CN107359232B - Cubic phase Cu 3 SbS 3 -based thermoelectric material and method for preparing thermoelectric material through element replacement - Google Patents
Cubic phase Cu 3 SbS 3 -based thermoelectric material and method for preparing thermoelectric material through element replacement Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 107
- 238000005245 sintering Methods 0.000 claims description 26
- 229910052787 antimony Inorganic materials 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 238000000713 high-energy ball milling Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000013590 bulk material Substances 0.000 claims 1
- -1 x is 0.025-0.200 Substances 0.000 abstract 1
- 238000002490 spark plasma sintering Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052969 tetrahedrite Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 239000010439 graphite Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
- H10N10/80—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
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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
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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
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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Abstract
The invention provides a cubic phase Cu 3 SbS 3 -based thermoelectric material, which has a chemical general formula of Cu 3 Sb 1-x A x S 3, wherein A is cobalt and/or nickel, x is 0.025-0.200, and a Cu 3 Sb 1- x A x S 3 cubic crystal structure with stable structure and thermodynamic property is synthesized by replacing Sb elements with Ni, Co and other elements.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a cubic phase Cu 3 SbS 3 -based thermoelectric material and a preparation method for synthesizing a stable cubic phase Cu 3 SbS 3 -based thermoelectric material through element replacement.
Background
energy safety is an important component of national safety, and the recovery of partial heat energy from waste heat generated in the use process of primary energy by adopting a new energy conversion and recovery technology is an important way for reducing the use amount of petroleum, natural gas and the like and relieving the pressure of China on foreign petroleum supply. The thermoelectric power generation technology is a new energy conversion technology for realizing direct conversion of heat energy and electric energy by utilizing the Seebeck effect of a semiconductor, wherein a thermoelectric material suitable for a medium-temperature interval has an important application prospect in power generation (solar energy, terrestrial heat, industrial waste heat, automobile exhaust waste heat and the like are recycled), and is an important new energy conversion material for dealing with global warming and energy shortage. Compared with the traditional telluride thermoelectric material, the Cu-Sb-S thermoelectric material has the advantages of no toxicity, low cost, easy obtainment of synthetic raw materials and the like, and gradually becomes one of new research hotspots required by the development trend of low carbon and green in the current society.
the Cu 357 SbS 3 compound has a chemical composition similar to that of Cu 3 SbS 3.25, and structural studies show that the compound has three completely defined components, namely Cu 3 SbS 3 is an orthogonal phase at low temperature, a space group is P2 1 1 1, a monoclinic phase is between 263K and 395K, a space group is P2 1/c, another orthogonal phase is between 395K and a melting point, and a space group is Pnma.
In the prior art, Zhong et al synthesizes Cu 3 SbS 3 nanorods by a solvothermal method, and Maiello et al synthesizes a Cu 68 SbS 3 thin film on a glass substrate by a two-step method (magnetron sputtering and vulcanization process), but both obtained products are metastable, so that the application of the thermoelectric material between the thermoelectric material and the substrate from a metastable state to a monoclinic state or an orthorhombic stable phase structure is inevitable in the heat treatment process or service process, and the good thermal and electrical contact between the thermoelectric material and the substrate is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cubic phase Cu 3 SbS 3 -based thermoelectric material and a preparation method thereof aiming at the defects in the prior art, namely Co and/or Ni elements are selected to replace part of Sb elements in a Cu 3 SbS 3 compound to stabilize the cubic structure of the Cu 3 SbS 3 -based thermoelectric material, and the prepared Cu 3 SbS 3 has a cubic phase crystal structure and stable thermodynamic properties in a medium temperature range, has excellent thermoelectric performance and lays a foundation for the application of the Cu 3 SbS 3 compound in the thermoelectric field.
The technical scheme adopted by the invention for solving the problems is as follows:
A Cu 3 SbS 3 -based thermoelectric material is a cubic phase and has a chemical general formula of Cu 3 Sb 1-x A x S 3, wherein A is Co and/or Ni, and x is 0.025-0.200.
the cubic phase Cu 3 SbS 3 -based thermoelectric material has the density of more than or equal to 4.85g/cm 3 (the theoretical density of cubic phase Cu 3 SbS 3 is 5.10g/cm 3), and the thermoelectric performance index ZT is not less than 0.55 at the maximum value in a 550-620K temperature region and is not less than 0.1 at 300K.
