Au-doped high-performance inorganic plastic thermoelectric material and preparation method thereof

Abstract

The invention relates to an Au-doped high-performance inorganic plastic thermoelectric material and a preparation method thereof. The chemical formula of the Au-doped high-performance inorganic plastic thermoelectric material is Ag2-xAuxS1-yTey, x is larger than or equal to 0.001 and smaller than 0.1, and y is larger than 0 and smaller than 1. The preparation method of the Au-doped high-performance inorganic plastic thermoelectric material comprises the following steps: weighing an Ag elementary substance, an Au elementary substance, an S elementary substance and a Te elementary substance according to the stoichiometric ratio of the Au-doped high-performance inorganic plastic thermoelectric material, mixing, packaging in a quartz tube in vacuum, and melting at high temperature to obtain a liquid mixture; and slowly cooling the liquid mixture to obtain the Au-doped high-performance inorganic plastic thermoelectric material.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of thermoelectric materials, and relates to an Au-doped high-performance inorganic plastic thermoelectric material and a preparation method thereof. BACKGROUND

[0002] With the vigorous development of flexible electronic products and the demand for green energy collection, flexible thermoelectric materials capable of realizing self-power supply of electronic devices have attracted widespread attention. However, the high-performance Bi2Te3 thermoelectric materials developed at present near room temperature do not have flexibility, and organic thermoelectric materials have flexibility but low thermoelectric performance, especially low carrier mobility, which limits the development of organic thermoelectric devices. Therefore, the exploration and development of high-performance inorganic flexible thermoelectric materials are particularly important.

[0003] The discovery of inorganic flexible semiconductor Ag2S provides a direction for the development of flexible thermoelectric materials. Ag2S has a sawtooth-shaped folded layered monoclinic structure at room temperature, and its structure characteristics of easy sliding and difficult cleavage make Ag2S have good plasticity. However, the power factor of alpha-Ag2S is lower than 0.3 μW·cm -1 ·K -2 , which limits its practical application in wearable devices. The method of solid solution of Se / Te at the S site of Ag2S can effectively optimize the energy band structure, control the carrier concentration and improve the power factor to optimize the electrical performance. The currently discovered inorganic plastic semiconductor family includes Ag2S and pseudo-binary compounds obtained by solid solution at the S site, InSe single crystal, ZnS single crystal, and p-type AgCu(S, Se, Te) thermoelectric materials.

[0004] The development of high-performance flexible thermoelectric devices requires high-performance flexible n-type and p-type thermoelectric materials. The reported n-type inorganic plastic semiconductor materials have low thermoelectric performance and cannot be matched with p-type AgCu(S, Se, Te) thermoelectric materials. Therefore, it is urgent to develop new n-type high-performance inorganic plastic thermoelectric materials. SUMMARY

[0005] In view of the above problems, the purpose of the present application is to provide an Au-doped high-performance inorganic plastic n-type thermoelectric material and a preparation method thereof.

[0006] In one aspect, the present application provides an Au-doped high-performance inorganic plastic thermoelectric material, the chemical formula of the Au-doped high-performance inorganic plastic thermoelectric material is Ag 2-x Au x S 1-y Te y , wherein 0.001≤x<0.1, 0<y<1.

[0007] The Au-doped high-performance inorganic plastic thermoelectric material in the present application is Ag2S 1-y Te y (0<y<1) as a base, and Au is introduced in a stoichiometric ratio to obtain Ag 2-x Au x S 1-y Te y series compounds, which, on the basis of retaining the excellent plasticity and processability of Ag2S, obtain thermoelectric materials with thermoelectric performance far superior to Ag2S, and expand the inorganic plastic semiconductor family. Specifically, since the electronegativity of Au element is about 2.54, which is much greater than that of the same group element Ag (1.93), and is close to that of S element (2.58) and Te element (2.1), the same group element Au doping at the Ag site of Ag2(S, Te) inorganic plastic thermoelectric material should effectively reduce the carrier concentration, optimize the thermoelectric performance, and retain good plasticity. The optimal carrier concentration of n-type Ag2(S, Te) inorganic plastic thermoelectric material with Ag interstitial ions as carriers is in the order of 10 18 cm -3 , and too much Au substitution for Ag may cause excessive reduction of carrier concentration, which cannot achieve the purpose of optimizing thermoelectric performance, so the doping of Au element needs to be appropriate.

[0008] Preferably, 0.001≤x≤0.03; 0.1≤y≤0.9.

[0009] In addition, preferably, 0.002≤x≤0.01; 0.5≤y≤0.7.

[0010] Preferably, the electrical conductivity of the Au-doped high-performance inorganic plastic thermoelectric material at 300-600K is 25-1000S·cm -1 , preferably 100-800S·cm -1 .

[0011] Preferably, the Seebeck coefficient of the Au-doped high-performance inorganic plastic thermoelectric material at 300-600K is -300 to -50μV·K -1 , preferably -250 to -50μV·K -1 .

[0012] Preferably, the power factor of the Au-doped high-performance inorganic plastic thermoelectric material at 300-600K is 0.5-7μW·cm -1 ·K -2 , preferably 4-7μW·cm -1 ·K -1 .

[0013] Preferably, the Au-doped high-performance inorganic plastic thermoelectric material has a thermal conductivity of 0.1-0.7 W·m -1 ·K -1 at 300-600 K. -1 ·K -1 .

