CN111162160B - P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof - Google Patents
P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof Download PDFInfo
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- CN111162160B CN111162160B CN201811327161.6A CN201811327161A CN111162160B CN 111162160 B CN111162160 B CN 111162160B CN 201811327161 A CN201811327161 A CN 201811327161A CN 111162160 B CN111162160 B CN 111162160B
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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Abstract
The invention relates to a p-type cubic phase Ge-Se-based thermoelectric material and a preparation method thereof, wherein the chemical molecular formula of the p-type cubic phase Ge-Se-based thermoelectric material is GeSeA 2x B 3x Wherein A is a positive trivalent metal Sb, B is a negative divalent non-metal Te or Se, and x has a value in the range of 0 to 1.GeSeA 2x B 3x The preparation method of the thermoelectric material comprises three steps of ball milling, mixing, melting reaction and solid sintering. First according to GeSeA 2x B 3x The simple substance powder of Ge, A, B and Se is weighed according to the mole fraction in the molecular formula, then the powder is ball-milled and mixed uniformly, the mixed powder is cold-pressed into blocks, the blocks are sealed in a quartz tube, and are subjected to fusion reaction at high temperature, and then the block thermoelectric material is sintered by utilizing a spark plasma sintering technology under proper pressure and temperature conditions. Cubic phase (GeSeA) 2x B 3x ) The thermoelectric material has glass-like electric transportation and thermal transportation and shows better thermoelectric performance.
Description
Technical Field
The invention belongs to the field of thermoelectricity, and particularly relates to a p-type cubic phase Ge-Se-based thermoelectric material and a preparation method thereof.
Background
The thermoelectric technology can realize the mutual conversion between heat energy and electric energy, and has wide application prospect as a clean energy technology. The performance of the thermoelectric material can be measured by a dimensionless thermoelectric figure of merit ZT calculated by zt= (S 2 Sigma/κ) T, where S is the Seebeck coefficient, σ is the electrical conductivity, T is the temperature, κ is the thermal conductivity, power factor pf=s 2 Sigma. Thermoelectric materials with high ZT values need to have high electrical conductivity and Seebeck coefficients, as well as low thermal conductivity. Most of the thermoelectric materials excellent in performance tend to have highly symmetrical crystal structures such as PbTe, skutterudite, half-Heusler alloy, tin telluride, etc. Recently, research on thermoelectric properties of GeSe having an orthorhombic structure and a trigonal structure has been receiving attention. GeSe with orthorhombic structure is a two-dimensional layered material with higher Seebeck coefficient and lower thermal conductivityBut at the same time has a very low electrical conductivity. At present, the ZT value of GeSe with an orthorhombic structure is 0.2 at most, so that the application of GeSe in the thermoelectric field is limited. The synthesis of GeSe polycrystal thermoelectric material with trigonal structure greatly improves the thermoelectric performance of GeSe. Due to its higher power factor and lower thermal conductivity, its ZT value eventually reaches 0.86. It can be seen that thermoelectric materials with high symmetry of crystal structure have higher thermoelectric performance. Therefore, geSe having a cubic crystal structure should have better thermoelectric performance. At present, there are reports that by combining GeSe and AgBiSe 2 Alloyed, n-type cubic phase GeSe has been synthesized. Therefore, the preparation of p-type GeSe-based thermoelectric materials having cubic crystal structures by a suitable method is of great significance.
Disclosure of Invention
The invention solves the technical problems: a Ge-Se-based thermoelectric material having a novel crystal structure is provided, which has high electric conductivity and power factor, low thermal conductivity, and exhibits good thermoelectric performance.
The technical proposal of the invention is as follows: in one aspect, a Ge-Se-based thermoelectric material is provided, the chemical formula of the Ge-Se-based thermoelectric material is GeSeA 2x B 3x Wherein A is metallic Sb, B is non-metallic Te or Se, the molar ratio of Ge: se: A: B is 1:1:2x:3x, and 0<x is less than or equal to 1; the molar fraction ratio of the metal A to the metal B is 2:3; the Ge-Se-based thermoelectric material has a cubic crystal structure, is a p-type thermoelectric material, and the cubic crystal structure is beneficial to improving the thermoelectric performance of the material; the microscopic particle size of the Ge-Se-based thermoelectric material is 1-40 mu m.
