CN111162160A - 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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- CN111162160A CN111162160A CN201811327161.6A CN201811327161A CN111162160A CN 111162160 A CN111162160 A CN 111162160A CN 201811327161 A CN201811327161 A CN 201811327161A CN 111162160 A CN111162160 A CN 111162160A
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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 GeSeA2xB3xWherein A is a positive trivalent metal Sb, B is a negative divalent nonmetal Te or Se, and x has a value in the range of 0 to 1. GeSeA2xB3xThe preparation method of the thermoelectric material comprises three steps of ball milling mixing, melting reaction and solid sintering. First according to GeSeA2xB3xWeighing elemental powder of Ge, A, B and Se according to the mole fraction in the molecular formula, then ball-milling and uniformly mixing the powder, cold-pressing the uniformly mixed powder into a block, sealing the block in a quartz tube, carrying out melting reaction at high temperature, and then sintering the block into the block thermoelectric material by using a spark plasma sintering technology under the conditions of proper pressure and temperature. Cubic phase (GeSeA)2xB3x) The thermoelectric material has the electric transportation and the heat transportation similar to glass, 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 a thermoelectric material can be measured by a dimensionless thermoelectric figure of merit, ZT, (S) calculated from the following equation2σ/κ) T, where S is Seebeck coefficient, σ is electrical conductivity, T is temperature, κ is thermal conductivity, power factor PF ═ S2And sigma. Thermoelectric materials with high ZT values need to have high electrical conductivity and Seebeck coefficient, as well as low thermal conductivity. Most thermoelectric materials with excellent properties often have highly symmetric crystal structures, such as PbTe, skutterudite, half-Heusler alloys, tin telluride, and the like. Recently, studies on thermoelectric properties of GeSe having an orthorhombic structure and a trigonal structure have been receiving much attention. GeSe with an orthorhombic structure is a two-dimensional layered material which has a high Seebeck coefficient and a low thermal conductivity, but which has a very low electrical conductivity. Currently, the ZT value of GeSe with an orthorhombic structure is 0.2 at most, so that the application of GeSe in the field of thermoelectricity is limited. The synthesis of GeSe polycrystal thermoelectric material with a trigonal crystal system structure greatly improves the thermoelectric property of GeSe. Due to the high power factor and low thermal conductivity, the ZT value of the ceramic material finally reaches 0.86. Therefore, the thermoelectric material with high symmetry of the crystal structure has higher thermoelectric performance. Therefore, GeSe having a cubic crystal structure should have better thermoelectric properties. At present, there are reports of the combination of GeSe and AgBiSe2Alloyed, n-type cubic phase GeSe has been synthesized. Therefore, it is of great significance to prepare p-type GeSe-based thermoelectric materials having a cubic crystal structure by an appropriate method.
Disclosure of Invention
The invention solves the problems: a Ge-Se based thermoelectric material having a novel crystal structure is provided, which has high electrical conductance and power factor, low thermal conductance, and exhibits good thermoelectric properties.
The technical scheme of the invention is as follows: in one aspect, a Ge-Se-based thermoelectric material is provided, wherein the general chemical formula of the Ge-Se-based thermoelectric material is GeSeA2xB3xWherein A is metal Sb, B is nonmetal Te or Se, Ge is Se, A is BThe molar ratio is 1:1:2x:3x, and 0<x is less than or equal to 1; the mole fraction ratio of the metals A and B is 2: 3; the Ge-Se-based thermoelectric material has a cubic crystal structure and is a p-type thermoelectric material, and the cubic crystal structure is favorable for improving the thermoelectric property of the material; the microscopic grain size of the Ge-Se-based thermoelectric material is 1-40 mu m.
Based on the technical scheme, the range of x is preferably 0.05-0.15.
Based on the technical scheme, preferably, the particle size of the Ge-Se-based thermoelectric material is 5-20 μm, so that the material is ensured to have high conductivity, and meanwhile, the material is ensured to have more crystal boundaries, and 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: according to the above GeSeA2xB3xWeighing the powder of the elemental Ge, A, B and Se according to the mole fraction ratio, putting the powder into a ball milling tank for ball milling and mixing, and carrying out ball milling on the powder uniformly at a certain rotating speed for ball milling time;
(2) melting reaction: cold pressing the powder after ball milling and mixing into blocks, putting the blocks into a quartz tube, sealing the tube in vacuum by using oxyhydrogen flame, putting the tube into a melting furnace, heating to the melting temperature, keeping for a period of reaction time, and cooling to room temperature to obtain a block material;
(3) solid sintering: grinding the melted block material into powder, placing the powder into a sintering mold, then placing the mold into a sintering furnace, pressurizing to a set pressure of 30-100MPa by using a spark plasma sintering technology, vacuumizing to 1-5Pa, then heating by adding current to a sintering temperature of 723-800K, keeping the sintering temperature for a period of time, then reducing the current, cooling to room temperature, finishing sintering to obtain GeSeA2xB3xA thermoelectric material.