[0014] Preferably, the Au-doped high-performance inorganic plastic thermoelectric material has a lattice thermal conductivity of 0.1-0.4 W·m -1 ·K -1 at 300-600 K, preferably 0.1-0.34 W·m -1 ·K -1 .

[0015] Preferably, the Au-doped high-performance inorganic plastic thermoelectric material has a thermoelectric figure of merit zT of 0.1-1, preferably 0.4-1, at 300-600 K.

[0016] Preferably, the Au-doped high-performance inorganic plastic thermoelectric material has a bending deformation of more than 15%.

[0017] Preferably, the Au-doped high-performance inorganic plastic thermoelectric material has a compressive deformation of more than 20%.

[0018] In another aspect, the present application provides a preparation method of the Au-doped high-performance inorganic plastic thermoelectric material, comprising: weighing Ag, Au, S and Te elements according to the stoichiometric ratio of the Au-doped high-performance inorganic plastic thermoelectric material, mixing and then vacuum packaging in a quartz tube, and then high-temperature melting to obtain a liquid mixture; slowly cooling the liquid mixture to obtain the Au-doped high-performance inorganic plastic thermoelectric material.

[0019] Preferably, the purity of the Ag, Au, S and Te elements is ≥99.99%; and the morphology of the Ag, Au, S and Te elements is block, wire, sheet and block, respectively.

[0020] Preferably, the vacuum packaging is performed by a flame gun; the protective gas for the vacuum packaging is an inert gas; and the quartz tube is evacuated to control the internal pressure to 0.1-10 Pa.

[0021] Preferably, the high-temperature melting is performed at a temperature of 1000-2000℃ for 12-48 hours; and preferably, the temperature rising rate is 60-70℃ / hour.

[0022] Preferably, the slow cooling process comprises: firstly, cooling to 500-550 DEG C at a cooling rate of 15-20 DEG C / hour, holding for 72-84 hours; secondly, continuing to cool to 100-120 DEG C at a cooling rate of 15-20 DEG C / hour, holding for 10-15 hours; and finally, cooling to room temperature with the furnace.