Based on the above technical solution, preferably, the range of x is 0.05-0.15.
Based on the technical scheme, preferably, the particle size of the Ge-Se-based thermoelectric material is 5-20 mu m, so that the material is guaranteed to have high electrical conductivity, and meanwhile, the material is guaranteed to have more crystal boundaries, so that the thermal conductivity is reduced.
The invention also provides a preparation method of the Ge-Se-based thermoelectric material, which comprises the following steps:
(1) Ball milling and mixing: geSeA as described above 2x B 3x Molar (mol) of (B)Weighing powder of Ge, A, B and Se element simple substances according to the fraction ratio, putting the powder into a ball milling tank for ball milling and mixing, and uniformly ball milling the powder in a certain rotating speed and ball milling time;
(2) And (3) melting reaction: cold-pressing the powder subjected to ball milling and mixing into blocks, putting the blocks into a quartz tube, sealing the tube by oxyhydrogen flame in vacuum, putting the tube into a melting furnace, heating to a melting temperature, keeping a period of reaction time, and cooling to room temperature to obtain a block material;
(3) And (3) solid sintering: grinding the melted block material into powder, placing into a sintering mold, placing the mold into a sintering furnace, pressurizing to a set pressure of 30-100MPa by using a discharge plasma sintering technology, vacuumizing to 1-5Pa, adding current, heating to a sintering temperature of 723-800K, maintaining the sintering temperature for a period of time, reducing the current, cooling to room temperature, ending sintering, and obtaining the GeSeA 2x B 3x Thermoelectric materials.
Based on the above technical scheme, preferably, in the step (1), the rotation speed of ball milling and mixing is 200-600rpm, preferably 450rpm, the ball milling time is 6-24h, preferably 12h, and the preferred rotation speed and time can ensure the sufficient mixing of materials.
Based on the above technical scheme, preferably, in the step (2), the melting temperature is 1073K, the reaction time is 2h-12h, preferably 2h, and the preferable time and temperature can ensure that the materials are sufficiently melted and reacted.
Based on the above technical solution, preferably, in the step (3), the pressure is set to be 50MPa, which is favorable for making the material have a high density, and the material is not broken after sintering.
Based on the above technical scheme, preferably, in the step (3), the sintering temperature is 743K, the holding time is 1-30min, preferably the holding time is 5min, and the preferred temperature and time can ensure that the material is completely sintered, so that the material has high density and the material is prevented from being decomposed.
Based on the above technical scheme, preferably, in the step (3), the sintering furnace is a spark plasma sintering instrument. The advantage is that the spark plasma sintering technology can make the material sinter and shape fast, and get the high density thermoelectric material.
Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the crystal structure of GeSe is effectively regulated and controlled through metal doping and nonmetal alloying, and the GeSe cubic crystal structure at room temperature is obtained.
(2) The cubic-phase GeSe-based thermoelectric material prepared by the invention is a p-type thermoelectric material and has high-concentration Ge vacancies; the Ge vacancies have the effect of improving their thermoelectric properties and stabilizing the cubic crystal structure.
(3) The method of the invention obviously improves the carrier concentration of GeSe by metal doping and nonmetal alloying, so that GeSeA 2x B 3x The thermoelectric material has very high conductivity, and the conductivity can reach 15000-40000S/m; and the S-n relation is deviated from the Pisarenko curve due to the Andersen local area induced by the vacancy, and the Seebeck coefficient which is unchanged with the increase of the carrier concentration is presented, so that the Seebeck coefficient can reach 100-250 mu V/K. Thus, geSeA 2x B 3x Has high power factor up to 1000-1300 mu W/mK 2 Whereas the GeSe conductivity and power factor reported in the literature for the single metal doping method are only 1000-2000S/m and 100-200. Mu.W/mK 2 (literature X.Zhang, J.Shen, S.Lin, J.Li, Z.Chen, W.Li and Y.Pei, J.Materiomics,2016,2,331-337.).