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 sufficient mixing of the materials.
Based on the technical scheme, preferably, in the step (2), the melting temperature is 1073K, the reaction time is 2h-12h, preferably 2h, and the preferred time and temperature can ensure that the materials are fully melted and reacted.
Based on the above technical solution, preferably, in the step (3), the pressure is set to be 50MPa, which is beneficial to make the material have high density, and the material is not fractured after sintering.
Based on the above technical scheme, preferably, in the step (3), the sintering temperature is 743K, the holding time is 1-30min, the heat preservation time is preferably 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 solution, preferably, in the step (3), the sintering furnace is a spark plasma sintering instrument. The method has the advantages that the discharge plasma sintering technology can rapidly sinter and form the material to obtain the high-density thermoelectric material.
Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) the invention effectively regulates and controls the crystal structure of GeSe through metal doping and nonmetal alloying, and obtains a GeSe cubic crystal structure at room temperature.
(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 vacancy has the functions of improving the thermoelectric property and stabilizing the cubic crystal structure.
(3) The invention obviously improves the carrier concentration of GeSe by the methods of metal doping and nonmetal alloying, so that GeSeA2xB3xThe thermoelectric material has high electric conductivity which can reach 15000-40000S/m; and the Anderson local area induced by the vacancy deviates the S-n relation from a Pisarenko curve, and presents a Seebeck coefficient which is unchanged along with the increase of the carrier concentration, so that the Seebeck coefficient can reach 100-grade 250 muV/K. Thus, GeSeA2xB3xHas very high power factor, can reach 1000-2The GeSe conductivity and power factor of the single metal doping method reported in the literature are only 1000-2000S/m and 100-200 muW/mK2(document: X.Zhan)g,J.Shen,S.Lin,J.Li,Z.Chen,W.Liand Y.Pei,J.Materiomics,2016,2,331-337.)。
(4) GeSeA prepared by the invention2xB3xHas a disordered structure caused by vacancies, thereby presenting a glass-like lattice thermal conductivity. The total thermal conductivity range is 0.8-1.5W/mK, and the lattice thermal conductivity does not change with the temperature. The thermoelectric figure of merit of GeSe is effectively improved through metal doping and non-metal alloying, the ZT value can reach 0.7-0.8 at 710K, and compared with a single doping method reported in the literature, the ZT value is improved by 4 times. (document: X.Zhang, J.Shen, S.Lin, J.Li, Z.Chen, W.Li and Y.Pei, J.Materials, 2016,2, 331-337.).
(5) The preparation method has lower requirements on preparation conditions, is easy for mass preparation, and is beneficial to the practical application of thermoelectric devices.
(6) GeSeA of the invention2xB3xThe material can also be applied to the fields of solar cells, photoelectrocatalysis and the like.
The invention mainly utilizes metal doping and nonmetal alloying to regulate the crystal structure of GeSe and form 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.Materials, 2016,2,331-2So that 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.Materials, 2016,2,331-2The thermoelectric figure of merit ZT can reach 0.7-0.8.
Drawings
FIG. 1 is a graph of the thermal conductivity κ as a function of temperature for examples 1,2 and 3 of the invention;
FIG. 2 is a graph of the change in conductivity σ with temperature for examples 1,2 and 3 of the present invention;
FIG. 3 is a graph showing the Seebeck coefficient S according to the temperature in examples 1,2 and 3 of the present invention;
FIG. 4 is a graph of power factor versus temperature for examples 1,2 and 3 of the present invention;
FIG. 5 is a graph of thermoelectric figure of merit (ZT) as a function of 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 inventive examples 1,2 and 3.
Detailed Description
The invention successfully prepares a novel high-performance thermoelectric material, and the chemical general formula of the thermoelectric material is GeSeA2xB3xWherein A is Sb metal, B is non-metal Te or Se, wherein: molar ratio of Ge to Se to A to B is 1:1:2x:3x and 0<x≤1。
The invention prepares metal-doped and nonmetal-alloyed GeSeA by tube-sealing melting and discharge plasma sintering technology2xB3xThermoelectric materials and effectively improve the electrical conductivity of GeSe materials, GeSeA2xB3xHas high power factor and low thermal conductivity, which makes GeSeA2xB3xHas higher thermoelectric figure of merit and good thermoelectric application potential.
