. At 3 wt%, the increase is nearly 55% compared to BST (FIG. 5 (b)).
Bi0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1,3,5, and 10), BST/Pc5，Cu0.02Bi0.5Sb1.5Te3(Cu0.02-BST) as shown in fig. 6; bi0.5Sb1.5Te3Thermoelectric figure of merit (zT) and average thermoelectric figure of merit (zT) for (BST) -based compositesavg) The comparative graph is shown in FIG. 7. As can be seen by comparing fig. 6 and fig. 7, the embodiment using the technical solution of the present invention has better thermoelectric performance.
Mixing BST/CuPc5The electrical performance of the single-leg device was measured and the results are shown in fig. 8, which shows that the open circuit voltage increased from 3.1mV to 36.3mV as the cold side temperature was set at 300K and the hot side temperature increased from 323K to 523K. When Δ T is 223K, the mostThe large output power reaches 42.5mW, and the power density at the moment is-0.18W cm-2. Because interface heat flow loss and contact thermal resistance exist at the heating module and the hot end of the thermoelectric device, the actual hot end temperature is lower than the temperature heated by one end of the heater. Therefore, the measured maximum output voltage is 4-5% lower than the theoretical calculation. In addition, the output power was reduced from a calculated value of-58 mW to a measured value of-52 mW due to an additional influence of the contact resistance. Fig. 8(b) shows the thermoelectric conversion efficiency as a function of current at different deltas. Finally, when Δ T is 223K, the peak ηmaxUp to about 6.8%, about 42% higher than pure BST (see fig. 8(c)), and also higher than previously reported BST-based composites (see fig. 8 (d)). The thermoelectric device made of the thermoelectric material in the technical scheme of the invention has higher conversion efficiency and better electrical property compared with commercial BST and partial BST-based composite thermoelectric materials.
Example 4
Based on example 1, this example utilizes lead phthalocyanine (PbPc) and melting method to prepare p-type bismuth telluride Bi0.5Sb1.5Te3Filling the mixture into a ball milling tank according to the metering ratio, and carrying out ball milling for 2-12 minutes to obtain composite material powder; wherein, the p-type bismuth telluride Bi0.5Sb1.5Te3High-energy ball milling is carried out for 4 hours. And then 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 400-500 ℃ and 50 MPa.
In this example, PbPc was 0.5% by mass, and the thermoelectric material obtained in this example was denoted as Bi0.5Sb1.5Te3/PbPc0.5I.e., BST/PbPc0.5。
Example 5
In example 4, PbPc was 1% by mass, and the rest was the same as in example 1. The thermoelectric material obtained in this example is denoted as Bi0.5Sb1.5Te3/PbPc1I.e., BST/PbPc1。
Example 6
In example 4, PbPc was 3% by mass, and the rest was the same as in example 1. This exampleThe resulting thermoelectric material is denoted as Bi0.5Sb1.5Te3/PbPc3I.e., BST/PbPc3。
Example 7
In example 4, PbPc accounts for 5% by mass, and the rest is the same as in example 1. The thermoelectric material obtained in this example is denoted as Bi0.5Sb1.5Te3/PbPc5I.e., BST/PbPc5。
Comparative example 5
In example 4, PbPc was contained in an amount of 10% by mass, and the rest was the same as in example 1. The thermoelectric material obtained in this example is denoted as Bi0.5Sb1.5Te3/PbPc10Namely BST/PbPc10。
Bi0.5Sb1.5Te3(BST) -based composite materials comprising BST/CuPcx(x ═ 0,1, and 5), BST/PbPcxThe temperature-dependent thermoelectric properties (x ═ 1 and 5) are shown in fig. 9, and it can be seen that PbPc is effective in increasing the conductivity of BST, which is significantly higher than CuPc at the same content. This is mainly due to the fact that the doping effect of Pb is more significant than that of Cu, and the diffusion of Pb element during the recombination process results in the carrier concentration from 1.0 × 1019cm-3To 2.4X 1020cm-3Is greatly enhanced. Therefore, the Seebeck coefficient is drastically reduced and the thermal conductivity is increased to a higher level, as compared to the CuPc composite material. Finally, both PF and zT of BST/PbPc composites exhibit lower levels, but this result is sufficient to confirm our speculation. Furthermore, under the same conditions, different types of metal elements can induce significantly different diffusion doping effects in all copper phthalocyanine analogues.
The TGA decomposition curves of the Pc, CuPc and PbPc samples are shown in FIG. 10, and it can be seen that CuPc has good thermal stability, with an initial decomposition temperature of 783K, slightly higher than the SPS sintering temperature of 753K. The TGA decomposition curve surface SPS process of the composite material has small thermal damage to the composite material, and the composite material is stable in the SPS sintering process. Meanwhile, the PbPc and the CuPc not only have similar crystal structures but also have similar thermal stability.