(4) GeSeA prepared by the invention 2x B 3x Has a disordered structure caused by vacancies, thereby exhibiting a glass-like lattice thermal conductivity. The total heat conductivity is in the range of 0.8-1.5W/mK, and the lattice heat conductivity does not change with temperature. The thermoelectric figure of merit of GeSe is effectively improved through metal doping and nonmetallic alloying, the ZT value can reach 0.7-0.8 at 710K, and compared with the single doping method reported in the literature, the ZT value is improved by 4 times. (literature X.Zhang, J.Shen, S.Lin, J.Li, Z.Chen, W.Li and Y.Pei, J.Materiomics,2016,2,331-337.).
(5) The preparation method has low requirements on preparation conditions, is easy for mass preparation and is beneficial to practical application of thermoelectric devices.
(6) GeSeA of the invention 2x B 3x The material can be applied to the fields of solar cells, photoelectrocatalysis and the like.
The invention mainly utilizes metal doping and nonmetallic alloying to regulate and control the crystal structure of GeSe, and forms a cubic crystal structure with high conductivity and power factor. Compared with the prior art (documents: X.Zhang, J.Shen, S.Lin, J.Li, Z.Chen, W.Li and Y.Pei, J.Materiomics,2016,2,331-337.), the GeSe conductivity and power factor of the single metal doping method are only 1000-2000S/m and 100-200. Mu.W/mK 2 The thermoelectric figure of merit ZT is only 0.2 (documents: X.Zhang, J.Shen, S.Lin, J.Li, Z.Chen, W.Li and Y.Pei, J.Materiomics,2016,2,331-337.) the conductivity and power factor in the present invention can reach 15000-40000S/m and 1000-1300. Mu.W/mK 2 The thermoelectric figure of merit ZT can reach 0.7-0.8.
Drawings
FIG. 1 is a graph of thermal conductivity κ versus temperature for examples 1,2 and 3 of the present invention;
FIG. 2 is a graph showing the conductivity σ as a function of temperature for examples 1,2 and 3 of the present invention;
FIG. 3 is a graph showing the Seebeck coefficient S of examples 1,2 and 3 according to the present invention, as a function of temperature;
FIG. 4 is a graph showing the power factor versus temperature for examples 1,2 and 3 of the present invention;
FIG. 5 is a graph showing thermoelectric figure of merit (ZT) versus temperature for examples 1,2 and 3 of the present invention;
FIG. 6 is a powder X-ray diffraction (XRD) pattern at room temperature for examples 1,2 and 3 of the present invention.
Detailed Description
The invention successfully prepares a novel high-performance thermoelectric material, and the chemical general formula of the thermoelectric material is GeSeA 2x B 3x Wherein a is Sb metal and B is non-metallic Te or Se, wherein: the molar ratio of Ge to Se to A to B is 1:1:2x to 3x and 0<x≤1。
The invention prepares the metal doped and nonmetallic alloyed GeSeA by a tube sealing melting and spark plasma sintering technology 2x B 3x Thermoelectric material and effectively improves the electric conductivity of GeSe material, geSeA 2x B 3x Has a high power factor and a low thermal conductivity, which leads to GeSeA 2x B 3x Has higher thermoelectric figure of merit and good thermoelectric application potential.
Embodiments of the invention include three steps of ball milling, melt reaction, spark plasma sintering, detailed embodiments are as follows:
(1) Ball milling and mixing: according to the chemical ratio in the chemical general formula, firstly, the needed simple substance powder of Ge, A, B and Se is weighed, put into a ball milling tank, inert gas is filled in the ball milling tank to prevent the powder from oxidation in the ball milling process, and ball milling is carried out for 12 hours under the condition of 450 revolutions per minute (rpm) to fully mix the simple substance powder.
(2) And (3) melting reaction: taking out the powder after ball milling, pressing the powder after ball milling into blocks by using a cold pressing tablet press, then putting the blocks into a quartz tube with the diameter of 20mm and the length of 25cm, mounting the quartz tube on an oxyhydrogen tube sealing device, vacuumizing for a period of time of 10-30min generally, then opening the oxyhydrogen machine, igniting, adjusting the positions of the quartz tube and a flame nozzle, rotating the quartz tube, sealing the quartz tube by using oxyhydrogen flame, and vacuum packaging the block material in the quartz tube.