The cubic phase Cu 3 SbS 3 -based thermoelectric material has the chemical composition of Cu 3 Sb 0.90 Co 0.10 S 3, the density of 4.90g/cm 3 and the maximum value of a thermoelectric performance index ZT in a 550-plus-620K temperature zone of 0.65, and the cubic phase Cu 3 SbS 3 -based thermoelectric material has the chemical composition of Cu 3 Sb 0.90 Ni 0.10 S 3, the density of 4.93g/cm 3 and the maximum value of the thermoelectric performance index ZT in the 550-plus-620K temperature zone of 0.62.
the preparation method of the cubic phase Cu 3 SbS 3 -based thermoelectric material mainly comprises the following steps:
1) Weighing simple substance copper, antimony, A and sulfur powder as reaction raw materials according to the molar ratio of each element in a chemical general formula of Cu 3 Sb 1-x A x S 3, wherein the ratio of the amount of the copper, antimony, A and sulfur is 3 (1-x) x:3, or slightly fluctuates around the stoichiometric ratio, the fluctuation range is less than 2 percent, wherein A is Co and/or Ni, and x is 0.025-0.200;
2) high-energy ball milling: carrying out high-energy ball milling on the reaction raw materials in the step 1) in an inert gas atmosphere;
3) and (3) densifying the powder obtained in the step (2) by adopting spark plasma sintering or hot-pressing sintering to obtain a high-density high-performance single-phase cubic phase Cu 3 SbS 3 -based thermoelectric material block.
According to the scheme, the quantity ratio of the copper, the antimony, the A and the sulfur in the step 1) is 3 (1-x) to x:3, or the fluctuation range is less than 2 percent near the stoichiometric ratio, wherein x is 0.05-0.1.
according to the scheme, the purity of the elementary substance powder of copper, antimony, cobalt, nickel and sulfur in the step 1) is not less than 99%, and the elementary substance powder is preferably selected.
according to the scheme, the high-energy ball milling time in the step 2) is 15-30 h.
According to the scheme, the rotation speed of the high-energy ball mill in the step 2) is 350-650 rpm.
According to the scheme, the material ratio of the high-energy ball milling balls in the step 2) is 10-30.
According to the scheme, the conditions of the spark plasma sintering in the step 3) are as follows: under vacuum or inert atmosphere, the sintering pressure is not less than 20MPa, the sintering temperature is 350-520 ℃, and the sintering time is 1-30 min; the hot-pressing sintering conditions are as follows: and under vacuum or inert atmosphere, the sintering pressure is not less than 20MPa, the sintering temperature is 370-540 ℃, and the sintering time is 10-120 min.
Compared with the prior art, the invention has the beneficial effects that:
1. The Cu 3 SbS 3 -based thermoelectric material prepared by the method has a stable cubic phase structure, the Cu 3 SbS 3 material prepared by the traditional method is a monoclinic structure, monoclinic-orthorhombic structure phase change exists near 395K, and the long-term service performance of the material is seriously influenced.
2. The invention utilizes the mature material treatment and preparation technology in industry or laboratory, takes copper, antimony, cobalt or nickel and sulfur as raw materials, and the replacement element Co and/or Ni is abundant relative to the replaced element Sb, has low price, no toxicity and no harm, and the prepared cubic phase Cu 3 SbS 3 -based thermoelectric material has high density, high purity, stable structure and excellent thermoelectric property, and is close to or superior to the commercial telluride thermoelectric material.
3. The raw materials used in the invention have stable physical and chemical properties, are easy to obtain and store, the preparation process is simple and controllable, the sintering method is flexible and selectable, no special process and treatment is needed, and the prepared cubic phase Cu 3 SbS 3 -based thermoelectric material has stable thermodynamic properties and excellent thermoelectric performance, thereby laying a foundation for the application of Cu 3 SbS 3 compounds in the thermoelectric field.