[0023] Beneficial effects: The Au-doped high-performance inorganic plastic thermoelectric material provided by the application has a power factor of 2-8.5 muW cm -1 ·K -1 , which is much higher than that of Ag2S inorganic plastic semiconductor. Moreover, the Au-doped high-performance inorganic plastic thermoelectric material has a room-temperature thermoelectric figure of merit zT of 0.2-0.5, and a maximum thermoelectric figure of merit zT of about 0.4-1.0 at 600 K, which belongs to n-type thermoelectric materials with excellent thermoelectric performance in the inorganic plastic semiconductor family. Thirdly, the Au-doped high-performance inorganic plastic thermoelectric material has excellent plastic deformation capacity and processability, and in the three-point bending test, the strain is greater than 15%, and in the compression test, the strain is greater than 20%, which is comparable to the plastic deformation capacity of the reported Ag2S material. The development of the Au-doped high-performance inorganic plastic thermoelectric material realizes the coexistence of excellent plasticity and high thermoelectric performance. Therefore, it is a potential n-type inorganic plastic semiconductor material applied to high-performance flexible thermoelectric devices. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 It is a preparation flowchart of the Au-doped high-performance inorganic plastic thermoelectric material of the application; Figure 2 It is the inorganic plastic thermoelectric material Ag 1.995 Au 0.005 S 0.5 Te 0.5 of Example 1; Figure 3 It is the inorganic plastic thermoelectric material Ag 1.995 Au 0.005 S 0.5 Te 0.5 of Example 1; wherein (a) is a curve graph of the electrical conductivity changing with temperature; (b) is a curve graph of the Seebeck coefficient changing with temperature; (c) is a curve graph of the power factor PF changing with temperature; (d) is a curve graph of the thermal conductivity changing with temperature; (e) is a curve graph of the lattice thermal conductivity changing with temperature; and (f) is a curve graph of the thermoelectric figure of merit zT changing with temperature; Figure 4 It is the inorganic plastic thermoelectric material Ag 1.995 Au 0.005 S 0.5 Te0.5 compressive stress-strain curve (a) and three-point bending stress-strain curve (b) of the inorganic plastic thermoelectric material Ag Figure 5 inorganic plastic thermoelectric material Ag 1.99 Au 0.01 S 0.5 Te 0.5 EDS element distribution map of the thermoelectric compound; Figure 6 inorganic plastic thermoelectric material Ag 1.99 Au 0.01 S 0.5 Te 0.5 thermoelectric performance curves with temperature; wherein (a) is the electrical conductivity curve with temperature; (b) is the Seebeck coefficient curve with temperature; (c) is the power factor PF curve with temperature; (d) is the thermal conductivity curve with temperature; (e) is the lattice thermal conductivity curve with temperature; (f) is the thermoelectric figure of merit zT curve with temperature; Figure 7 inorganic plastic thermoelectric material Ag 1.99 Au 0.01 S 0.5 Te 0.5 compressive stress-strain curve (a) and three-point bending stress-strain curve (b) of the inorganic plastic thermoelectric material Ag Figure 8 inorganic plastic thermoelectric material Ag 1.97 Au 0.03 S 0.5 Te 0.5 EDS element distribution map of the thermoelectric compound; Figure 9 inorganic plastic thermoelectric material Ag 1.97 Au 0.03 S 0.5 Te 0.5 thermoelectric performance curves with temperature; wherein (a) is the electrical conductivity curve with temperature; (b) is the Seebeck coefficient curve with temperature; (c) is the power factor PF curve with temperature; (d) is the thermal conductivity curve with temperature; (e) is the lattice thermal conductivity curve with temperature; (f) is the thermoelectric figure of merit zT curve with temperature; Figure 10 inorganic plastic thermoelectric material Ag 1.97 Au 0.03 S 0.5 Te 0.5 compressive stress-strain curve (a) and three-point bending stress-strain curve (b) of the inorganic plastic thermoelectric material Ag Figure 11 Ag for Example 4 inorganic plastic thermoelectric material 1.998 Au 0.002 S 0.3 Te 0.7 EDS element mapping of the thermoelectric compound; Figure 12 Ag for Example 4 inorganic plastic thermoelectric material 1.998 Au 0.002 S 0.3 Te 0.7 plots of thermoelectric properties as a function of temperature; where (a) is a plot of electrical conductivity as a function of temperature; (b) is a plot of Seebeck coefficient as a function of temperature; (c) is a plot of power factor PF as a function of temperature; (d) is a plot of thermal conductivity as a function of temperature; (e) is a plot of lattice thermal conductivity as a function of temperature; (f) is a plot of thermoelectric figure of merit zT as a function of temperature; Figure 13 Ag for Example 4 inorganic plastic thermoelectric material 1.998 Au 0.002 S 0.3 Te 0.7 compressive stress-strain curve (a) and three-point bending stress-strain curve (b) of Figure 14 Ag for Example 5 inorganic plastic thermoelectric material 1.995 Au 0.005 S 0.3 Te 0.7 EDS element mapping of the thermoelectric compound; Figure 15 Ag for Example 5 inorganic plastic thermoelectric material 1.995 Au 0.005 S 0.3 Te 0.7 plots of thermoelectric properties as a function of temperature; where (a) is a plot of electrical conductivity as a function of temperature; (b) is a plot of Seebeck coefficient as a function of temperature; (c) is a plot of power factor PF as a function of temperature; (d) is a plot of thermal conductivity as a function of temperature; (e) is a plot of lattice thermal conductivity as a function of temperature; (f) is a plot of thermoelectric figure of merit zT as a function of temperature; Figure 16 Ag for Example 5 inorganic plastic thermoelectric material 1.995 Au 0.005 S 0.3 Te 0.77 compressive stress-strain curve (a) and three-point bending stress-strain curve (b) of Figure 17 Ag for Example 6 inorganic plastic thermoelectric material 1.99 Au 0.01 S0.3 Te 0.7 EDS elemental distribution diagram of thermoelectric compounds; Figure 18 Example 6: Inorganic Plastic Thermoelectric Material Ag 1.99 Au 0.01 S 0.3 Te 0.7 Thermoelectric properties as a function of temperature are shown in the following graphs: (a) Electrical conductivity as a function of temperature; (b) Seebeck coefficient as a function of temperature; (c) Power factor PF as a function of temperature; (d) Thermal conductivity as a function of temperature; (e) Lattice thermal conductivity as a function of temperature; and (f) Thermoelectric figure of merit zT as a function of temperature. Figure 19 Example 6: Inorganic Plastic Thermoelectric Material Ag 1.99 Au 0.01 S 0.3 Te 0.7 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b); Figure 20 Comparative Example 1: Inorganic Plastic Thermoelectric Material Ag2S 0.3 Te 0.7 EDS elemental distribution diagram of thermoelectric compounds; Figure 21 Comparative Example 1: Inorganic Plastic Thermoelectric Material Ag2S 0.3 Te 0.7 Thermoelectric properties as a function of temperature are shown in the following graphs: (a) Electrical conductivity as a function of temperature; (b) Seebeck coefficient as a function of temperature; (c) Power factor PF as a function of temperature; (d) Thermal conductivity as a function of temperature; (e) Lattice thermal conductivity as a function of temperature; and (f) Thermoelectric figure of merit zT as a function of temperature. Figure 22 Comparative Example 1: Inorganic Plastic Thermoelectric Material Ag2S 0.3 Te 0.7 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b); Figure 23 Comparative Example 2: Inorganic Plastic Thermoelectric Material Ag2S 0.5 Te 0.5 EDS elemental distribution diagram of thermoelectric compounds; Figure 24 Comparative Example 2: Inorganic Plastic Thermoelectric Material Ag2S 0.5 Te 0.5Thermoelectric properties as a function of temperature are shown in the following graphs: (a) Electrical conductivity as a function of temperature; (b) Seebeck coefficient as a function of temperature; (c) Power factor PF as a function of temperature; (d) Thermal conductivity as a function of temperature; (e) Lattice thermal conductivity as a function of temperature; and (f) Thermoelectric figure of merit zT as a function of temperature. Figure 25 Comparative Example 2: Inorganic Plastic Thermoelectric Material Ag2S 0.5 Te 0.5 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b); Figure 26 Comparative Example 3: Inorganic Plastic Thermoelectric Material Ag 1.99 Au 0.01 EDS elemental distribution diagram of S thermoelectric compound; Figure 27 Comparative Example 4: Inorganic Plastic Thermoelectric Material Ag 1.9 Au 0.1 S 0.5 Te 0.5 EDS elemental distribution diagram of thermoelectric compounds. Detailed Implementation

[0025] To further illustrate the invention's content, features, and practical effects, the invention will be described in detail below with reference to embodiments. It should be noted that the modification methods of the invention are not limited to these specific implementation methods. Equivalent substitutions and modifications made by those skilled in the art based on their reading of the invention's content, without departing from the spirit and essence of the invention, are also within the scope of protection claimed by the invention. Unless otherwise specified, each percentage refers to atomic percentage content.