(3) And (3) solid sintering: the material obtained by the melting reaction is further sintered into blocks by using a spark plasma sintering technique (SPS). Firstly, grinding the obtained block material into powder, selecting a graphite mould, adding a layer of carbon paper for protecting the mould into the graphite mould, putting the powder into the mould, compacting by a graphite pressure head, then putting into a discharge plasma sintering device, applying a certain pressure, applying the pressure range to be 30-100MPa, vacuumizing for a period of time, filling a certain amount of Ar gas, and vacuumizing again, thus repeating the operation for more than three times, ensuring an inert vacuum environment in a furnace body, and preventing the material from being oxidized during sintering. Vacuumizing, and starting to heat and sinter when the pressure is less than 5 Pa. Slowly increasing current to increase the temperature from room temperature to sintering temperature 743K for 20-30min at 15-25K/min, maintaining the temperature at sintering temperature for a period of time, typically 5min, and then starting cooling to maintain the pressure at two ends of the die during coolingThe current is reduced, so that the die is slowly cooled, and breakage caused by rapid cooling is prevented. After cooling to room temperature, geSeA with high density is obtained 2x B 3x Bulk thermoelectric material.
Example 1
Sb doped and Te alloyed geselb 0.16 Te 0.24 The specific preparation method comprises the following steps:
(1) Ball milling and mixing: x=0.08 according to geselb 0.16 Te 0.24 The simple substance powder of Ge, te, sb and Se is weighed, the total mass is 8g, then the powder is put into a ball milling tank, argon is filled for protection, and ball milling is carried out for 12h under the condition of 450 rpm.
(2) And (3) melting reaction: taking out the powder after ball milling from a ball milling tank, pressing into sheets, putting the sheets into a quartz tube, sealing the tube by oxyhydrogen flame, putting the quartz tube into a furnace, heating to 773K at 3K/min, preserving heat for 30min at 773K, heating to 1073K at 3K/min, preserving heat for 2h, then starting cooling, cooling to 723K, preserving heat for 30min, then naturally cooling, cooling to room temperature, and taking out.
(3) And (3) solid sintering: grinding the materials obtained by the melting reaction into powder by using a mortar, adding a layer of carbon paper into a mold, then placing the powder into a graphite mold with an inner diameter of 12.7mm, placing into an SPS device, pressurizing at two ends of the mold, wherein the pressure is 50MPa, vacuumizing to 5Pa, then starting to heat up to 743K at 20K/min, then preserving heat for 5min, then starting to cool down, maintaining the pressure at 50MPa, gradually reducing the current, gradually reducing the temperature to room temperature, and then taking out.
Example 2
Sb doped and Te alloyed geselb 0.20 Te 0.30 The specific preparation method comprises the following steps:
(1) Ball milling and mixing: x=0.1, according to the chemical formula geselb 0.20 Te 0.30 Firstly, weighing simple substance powder of Ge, te, sb and Se, putting the simple substance powder into a ball milling tank for ball milling for 12 hours, wherein the rotating speed is 450rpm, and fully mixing the simple substance powder.
(2) And (3) melting reaction: taking out the ball-milled powder, pressing the ball-milled powder into pieces, vacuum packaging the pieces in a quartz tube, putting the quartz tube into a heating furnace, heating to 773K, preserving heat for 30min, heating to 1073K, preserving heat for 2h, heating up to 3K/min in a heating section, cooling to 823K, preserving heat for 30min, and naturally cooling.
(3) And (3) solid sintering: and (3) placing the melted material into a die by using a spark plasma sintering technology, heating and sintering under the conditions of 50MPa and 5Pa, keeping the temperature at a temperature of 25K/min, keeping the temperature at 743K for 5min, slowly cooling, keeping the pressure gradually reducing the current, and taking out after cooling to room temperature.
Example 3
Sb doped and Te alloyed geselb 0.30 Te 0.45 The specific preparation method comprises the following steps:
(1) Ball milling and mixing: x=0.15, according to geselb 0.30 Te 0.45 The chemical molar ratio of the powder is measured, and the powder is ball-milled for 12 hours under inert atmosphere, so that the powder is fully mixed.
(2) And (3) melting reaction: and (3) packaging the ball-milled mixed powder in a quartz tube by oxyhydrogen flame under vacuum, heating to 773K under inert gas, preserving heat for 30min, heating to 1073K, preserving heat for 2h, and then starting cooling. Incubate at 823K for 30min. Then cooled to room temperature and taken out.