Drawings
Figure 1 is a powder x-ray diffraction pattern (XRD) of the bulk cubic phase Cu 3 SbS 3 -based thermoelectric material prepared in example 1 (after the spark plasma sintering step) showing the XRD pattern of tetrahedrite for embodying the same cubic structure of the product obtained in accordance with the present invention as tetrahedrite (Cu 3 SbS 3.25).
FIG. 2 is a thermoelectric performance diagram of a cubic phase Cu 3 SbS 3 -based thermoelectric material prepared in example 1.
Figure 3 is a powder x-ray diffraction pattern (XRD) of the bulk cubic phase Cu 3 SbS 3 -based thermoelectric material prepared in example 2 (after the spark plasma sintering step) showing the XRD pattern of tetrahedrite for embodying the same cubic structure of the resulting product of the invention as tetrahedrite (Cu 3 SbS 3.25).
FIG. 4 is a thermoelectric performance graph of the cubic phase Cu 3 SbS 3 -based thermoelectric material prepared in example 2.
Figure 5 is a powder x-ray diffraction pattern (XRD) of the bulk cubic phase Cu 3 SbS 3 -based thermoelectric material prepared in example 3 (after the spark plasma sintering step) showing the XRD pattern of tetrahedrite for embodying the same cubic structure of the resulting product of the invention as tetrahedrite (Cu 3 SbS 3.25).
FIG. 6 is a thermoelectric performance diagram of the cubic phase Cu 3 SbS 3 -based thermoelectric material prepared in example 3.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
A cubic phase Cu 3 SbS 3 -based thermoelectric material is prepared by the following steps:
1) The method comprises the following steps of proportioning, calculating the mass of each element according to the proportion of each element in Cu 3 Sb 1-x A x S 3 (A is Co or Ni), respectively weighing copper, antimony, cobalt or nickel and sulfur with required mass as reaction raw materials, wherein the mass ratio of the copper, antimony, cobalt or nickel and sulfur is 3 (1-x) x:3, wherein x is 0.10, the mass purity of copper is better than 99.5%, the mass purity of antimony is better than 99.5%, elemental sulfur is analytically pure, and the purity of elemental cobalt (nickel) is 99%;
2) Mechanical alloying: pouring the reaction raw materials in the step 1) into a stainless steel ball milling tank, and carrying out high-energy ball milling under the protection atmosphere of inert gas, wherein the ball milling rotation speed is 450rpm, the ball-to-material ratio is 20, and the ball milling time is 20 hours;
3) And (3) discharge plasma sintering, namely putting the powder obtained in the step 2) into a graphite die with the diameter of 15mm, and performing discharge plasma sintering at the sintering temperature of 400 ℃ for 5min under the pressure of 35MPa to obtain the high-density cubic-phase Cu 3 SbS 3 -based thermoelectric material block.
In the embodiment, Co or Ni is taken as A to carry out the preparation process, wherein when A is Ni, the chemical composition of the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block is Cu 3 Sb 0.90 Ni 0.10 S 3, and the density is 4.93g/cm 3, and when A is Co, the chemical composition of the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block is Cu 3 Sb 0.90 Co 0.10 S 3, and the density is 4.90g/cm 3.
As shown in figure 1, A is respectively Co or Ni, the thermoelectric material blocks obtained after spark plasma sintering in the step 3) are single-phase cubic phase Cu 3 SbS 3 compounds, no impurity peak occurs, and the starting raw materials are completely converted into the target product cubic phase Cu 3 SbS 3 compounds.
The thermoelectric property of the cubic phase Cu 3 SbS 3 -based thermoelectric material obtained in the embodiment is shown in figure 2 and is characterized by ZT value, when the chemical composition of the thermoelectric material block obtained after the step 3) of spark plasma sintering is Cu 3 Sb 0.90 Co 0.10 S 3, the maximum value of the thermoelectric property index ZT in the 550-620K temperature zone reaches 0.65, and when the chemical composition of the thermoelectric material block obtained after the step 3) of spark plasma sintering is Cu 3 Sb 0.90 Ni 0.10 S 3, the maximum value of the thermoelectric property index ZT in the 550-620K temperature zone reaches 0.62.