[0026] Currently discovered inorganic plastic semiconductor families include Ag₂S and its pseudobinary compounds obtained by solid solution at the S-site, InSe single crystals, ZnS single crystals, and p-type AgCu(S,Se,Te) thermoelectric materials. While the developed p-type flexible thermoelectric materials exhibit excellent thermoelectric properties, further expansion of the inorganic plastic semiconductor family is needed to develop n-type inorganic plastic thermoelectric materials with thermoelectric properties matching those of p-type flexible thermoelectric materials for the development of flexible thermoelectric devices. Therefore, this invention provides an Au-doped high-performance inorganic plastic thermoelectric material with the chemical composition Ag₂. 2-x Au x S 1-y Te yWhere 0 < x < 0.1 (e.g., 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, etc.), and 0 < y < 1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc.). While retaining the excellent plasticity and processability of Ag2S, thermoelectric materials with thermoelectric properties far superior to Ag2S were obtained, expanding the family of inorganic plastic semiconductors. The Au-doped high-performance inorganic plastic thermoelectric material exhibits a strain of over 15% in the three-point bending test, demonstrating excellent plastic deformation capacity similar to Ag₂S. Furthermore, its room-temperature thermoelectric figure of merit (zT) is 0.2–0.5, and its maximum zT at 600K is 0.4–1.0. Within the inorganic plastic semiconductor family, it belongs to the n-type thermoelectric material category, characterized by superior thermoelectric performance.

[0027] In this invention, the chemical composition of the Au-doped high-performance inorganic plastic thermoelectric material is Ag. 2-x Au x S 1-y Te y Where 0.001 ≤ x < 0.1, 0 < y < 1, this invention utilizes special material design to dope Ag2(S,Te) plastic thermoelectric materials with Au, a member of the same group, at the Ag sites. Au's high electronegativity optimizes the carrier concentration of this system, achieving optimized thermoelectric performance while maintaining its excellent plastic deformation capability. When the gold doping amount exceeds 0.1%, the gold element distribution becomes uneven, resulting in the formation of a gold-silver alloy second phase. This leads to poor reproducibility in material preparation, and the presence of a second phase indicates that gold doping is incomplete.

[0028] In this invention, Ag2S is required. 1-y Te y Ag can only be prepared by using (0 < y < 1) as a substrate and introducing a certain amount of Au doping. 2-x Au x S 1-y Te y This invention uses a series of compounds, rather than directly doping Au into an Ag₂S substrate, possibly because Ag₂S is a monoclinic phase at room temperature, and trace amounts of Au cannot be incorporated, resulting in a distinct second phase. Furthermore, due to the extremely low electrical conductivity of Ag₂S, its thermoelectric properties need to be optimized by increasing its carrier concentration. However, Au has a much higher electronegativity than Ag, and doping with Au would further reduce the number of Ag interstitial ions, further decreasing the carrier concentration and thus hindering the improvement of Ag₂S thermoelectric properties. This invention obtains Ag₂S through solid solution solution of Te. 1-y Te yThe material properties are superior to Ag2S, but still worse than the thermoelectric properties predicted by the SPB model, mainly due to the properties of Ag2S. 1-y Te y The carrier concentration of the series of materials is relatively high, so gold doping is needed to further reduce the carrier concentration and improve the material performance. In addition, the present invention first dissolves Te and then does not dope it with gold because dissolving Te will change the crystal phase from monoclinic to cubic, thereby achieving Au doping.

[0029] The following exemplarily illustrates the preparation method of the Au-doped high-performance inorganic plastic thermoelectric material provided by the present invention, such as... Figure 1 As shown.

[0030] According to the stoichiometric ratio of Au-doped high-performance inorganic plastic thermoelectric material, Ag, Au, S and Te elements were weighed, mixed and vacuum-sealed in a quartz tube, and then melted at high temperature to obtain a liquid mixture.

[0031] In an optional embodiment, the purity of the Ag, Au, S, and Te elements is ≥99.99%. The morphologies of the Ag, Au, S, and Te elements are blocky, linear, flake-like, and blocky, respectively.

[0032] In an optional implementation, the vacuum sealing method can be flame gun sealing.

[0033] A high-performance inorganic plastic thermoelectric material doped with Au was obtained by slowly cooling the liquid mixture.

[0034] In an optional embodiment, the melting process includes: heating to 1000-2000°C at a heating rate of 60-70°C / hour, and melting at a constant temperature for 12-48 hours.