Example 9
In this example, on the basis of example 1, Bi is used as the p-type bismuth telluride0.3Sb1.7Te3The mass percentage of CuPc was 5%, and the rest was the same as in example 1. The thermoelectric material obtained in this example is denoted as Bi0.3Sb1.7Te3/CuPc5。
Comparative example 5
The comparative example is Bi0.3Sb1.7Te3Which is obtained by a smelting method in the prior art.
Example 10
In this example, Bi was used as the p-type bismuth telluride based on example 11.5Sb0.5Te3The mass percentage of CuPc was 5%, and the rest was the same as in example 1. The thermoelectric material obtained in this example is denoted as Bi1.5Sb0.5Te3/CuPc5。
Comparative example 7
The comparative example is Bi0.3Sb1.7Te3Which is obtained by a smelting method in the prior art.
Comparative example 8
In this example, on the basis of example 1, Bi is used as the p-type bismuth telluride1.5Sb0.5Te3Phthalocyanine (Pc) and smelting process to prepare p-type bismuth telluride Bi1.5Sb0.5Te3Filling the mixture 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 p-type bismuth telluride Bi1.5Sb0.5Te3High-energy ball milling is carried out for 4 hours. Then the obtained composite material powder is put into a graphite die and is hot-pressed for 5 minutes in a discharge plasma sintering process at the temperature of 450 ℃ and under the pressure of 50 MPa. Pc accounts for 5% by mass, and the thermoelectric material obtained in this example is referred to as Bi1.5Sb0.5Te3/Pc5。
Table 2 shows comparative thermoelectric properties of examples 1 to 10 and comparative examples 1 to 8.
TABLE 2
Figure BDA0003512923660000101
As can be seen from the comparison of the data in Table 2, by adopting the technical scheme of the invention, the electrical and thermal properties of the inorganic material are synergistically optimized by compounding the representative micromolecular metal phthalocyanine or derivative material thereof in the metal organic polymer and the inorganic thermoelectric material.
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 (10)

1. A method for preparing a room temperature based thermoelectric material containing a metal organic polymer is characterized in that: it comprises the following steps:
mixing a metal organic polymer and 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 400-500 ℃ to obtain a thermoelectric material;
wherein the metal organic polymer is metal phthalocyanine or metal phthalocyanine derivative.
2. The method for preparing a room temperature-based thermoelectric material comprising a metal organic polymer according to claim 1, wherein: the p-type bismuth telluride Bi2-xSbxTe3Ball milling is carried out for 3-5 hours, and then the mixture is mixed with the metal organic polymer for ball milling.
3. The method for preparing a room temperature-based thermoelectric material comprising a metal-organic polymer according to claim 1, wherein: the pressure for sintering the hot-pressing discharge plasma is 40-60 MPa.
4. The method for preparing a room temperature-based thermoelectric material comprising a metal organic polymer according to claim 1, wherein: the ball milling time is 2 to 12 minutes.
5. The method for preparing a room temperature-based thermoelectric material comprising a metal organic polymer according to claim 1, wherein: the p-type bismuth telluride Bi2-xSbxTe3Is Bi0.5Sb1.5Te3、Bi0.3Sb1.7Te3 Or Bi1.5Sb0.5Te3。
6. The method for producing a room temperature-based thermoelectric material comprising a metal organic polymer according to any one of claims 1 to 5, wherein: the coordination metal in the metal phthalocyanine is at least one of Cu, Pb, Mg, Zn and Co.
7. The method for preparing a room temperature-based thermoelectric material comprising a metal organic polymer according to claim 6, wherein: the metal organic polymer is copper phthalocyanine, lead phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine or copper phthalocyanine.
8. The method for preparing a room temperature-based thermoelectric material comprising a metal-organic polymer according to claim 6, wherein: the coordination metal of the metal organic polymer is Cu, and the metal organic polymer and the p-type bismuth telluride Bi are mixed2-xSbxTe3When the ball milling is carried out, the mass percentage of the metal organic polymer is 1-5%.
9. The method for preparing a room temperature-based thermoelectric material comprising a metal organic polymer according to claim 6, wherein: the coordination metal of the metal organic polymer is Pb, and the metal organic polymer and the p-type bismuth telluride Bi are prepared2-xSbxTe3When the mixture is ball-milled, the mass percentage of the metal organic polymer is 0.5-5%.
10. A room temperature based thermoelectric material comprising a metal organic polymer, characterized by: the metal-containing organic polymer room temperature-based thermoelectric material is prepared by the method for preparing the metal-containing organic polymer room temperature-based thermoelectric material as claimed in any one of claims 1 to 9.
CN202210157806.6A 2022-02-21 2022-02-21 Room temperature base thermoelectric material containing metal organic polymer and preparation method thereof Pending CN114639770A (en)

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