(3) And (3) solid sintering: to obtain GeSeSb after melting 0.30 Te 0.45 Grinding into powder, pressurizing under 50MPa, vacuumizing, heating to 743K at 25K/min, maintaining for 5min, slowly cooling to room temperature, and taking out.
Example 4
Thermal conductivity properties
As shown in FIG. 1, the thermal diffusivity D and specific heat C of examples 1,2,3 were measured by laser light scattering analysis (LFA) and Differential Scanning Calorimetry (DSC), respectively p Using the formula κ=c p ρd (where ρ is the density of the thermoelectric material), the thermal conductivity κ of the thermoelectric material is obtained by calculation. The instruments used in the test were NETZSCH LFA457 and NETZSCH STA, temperature range: 300-710K. As can be seen from FIG. 1, examples 1 and 2 have lower thermal conductivities, 1.02W/mK and 0.90W/mK at 300K, respectively, and example 3 has the lowest thermal conductivity at room temperature, 0.84W/mK at 300K. Warm temperatureThe thermal conductivities of example 1 and example 2 were 1.25W/mK and 1.15W/mK, respectively, and the thermal conductivity of example 3 was 1.17W/mK, respectively, at a temperature of 710K, both of which were relatively low.
Example 5
Electrical properties
Systematic tests were performed on the electrical properties of examples 1,2,3, including conductivity σ and Seebeck coefficient S, as shown in fig. 2,3, and 4. The instrument used for the electrical test was ULVAC ZEM-3. The conductivity and power factor were highest for example 1, and for example 1 at 710K were 35148S/m and 1297. Mu.W/mK, respectively 2 Examples 2 and 3 showed reduced conductivities, conductivities of examples 2 and 3 were 33111S/m and 30220S/m, respectively, at 710K, and Seebeck coefficients of examples 2 and 3 were 184 μv/K and 193 μv/K, respectively, at 710K, such that the power factor (pf=s 2 Sigma) is lower than in example 1, the power factor of examples 2 and 3 is 1118 mu W/mK, respectively, at 710K 2 And 1130. Mu.W/mK 2 。
From the thermal conductivity and electrical data, a thermoelectric figure of merit ZT can be calculated. FIG. 5 is a graph showing the thermoelectric figure of merit of examples 1,2, and 3 as a function of temperature. As can be seen from fig. 5, the ZT value of example 1 is high, the ZT value at 710K is 0.73, the ZT decreases with increasing doping amount, and the ZT values of example 2 and example 3 are 0.69 and 0.68, respectively, at 710K.
XRD characterization figure 6 is an XRD characterization of examples 1,2, 3. At room temperature, examples 1,2 and 3 all exhibit a cubic crystal structure (Fm-3 m) with good thermoelectric properties.
The above examples are provided for the purpose of describing the present invention only and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalents and modifications that do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A Ge-Se based thermoelectric material characterized in that: the chemical general formula of the material is GeSeA 2x B 3x Wherein: the molar ratio of Ge to Se to A to B is 1:1:2x to 3x, and x is more than or equal to 0.08 and less than or equal to 0.15; a is metal Sb, B is non-A metal Te; the Ge-Se-based thermoelectric material has a cubic crystal structure and is a p-type thermoelectric material; the particle size of the Ge-Se-based thermoelectric material is 1-40 mu m.
2. The Ge-Se based thermoelectric material according to claim 1, wherein the Ge-Se based thermoelectric material has a particle size of 5-20 μm.
3. A method for preparing the Ge-Se based thermoelectric material according to claim 1, comprising the steps of:
(1) Ball milling and mixing: geSeA according to claim 1 2x B 3x The molar ratio of Ge, A, B and Se element simple substance powder is weighed, ball-milled and mixed to obtain mixed powder;
(2) And (3) melting reaction: cold-pressing the mixed powder into blocks, putting the blocks into a quartz tube, vacuum sealing the tube, putting the quartz tube into a melting furnace, heating to a melting temperature, maintaining a period of reaction time, and cooling to room temperature to obtain a block material;
(3) And (3) solid sintering: grinding the block material into powder, placing the powder into a sintering mold, placing the mold into a sintering furnace, pressurizing to a set pressure of 30-100MPa by using a discharge plasma sintering technology, vacuumizing to 1-5Pa, adding current, heating to a sintering temperature of 723-800K, maintaining the sintering temperature for a period of time, reducing the current, cooling to room temperature, ending sintering, and obtaining the p-type cubic phase GeSeA 2x B 3x Thermoelectric materials.