[0035] In an optional embodiment, the slow cooling process includes: first cooling to 500-550°C at a cooling rate of 5-20°C / hour and holding at that temperature for 72-84 hours; then cooling to 100-120°C at a cooling rate of 15-20°C / hour and holding at that temperature for 10-15 hours; and finally cooling to room temperature with the furnace.

[0036] In one embodiment of the present invention, Ag, Au, Te, and S are weighed in a molar ratio of 1.995:0.005:0.5:0.5 and then vacuum-sealed. The vacuum sealing is performed under an inert gas atmosphere. The vacuum sealing is performed using a flame torch. The raw materials used are preferably high-purity elements. As an example, the Ag, Au, Te, and S elements are sealed in a quartz tube according to a stoichiometric ratio and vacuum-sealed using a flame torch, with an internal pressure of 0.1–10 Pa.

[0037] Then, the vacuum-sealed raw materials are melted to form a liquid mixture. As an example, the sealed quartz tube is heated to 1150°C at a heating rate of 70°C / hour, melted at a constant temperature for 48 hours, then cooled to 550°C and held for 72 hours, then cooled to 120°C and held for 10 hours before being cooled in the furnace.

[0038] In this invention, the elemental distribution was confirmed using a field emission scanning electron microscope equipped with energy-dispersive X-ray analysis. The mechanical properties (bending and compressive deformation) were tested using a dynamic thermomechanical analyzer and a universal testing machine. The thermoelectric properties (power factor and zT value) were tested using a ZEM-3 electrical performance testing device and a laser thermal conductivity meter (LFA). The thermal diffusivity λ of the thermoelectric material was measured using a laser thermal conductivity meter, and the specific heat C of the material was estimated using the Neumann-Kopp rule. p The density D of a material is measured using Archimedes' principle, and the formula κ = λC is used. p The thermal conductivity of the material is calculated using D. Then, it is cut into the desired shape (e.g., a strip) using diamond, and the electrical conductivity σ of the sample is measured using the classic four-terminal method. The Seebeck coefficient S is measured as the ratio of the potential difference across the sample to the temperature difference. Lattice thermal conductivity κ L =κ-κ e κ e =LσT. Using the formula zT = S 2 The thermoelectric figure of merit of the material is calculated using σT / κ.

[0039] In this invention, the electrical conductivity of the obtained Au-doped high-performance inorganic plastic thermoelectric material is 25–1000 S·cm. -1 Preferably, the value is 100–800 S·cm. -1 The Seebeck coefficient is -300 to -50 μV·K. -1 Preferably -250 to -50 μV·K -1 The power factor is 2–8.5 μW·cm. -1 ·K -2 Preferably 4–7 μW·cm -1 ·K -1 Thermal conductivity is 0.1–0.7 W·m -1 ·K -1 Preferably, it is 0.1–0.6 W·m -1 ·K -1 The lattice thermal conductivity is 0.1–0.4 W·m. -1 ·K -1 Preferably, it is 0.1–0.34 W·m -1 ·K -1The thermoelectric figure of merit zT is 0.1 to 1, preferably 0.4 to 1; the bending deformation is 15% or more; and the compression deformation is 20% or more.

[0040] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0041] Example 1

[0042] In this embodiment 1, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0.005,y=0.5) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.995:0.005:0.5:0.5 respectively, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain the ingot sample.

[0043] Figure 2 Example 1: Inorganic Plastic Thermoelectric Material Ag 1.995 Au 0.005 S 0.5 Te 0.5 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, gold doping yields Ag... 1.995 Au 0.005 S 0.5 Te 0.5 In the polycrystalline bulk semiconductor material, the four elements Ag, Au, S and Te are all uniformly distributed.

[0044] Figure 3 Example 1: Inorganic Plastic Thermoelectric Material Ag 1.995 Au 0.005 S 0.5 Te 0.5 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag... 1.995 Au 0.005 S 0.5 Te 0.5The electrical conductivity of the polycrystalline bulk material is 200–600 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -150 and -70 μV·K. -1 The power factor of the material, calculated from electrical performance measurements, ranges from 4.5 to 7.5 μW·cm. -1 ·K -2 The thermal conductivity is between 0.45 and 0.65 W·m. -1 ·K -1 Between these ranges, the lattice thermal conductivity is 0–0.2 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.25, and the maximum zT value at 600 K is approximately 0.75.

[0045] Figure 4 Example 1: Inorganic Plastic Thermoelectric Material Ag 1.995 Au 0.005 S 0.5 Te 0.5 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold doping produces Ag... 1.995 Au 0.005 S 0.5 Te 0.5 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0046] Example 2

[0047] In this embodiment 2, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0.01,y=0.5) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.99:0.01:0.5:0.5, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain the ingot sample.

[0048] Figure 5 Example 2: Inorganic plastic thermoelectric material Ag 1.99 Au 0.01 S 0.5 Te 0.5EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, gold doping yields Ag... 1.99 Au 0.01 S 0.5 Te 0.5 In the polycrystalline bulk semiconductor material, the four elements Ag, Au, S and Te are all uniformly distributed.

[0049] Figure 6 Example 2: Inorganic plastic thermoelectric material Ag 1.99 Au 0.01 S 0.5 Te 0.5 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag... 1.99 Au 0.01 S 0.5 Te 0.5 The electrical conductivity of the polycrystalline bulk material is 200–500 S·cm within the measured temperature range (300–600 K). -1 Seebeck coefficient ranges from -175 to -100 μV·K. -1 The power factor of the material was calculated to be between 4.5 and 6 μW·cm based on electrical performance measurements. -1 ·K -2 The thermal conductivity is between 0.3 and 0.4 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.05–0.15 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.45, and the maximum zT value at 600 K is approximately 0.95.