The embodiment of the invention comprises three steps of ball milling, melting reaction and spark plasma sintering, and the detailed embodiment is as follows:
(1) ball milling and mixing: according to the chemical ratio in the chemical general formula, firstly, weighing the required elementary substance powder of Ge, A, B and Se, putting the elementary substance powder into a ball milling tank, filling inert gas into the ball milling tank to prevent the powder from being oxidized in the ball milling process, and carrying out ball milling for 12 hours under the condition of 450 revolutions per minute (rpm) to fully mix the elementary substance powder.
(2) 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, installing the quartz tube on an oxyhydrogen tube sealing device, vacuumizing for a period of time, generally 10-30min, then opening the oxyhydrogen machine, igniting, adjusting the positions of the quartz tube and a flame nozzle, rotating the quartz tube, completing tube sealing of the quartz tube by using oxyhydrogen flame, and vacuum-packaging the block materials in the quartz tube.
(3) Solid sintering: by means of electric dischargesAnd (3) a plasma sintering technology (SPS), and further sintering the material obtained by the melting reaction into a block. Grinding a bulk material obtained after melting into powder, selecting a graphite mould, adding a layer of carbon paper for protecting the mould in the graphite mould, putting the powder into the mould, compacting by using a graphite pressure head, then putting the mould into a discharge plasma sintering device, applying a certain pressure, vacuumizing for a period of time, filling a certain amount of Ar gas, and vacuumizing again, wherein the operation is repeated for more than three times, so that the inert vacuum environment in a furnace body is ensured, and the material is prevented from being oxidized during sintering. Vacuumizing, and when the pressure is less than 5Pa, heating and sintering. Slowly increasing current to raise the temperature from room temperature to 743K at sintering temperature after 20-30min, wherein the heating rate is 15-25K/min, keeping the sintering temperature for a period of time, generally 5min, then starting to cool, keeping the pressure at two ends of the mold during cooling, gradually reducing the current to slowly cool the mold, and preventing the mold from breaking due to rapid cooling. After cooling to room temperature, GeSeA with high density is obtained2xB3xA bulk thermoelectric material.
Example 1
Sb-doped and Te-alloyed GeSeSb0.16Te0.24The specific preparation method comprises the following steps:
(1) ball milling and mixing: x is 0.08 according to GeSeSb0.16Te0.24Weighing simple substance powder of Ge, Te, Sb and Se, wherein the total mass is 8g, then putting the powder into a ball milling tank, introducing argon for protection, and carrying out ball milling for 12h under the condition of 450 rpm.
(2) Melting reaction: taking the ball-milled powder out of the ball milling tank, pressing into pieces, putting the pieces into a quartz tube, sealing the tube by using oxyhydrogen flame, putting the tube into a furnace, heating to 773K at a rate of 3K/min, preserving heat at 773K for 30min, heating to 1073K at a rate of 3K/min, preserving heat for 2h, then cooling to 723K, preserving heat for 30min, naturally cooling, cooling to room temperature, and taking out.
(3) Solid sintering: grinding the materials obtained by the melting reaction into powder by using a mortar, adding a layer of carbon paper in a mould, then putting the powder into a graphite mould with the inner diameter of 12.7mm, putting the graphite mould into an SPS device, pressurizing at two ends of the mould with the pressure of 50MPa, vacuumizing to 5Pa, then starting to heat up to 743K at the rate of 20K/min, then preserving heat for 5min, then starting to cool down, keeping the pressure of 50MPa, gradually reducing the current to gradually reduce the temperature, cooling to room temperature, and then taking out.
Example 2
Sb-doped and Te-alloyed GeSeSb0.20Te0.30The specific preparation method comprises the following steps:
(1) ball milling and mixing: x is 0.1, according to the formula GeSeSb0.20Te0.30The method comprises the following steps of weighing simple substance powder of Ge, Te, Sb and Se, putting the simple substance powder into a ball milling tank, and ball milling for 12 hours at the rotating speed of 450rpm to fully mix the simple substance powder.
(2) Melting reaction: taking out the ball-milled powder, pressing the ball-milled powder into pieces, vacuum-packaging in a quartz tube, putting in a heating furnace, heating to 773K, keeping the temperature for 30min, then heating to 1073K, keeping the temperature for 2h, wherein the heating rate of the heating section is 3K/min, then cooling to 823K, keeping the temperature for 30min, and then naturally cooling.