Example 2
A cubic phase Cu 3 SbS 3 -based thermoelectric material is prepared by the following steps:
1) The method comprises the following steps of preparing materials, namely calculating the mass of each element according to the proportion of each element in Cu 3 Sb 1-x A x S 3 (A is Co or Ni), respectively weighing copper, antimony, cobalt (nickel) and sulfur with required mass as reaction raw materials, wherein the mass ratio of the copper, antimony, cobalt (nickel) and sulfur is 3 (1-x) x:3, wherein x is 0.05, the mass purity of copper is better than 99.5%, the mass purity of antimony is better than 99.5%, elemental sulfur is analytically pure, and the purity of elemental cobalt (nickel) is 99%;
2) Mechanical alloying: pouring the reaction raw materials in the step 1) into a stainless steel ball milling tank, and carrying out high-energy ball milling under the protection atmosphere of inert gas, wherein the ball milling rotation speed is 450rpm, the ball-to-material ratio is 20, and the ball milling time is 20 hours;
3) And (2) carrying out spark plasma sintering, namely putting the powder obtained in the step 2) into a graphite die with the diameter of 15mm, and carrying out spark plasma sintering at the sintering temperature of 400 ℃ for 5min under the pressure of 35MPa to obtain the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block, wherein when A is Ni, the chemical composition of the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block is Cu 3 Sb 0.95 Ni 0.05 S 3 and the density is 4.94g/cm 3, and when A is Co, the chemical composition of the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block is Cu 3 Sb 0.95 Co 0.05 S 3 and the density is 4.90g/cm 3.
As shown in figure 3, A is respectively Co or Ni, the thermoelectric material blocks obtained after spark plasma sintering in the step 3) are single-phase cubic phase Cu 3 SbS 3 compounds, no impurity peak occurs, and the starting raw materials are completely converted into the target product cubic phase Cu 3 SbS 3 compounds.
the thermoelectric property of the cubic phase Cu 3 SbS 3 -based thermoelectric material obtained in the embodiment is shown in FIG. 4, the thermoelectric property index ZT reaches 0.62 at the maximum in the 550-plus-620K temperature region when the chemical composition is Cu 3 Sb 0.95 Co 0.05 S 3, and the thermoelectric property index ZT reaches 0.60 at the maximum in the 550-plus-620K temperature region when the chemical composition is Cu 3 Sb 0.95 Ni 0.05 S 3.
Example 3
A method of making a cubic phase Cu 3 SbS 3 -based thermoelectric material, comprising the steps of:
1) The method comprises the following steps of preparing materials, namely calculating the mass of each element according to the proportion of each element in Cu 3 Sb 1-x A x S 3 (A is Co or Ni), respectively weighing copper, antimony, cobalt (nickel) and sulfur with required mass as reaction raw materials, wherein the mass ratio of the copper, antimony, cobalt (nickel) and sulfur is 3 (1-x) x:3, wherein x is 0.20, the mass purity of copper is better than 99.5%, the mass purity of antimony is better than 99.5%, elemental sulfur is analytically pure, and the purity of elemental cobalt (nickel) is 99%;
2) Mechanical alloying: pouring the reaction raw materials in the step 1) into a stainless steel ball milling tank, and carrying out high-energy ball milling under the protection atmosphere of inert gas, wherein the ball milling rotation speed is 350rpm, the ball-material ratio is 15, and the ball milling time is 30 hours;
3) And (3) hot-pressing sintering, namely loading the powder obtained in the step (2) into a graphite die with the diameter of 15mm, and carrying out hot-pressing densification sintering at the sintering temperature of 5000 ℃, for 20min and under the pressure of 40MPa to obtain the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block, wherein when A is Ni, the chemical composition of the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block is Cu 3 Sb 0.80 Ni 0.20 S 3 and the density is 4.90g/cm 3, and when A is Co, the chemical composition of the high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block is Cu 3 Sb 0.80 Co 0.20 S 3 and the density is 4.88g/cm 3.
as shown in FIG. 5, A is respectively Co or Ni, the thermoelectric material blocks obtained after spark plasma sintering in the step 3) are single-phase cubic phase Cu 3 SbS 3 compounds, no impurity peak occurs, and the starting raw materials are completely converted into the target product cubic phase Cu 3 SbS 3 compounds.