[0050] Figure 7 Example 2: Inorganic plastic thermoelectric material Ag 1.99 Au 0.01 S 0.5 Te 0.5 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold doping produces Ag... 1.99 Au 0.01 S 0.5 Te 0.5 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0051] Example 3

[0052] In this embodiment 3, Ag 2-x Au x S 1-y Te yThe preparation method of polycrystalline bulk semiconductor material (x=0.03,y=0.5) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.97:0.03:0.5:0.5 respectively, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain the ingot sample.

[0053] Figure 8 Example 3: Inorganic Plastic Thermoelectric Material Ag 1.97 Au 0.03 S 0.5 Te 0.5 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, gold doping yields Ag... 1.97 Au 0.03 S 0.5 Te 0.5 In the polycrystalline bulk semiconductor material, the four elements Ag, Au, S and Te are all uniformly distributed.

[0054] Figure 9 Example 3: Inorganic Plastic Thermoelectric Material Ag 1.97 Au 0.03 S 0.5 Te 0.5 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag... 1.97 Au 0.03 S 0.5 Te 0.5 The electrical conductivity of the polycrystalline bulk material is 60–120 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -250 and -200 μV·K. -1 The power factor of the material, calculated from electrical performance measurements, ranges from 4 to 5.5 μW·cm. -1 ·K -2 The thermal conductivity is between 0.3 and 0.4 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.25–0.3 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.25, and the maximum zT value at 600 K is approximately 0.7.

[0055] Figure 10 Example 3: Inorganic Plastic Thermoelectric Material Ag 1.97 Au 0.03 S 0.5 Te 0.5The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold doping produces Ag... 1.97 Au 0.03 S 0.5 Te 0.5 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0056] Example 4

[0057] In Example 4, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0.002,y=0.7) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.998:0.002:0.3:0.7, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain the ingot sample.

[0058] Figure 11 Example 4: Inorganic Plastic Thermoelectric Material Ag 1.998 Au 0.002 S 0.3 Te 0.7 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, gold doping yields Ag... 1.998 Au 0.002 S 0.3 Te 0.7 In the polycrystalline bulk semiconductor material, the four elements Ag, Au, S and Te are all uniformly distributed.

[0059] Figure 12 Example 4: Inorganic Plastic Thermoelectric Material Ag 1.998 Au 0.002 S 0.3 Te 0.7 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag... 1.998 Au 0.002 S 0.3 Te 0.7 The electrical conductivity of the polycrystalline bulk material is 300–700 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -170 and -100 μV·K. -1The power factor of the material, calculated from electrical performance measurements, ranges from 7 to 8.5 μW·cm. -1 ·K -2 The thermal conductivity is between 0.45 and 0.7 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.15–0.3 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.42, and the maximum zT value at 600 K is approximately 0.7.

[0060] Figure 13 Example 4: Inorganic Plastic Thermoelectric Material Ag 1.998 Au 0.002 S 0.3 Te 0.7 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold doping produces Ag... 1.998 Au 0.002 S 0.3 Te 0.7 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0061] Example 5

[0062] In Example 5, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0.005,y=0.7) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.995:0.005:0.3:0.7, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain an ingot sample.

[0063] Figure 14 Example 5: Inorganic plastic thermoelectric material Ag 1.995 Au 0.005 S 0.3 Te 0.7 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, gold doping yields Ag... 1.995 Au 0.005 S 0.3 Te 0.7In the polycrystalline bulk semiconductor material, the four elements Ag, Au, S and Te are all uniformly distributed.

[0064] Figure 15 Example 5: Inorganic plastic thermoelectric material Ag 1.995 Au 0.005 S 0.3 Te 0.7 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag... 1.995 Au 0.005 S 0.3 Te 0.7 The electrical conductivity of the polycrystalline bulk material is 200–600 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -175 and -100 μV·K. -1 The power factor of the material, calculated from electrical performance measurements, ranges from 5.5 to 6.5 μW·cm. -1 ·K -2 The thermal conductivity is between 0.3 and 0.45 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.05–0.15 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.42, and the maximum zT value at 600 K is approximately 0.8.

[0065] Figure 16 Example 5: Inorganic plastic thermoelectric material Ag 1.995 Au 0.005 S 0.3 Te 0.7 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold doping produces Ag... 1.995 Au 0.005 S 0.3 Te 0.7 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0066] Example 6

[0067] In Example 6, Ag 2-x Au x S 1-y Te yThe preparation method of polycrystalline bulk semiconductor material (x=0.01,y=0.7) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.99:0.01:0.3:0.7, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain the ingot sample.

[0068] Figure 17 Example 6: Inorganic Plastic Thermoelectric Material Ag 1.99 Au 0.01 S 0.3 Te 0.7 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, gold doping yields Ag... 1.99 Au 0.01 S 0.3 Te 0.7 In the polycrystalline bulk semiconductor material, the four elements Ag, Au, S and Te are all uniformly distributed.