4. The method for producing a Ge-Se based thermoelectric material according to claim 3, wherein: in the step (1), the rotating speed of ball milling and mixing is 200-600rpm, and the time of ball milling and mixing is 8-24h.
5. The method for producing a Ge-Se based thermoelectric material according to claim 3, wherein: in the step (2), the melting temperature is 973K-1273K, and the reaction time is 1h-12 h.
6. The method for producing a Ge-Se based thermoelectric material according to claim 3, wherein: in the step (3), the set pressure is 50 MPa.
7. The method for producing a Ge-Se based thermoelectric material according to claim 3, wherein: in the step (3), the sintering temperature is 743 and K, and the sintering temperature is kept for 1-30 min.
8. The method for producing a Ge-Se based thermoelectric material according to claim 3, wherein: in the step (3), the sintering furnace is a discharge plasma sintering instrument.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280706A (en) * | 1997-10-24 | 2001-01-17 | 住友特殊金属株式会社 | Thermoelectric transducing material and method of producing the same |
| US6222242B1 (en) * | 1998-07-27 | 2001-04-24 | Komatsu Ltd. | Thermoelectric semiconductor material and method of manufacturing same |
| CN102414121A (en) * | 2009-03-24 | 2012-04-11 | 巴斯夫欧洲公司 | Self-organising thermoelectric materials |
| CN102655204A (en) * | 2012-04-28 | 2012-09-05 | 北京航空航天大学 | Sr-doping oxide BiCuSeO thermoelectric material and preparation method thereof |
| CN103985812A (en) * | 2014-06-03 | 2014-08-13 | 西华大学 | Thermoelectric material and manufacturing method thereof |
| CN106830940A (en) * | 2017-01-10 | 2017-06-13 | 同济大学 | A kind of GeTe base high-performances thermoelectric material and preparation method thereof |
| CN107293637A (en) * | 2016-03-30 | 2017-10-24 | 武汉理工大学 | A kind of preparation method of high-performance GeSbTe base thermoelectricity materials |
| CN107359232A (en) * | 2017-06-30 | 2017-11-17 | 河南理工大学 | A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material and the method that the thermoelectric material is prepared by element substitution |
| CN108735888A (en) * | 2018-04-27 | 2018-11-02 | 同济大学 | Novel Ge antimony tellurium compound thermoelectric material with high concentration vacancy and preparation method thereof |
-
2018
- 2018-11-08 CN CN201811327161.6A patent/CN111162160B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280706A (en) * | 1997-10-24 | 2001-01-17 | 住友特殊金属株式会社 | Thermoelectric transducing material and method of producing the same |
| US6222242B1 (en) * | 1998-07-27 | 2001-04-24 | Komatsu Ltd. | Thermoelectric semiconductor material and method of manufacturing same |
| CN102414121A (en) * | 2009-03-24 | 2012-04-11 | 巴斯夫欧洲公司 | Self-organising thermoelectric materials |
| CN102655204A (en) * | 2012-04-28 | 2012-09-05 | 北京航空航天大学 | Sr-doping oxide BiCuSeO thermoelectric material and preparation method thereof |
| CN103985812A (en) * | 2014-06-03 | 2014-08-13 | 西华大学 | Thermoelectric material and manufacturing method thereof |
| CN107293637A (en) * | 2016-03-30 | 2017-10-24 | 武汉理工大学 | A kind of preparation method of high-performance GeSbTe base thermoelectricity materials |
| CN106830940A (en) * | 2017-01-10 | 2017-06-13 | 同济大学 | A kind of GeTe base high-performances thermoelectric material and preparation method thereof |
| CN107359232A (en) * | 2017-06-30 | 2017-11-17 | 河南理工大学 | A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material and the method that the thermoelectric material is prepared by element substitution |
| CN108735888A (en) * | 2018-04-27 | 2018-11-02 | 同济大学 | Novel Ge antimony tellurium compound thermoelectric material with high concentration vacancy and preparation method thereof |
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