The thermoelectric property of the cubic phase Cu 3 SbS 3 -based thermoelectric material obtained in the embodiment is shown in FIG. 6, the thermoelectric property index ZT reaches 0.58 at the temperature range of 550-620K when the chemical composition is Cu 3 Sb 0.80 Ni 0.20 S 3, and the thermoelectric property index ZT reaches 0.56 at the temperature range of 550-620K when the chemical composition is Cu 3 Sb 0.80 Ni 0.20 S 3.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (9)
1. A Cu 3 SbS 3 -based thermoelectric material is characterized by having a cubic crystal structure and having a chemical general formula of Cu 3 Sb 1-x A x S 3, wherein A is cobalt and/or nickel, and x is 0.025-0.200.
2. The Cu 3 SbS 3 -based thermoelectric material as claimed in claim 1, wherein the density of the sintered bulk material is not less than 4.85g/cm 3, and the maximum value of the thermoelectric performance index ZT in a temperature range of 550-620K is not less than 0.55.
3. The Cu 3 SbS 3 -based thermoelectric material as claimed in claim 1, wherein the density of the Cu 3 SbS 3 -based thermoelectric material is 4.90g/cm 3 and the thermoelectric performance index ZT reaches 0.65 at the maximum temperature range of 550-620K when the chemical composition of the Cu 3 Sb 0.90 Co 0.10 S 3, and the density of the Cu 3 SbS 3 -based thermoelectric material is 4.93g/cm 3 and the thermoelectric performance index ZT reaches 0.62 at the maximum temperature range of 550-620K when the chemical composition of the Cu 3 SbS 0.90 Ni 0.10 S 3.
4. A preparation method of a cubic phase Cu 3 SbS 3 -based thermoelectric material is characterized by mainly comprising the following steps:
1) The preparation method comprises the steps of weighing required simple substances of copper, antimony, A and sulfur as reaction raw materials according to the molar ratio of each element in a chemical general formula of Cu 3 Sb 1-x A x S 3, wherein the molar ratio of the elements of copper, antimony, A and sulfur is 3 (1-x): x:3, or slightly fluctuates around the molar ratio, the fluctuation amplitude is less than 2%, wherein A is cobalt and/or nickel, and x is 0.025-0.200;
2) carrying out high-energy ball milling on the reaction raw materials in the step 1) in an inert gas atmosphere, and then densifying by adopting a discharge plasma sintering or hot-pressing sintering process to obtain a high-performance high-density cubic phase Cu 3 SbS 3 -based thermoelectric material block.
5. The method for preparing the cubic phase Cu 3 SbS 3 -based thermoelectric material as claimed in claim 4, wherein the high energy ball milling speed in step 2) is 350-650rpm, the time is 15-30 h, and the ball-to-material ratio is 10-30.
6. the method for preparing the cubic-phase Cu 3 SbS 3 -based thermoelectric material as claimed in claim 4, wherein the sintering conditions of the spark plasma are that the sintering pressure is not less than 20MPa, the sintering temperature is 350-520 ℃, and the sintering time is 1-30 min under vacuum or inert atmosphere.
7. the method for preparing the cubic-phase Cu 3 SbS 3 -based thermoelectric material as claimed in claim 4, wherein the hot-pressing sintering conditions are that the sintering pressure is not less than 20MPa, the sintering temperature is 370-540 ℃ and the sintering time is 10-120 min under vacuum or inert atmosphere.
8. The method for preparing a cubic phase Cu 3 SbS 3 -based thermoelectric material as claimed in claim 4, wherein the ratio of the amounts of the Cu, Sb, A and S in step 1) is 3 (1-x) x:3, wherein x is 0.05-0.1.
9. The method of claim 4, wherein the Cu 3 SbS 3 -based thermoelectric material in step 1) is elemental powder with purity not less than 99%.
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