[0069] Figure 18 Example 6: Inorganic Plastic Thermoelectric Material Ag 1.99 Au 0.01 S 0.3 Te 0.7 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag... 1.99 Au 0.01 S 0.3 Te 0.7 The electrical conductivity of the polycrystalline bulk material is 100–300 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -200 and -100 μV·K. -1 The power factor of the material, calculated from electrical performance measurements, ranges from 4.5 to 6.5 μW·cm. -1 ·K -2 The thermal conductivity is between 0.35 and 0.6 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.2–0.4 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.4, and the maximum zT value at 600 K is approximately 0.65.

[0070] Figure 19 Example 6: Inorganic Plastic Thermoelectric Material Ag 1.99 Au 0.01 S 0.3 Te0.7 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold doping produces Ag... 1.99 Au 0.01 S 0.3 Te 0.7 In the three-point bending test, the bending strain of the polycrystalline bulk semiconductor material can reach more than 15%, and in the compression test, the compressive strain can reach more than 20%, demonstrating excellent plastic deformation ability.

[0071] Comparative Example 1

[0072] In this comparative example 1, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0,y=0.7) includes: weighing Ag, S and Te elements in a molar ratio of 2:0.3:0.7, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain an ingot sample.

[0073] Figure 20 Comparative Example 1: Inorganic Plastic Thermoelectric Material Ag2S 0.3 Te 0.7 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, Ag₂S… 0.3 Te 0.7 In the polycrystalline bulk semiconductor material, the three elements Ag, S and Te are all uniformly distributed.

[0074] Figure 21 Comparative Example 1: Inorganic Plastic Thermoelectric Material Ag2S 0.3 Te 0.7 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag₂S… 0.3 Te 0.7 The electrical conductivity of the polycrystalline bulk material is 400–1050 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -150 and -70 μV·K. -1 The power factor of the material, calculated from electrical performance measurements, ranges from 4 to 7 μW·cm. -1 ·K -2 The thermal conductivity is between 0.5 and 0.75 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.05–0.35 W·m. -1 ·K-1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.25, and the maximum zT value at 600 K is approximately 0.55.

[0075] Figure 22 Comparative Example 1: Inorganic Plastic Thermoelectric Material Ag2S 0.3 Te 0.7 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold-doped Ag₂S… 0.3 Te 0.7 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0076] Comparative Example 2

[0077] In this comparative example 2, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0,y=0.5) includes: weighing Ag, S and Te elements in a molar ratio of 2:0.5:0.5, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain the ingot sample.

[0078] Figure 23 Comparative Example 2: Inorganic Plastic Thermoelectric Material Ag2S 0.5 Te 0.5 EDS elemental distribution diagram of thermoelectric compounds. As shown in the diagram, Ag₂S… 0.5 Te 0.5 In the polycrystalline bulk semiconductor material, the three elements Ag, S and Te are all uniformly distributed.

[0079] Figure 24 Comparative Example 2: Inorganic Plastic Thermoelectric Material Ag2S 0.5 Te 0.5 Thermoelectric properties as a function of temperature are shown in the graph. As can be seen from the graph, the obtained Ag₂S… 0.5 Te 0.5 The electrical conductivity of the polycrystalline bulk material is 300–1000 S·cm within the measured temperature range (300–600 K). -1 The Seebeck coefficient is between -150 and -70 μV·K. -1 The power factor of the material, calculated from electrical performance measurements, ranges from 4 to 7 μW·cm. -1·K -2 The thermal conductivity is between 0.54 and 0.56 W·m. -1 ·K -1 Between these values, the lattice thermal conductivity is 0.05–0.25 W·m. -1 ·K -1 The zT value of this material at room temperature, calculated based on performance measurements, is approximately 0.25, and the maximum zT value at 600K is approximately 0.7.

[0080] Figure 25 Comparative Example 2: Inorganic Plastic Thermoelectric Material Ag2S 0.5 Te 0.5 The compressive stress-strain curve (a) and the three-point bending stress-strain curve (b) are shown in the figure. As can be seen from the figure, gold-doped Ag₂S… 0.5 Te 0.5 The polycrystalline bulk semiconductor material exhibits excellent plastic deformation capabilities, with bending strain exceeding 15% in the three-point bending test and compressive strain exceeding 20% ​​in the compression test.

[0081] Comparative Example 3

[0082] In this comparative example 3, Ag 2-x Au x S 1-y Te y The preparation method of polycrystalline bulk semiconductor material (x=0.01,y=0) includes: weighing Ag, Au and S elements in a molar ratio of 1.99:0.01:1, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain an ingot sample.

[0083] like Figure 26 As shown, Ag obtained by gold doping 1.99 Au 0.01 Significant gold enrichment occurs in the polycrystalline bulk of S semiconductor material, making direct gold doping impossible within the Ag2S system.

[0084] Comparative Example 4

[0085] In Comparative Example 4, Ag 2-x Au x S 1-y Te yThe preparation method of polycrystalline bulk semiconductor material (x=0.1,y=0.5) includes: weighing Ag, Au, S and Te elements in a molar ratio of 1.9:0.1:0.5:0.5, vacuum sealing them in a quartz tube, heating to 1150℃ at a heating rate of 70℃ / hour, melting at a constant temperature for 48 hours, then cooling to 550℃ at a rate of 20℃ / hour, holding at that temperature for 72 hours, then continuing to cool to 120℃ at a rate of 20℃ / hour, holding at that temperature for 10 hours, and then cooling with the furnace to obtain an ingot sample.

[0086] like Figure 27 As shown, Ag obtained by gold doping 1.9 Au 0.1 S 0.5 Te 0.5 Significant gold enrichment occurs in the polycrystalline bulk of semiconductor materials, so the maximum gold doping level is around 0.1.

[0087] Table 1: x y zT (room temperature / 300 K) zT (600 K) Example 1 0.005 0.5 0.25 0.75 Example 2 0.01 0.5 0.45 0.95 Example 3 0.03 0.5 0.25 0.7 Example 4 0.002 0.7 0.42 0.7 Example 5 0.005 0.7 0.42 0.8 Example 6 0.01 0.7 0.4 0.65 Comparative Example 1 0 0.7 0.23 0.55 Comparative Example 2 0 0.5 0.25 0.7

[0088] As shown in Table 1, the thermoelectric properties of the material first increase and then decrease with increasing gold doping concentration, with the optimal doping concentration around 0.002–0.01%. This is because the more electronegative Au replaces Ag, reducing the carrier concentration to an optimal range, thus optimizing electrical performance (increased power factor) while reducing thermal conductivity. Excessive doping leads to a significant decrease in carrier concentration, resulting in deterioration of electrical performance and consequently, thermoelectric performance. Therefore, trace gold doping can optimize thermoelectric properties while maintaining good plasticity in the Ag2(S,Te) material system.

Claims

1. An Au-doped high-performance inorganic plastic thermoelectric material, characterized in that, The chemical formula of the Au-doped high-performance inorganic plastic thermoelectric material is Ag. 2-x Au x S 1-y Te y , where 0.001≤x<0.1, 0<y<1.

2. The Au-doped high-performance inorganic plastic thermoelectric material according to claim 1, characterized in that, 0.001≤x≤0.03; 0.1≤y≤0.

9.

3. The Au-doped high-performance inorganic plastic thermoelectric material according to claim 2, characterized in that, 0.002≤x≤0.01; 0.5≤y≤0.

7.

4. The Au-doped high-performance inorganic plastic thermoelectric material according to any one of claims 1-3, characterized in that, The Au-doped high-performance inorganic plastic thermoelectric material has an electrical conductivity of 25–1000 S·cm at 300–600 K. -1 Preferably, the value is 100–800 S·cm. -1 ; The Au-doped high-performance inorganic plastic thermoelectric material has a Seebeck coefficient of -300 to -50 μV·K at 300–600 K. -1 Preferably -250 to -50 μV·K -1 ; The Au-doped high-performance inorganic plastic thermoelectric material has a thermal conductivity of 0.1–0.7 W·m at 300–600 K. -1 ·K -1 Preferably, it is 0.1–0.6 W·m -1 ·K -1 .

5. The Au-doped high-performance inorganic plastic thermoelectric material according to any one of claims 1-4, characterized in that, The Au-doped high-performance inorganic plastic thermoelectric material has a power factor of 2–8.5 μW·cm at 300–600 K. -1 ·K -2 Preferably 4–7 μW·cm -1 ·K -1 ; The Au-doped high-performance inorganic plastic thermoelectric material has a lattice thermal conductivity of 0.1–0.4 W·m at 300–600 K. -1 ·K -1 Preferably, it is 0.1–0.34 W·m -1 ·K -1 .

6. The Au-doped high-performance inorganic plastic thermoelectric material according to any one of claims 1-5, characterized in that, The Au-doped high-performance inorganic plastic thermoelectric material has a thermoelectric figure of merit zT of 0.1 to 1, preferably 0.4 to 1, at 300 to 600 K; The Au-doped high-performance inorganic plastic thermoelectric material exhibits a bending deformation of more than 15%. The Au-doped high-performance inorganic plastic thermoelectric material exhibits a compression deformation of over 20%.

7. A method for preparing an Au-doped high-performance inorganic plastic thermoelectric material according to any one of claims 1-6, characterized in that, include: According to the stoichiometric ratio of Au-doped high-performance inorganic plastic thermoelectric material, Ag, Au, S and Te elements are weighed, mixed and vacuum-sealed in a quartz tube, and then melted at high temperature to obtain a liquid mixture. The liquid mixture is then slowly cooled to obtain the Au-doped high-performance inorganic plastic thermoelectric material.

8. The preparation method according to claim 7, characterized in that, The vacuum sealing method is flame gun sealing; the protective gas for the vacuum sealing is an inert gas; the quartz tube is evacuated to control its internal pressure to 0.1-10 Pa.

9. The preparation method according to claim 7 or 8, characterized in that, The high-temperature melting process includes: a high-temperature melting temperature of 1000–2000°C and a high-temperature melting time of 12–48 hours; preferably, the high-temperature melting heating rate is 60–70°C / hour.

10. The preparation method according to any one of claims 7-9, characterized in that, The slow cooling process includes: First, cool the furnace to 500-550℃ at a cooling rate of 15-20℃ / hour and hold for 72-84 hours; then continue cooling the furnace to 100-120℃ at a cooling rate of 15-20℃ / hour and hold for 10-15 hours; finally, cool the furnace to room temperature.

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