(3) Solid sintering: and (2) by using a spark plasma sintering technology, putting the melted material into a mold, heating and sintering under the conditions of pressure of 50MPa and vacuum of 5Pa, wherein the heating rate is 25K/min, keeping the temperature at 743K for 5min, then slowly cooling, keeping the pressure, gradually reducing the current, cooling to room temperature, and taking out.
Example 3
Sb-doped and Te-alloyed GeSeSb0.30Te0.45The specific preparation method comprises the following steps:
(1) ball milling and mixing: x is 0.15 according to GeSeSb0.30Te0.45Weighing simple substance powder according to the chemical molar ratio, and ball-milling for 12 hours in an inert atmosphere to fully mix the simple substance powder.
(2) Melting reaction: and encapsulating the ball-milled and mixed powder in a quartz tube by using oxyhydrogen flame under a vacuum condition, heating to 773K under inert gas, preserving heat for 30min, heating to 1073K, preserving heat for 2h, and then beginning to cool. Incubate at 823K for 30 min. Then cooled to room temperature and taken out.
(3) Solid sintering: melting the GeSeSb0.30Te0.45Grinding into powder, pressurizing to 50MPa, vacuumizing, heating to 743K at 25K/min, keeping the temperature for 5min, slowly cooling to room temperature, and taking out.
Example 4
Thermal conductivity property
As shown in FIG. 1, the thermal diffusivity, D, and specific heat, C, of examples 1,2, and 3 were measured by laser light scattering analysis (LFA) and Differential Scanning Calorimetry (DSC), respectivelypUsing the formula k ═ Cpρ D (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-. 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 and 0.84W/mK at 300K. The thermal conductivities of the embodiment 1 and the embodiment 2 are 1.25W/mK and 1.15W/mK respectively when the temperature is 710K, and the thermal conductivity of the embodiment 3 is 1.17W/mK, so that the thermal conductivities are lower.
Example 5
Electric properties
The electrical properties of examples 1,2 and 3, including the conductivity σ and the Seebeck coefficient S, were systematically tested as shown in fig. 2,3 and 4. The instrument used for the electrical test was ULVAC ZEM-3. The conductivity and power factor of example 1 were highest, at 710K the conductivity and power factor of example 1 were 35148S/m and 1297. mu.W/mK, respectively2Examples 2 and 3 showed reduced conductivity, the conductivities of examples 2 and 3 were 33111S/m and 30220S/m, respectively, at 710K, and the Seebeck coefficients of examples 2 and 3 were 184 μ V/K and 193 μ V/K, respectively, at 710K, such that the power factor (PF ═ S @2σ) is lower than example 1, and at 710K, the power factors of examples 2 and 3 are 1118 μ W/mK, respectively2And 1130. mu.W/mK2。
From the thermal conductivity and electrical data, the thermoelectric figure of merit ZT can be calculated. FIG. 5 is a graph of thermoelectric figure of merit versus temperature for examples 1,2, and 3. It can be seen from fig. 5 that the ZT value of example 1 is higher, 0.73 at 710K, and as the doping amount is increased, ZT is reduced, and that the ZT values of examples 2 and 3 are 0.69 and 0.68 at 710K, respectively.
XRD characterization figure 6 is an XRD characterization of examples 1,2, 3. Under room temperature conditions, examples 1,2 and 3 all exhibit a cubic crystal structure (Fm-3m) which has good thermoelectric properties.
The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.
Claims (9)
1. A Ge-Se based thermoelectric material characterized by: the chemical general formula of the material is GeSeA2xB3xWherein: molar ratio of Ge to Se to A to B is 1:1:2x:3x and 0<x is less than or equal to 1; a is metal Sb, B is nonmetal Te or Se; the Ge-Se based thermoelectric material has a cubic crystal structure and is a p-type thermoelectric material; the Ge-Se based thermoelectric material has a particle size of 1-40 μm.
2. The Ge-Se based thermoelectric material according to claim 1, wherein x is in the range of 0.05-0.15.
3. The Ge-Se based thermoelectric material according to claim 1, wherein the Ge-Se based thermoelectric material has a particle size of 5 to 20 μm.
4. 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 12xB3xWeighing the powder of the simple substance Ge, A, B and Se according to the molar ratio, and performing ball milling and mixing to obtain mixed powder;
(2) melting reaction: cold pressing the mixed powder into blocks, putting the blocks into a quartz tube, then sealing the tube in vacuum, putting the quartz tube into a melting furnace, heating to a melting temperature, keeping the reaction for a period of time, and cooling to room temperature to obtain a block material;
(3) solid sintering: grinding the block material into powder, placing the powder into a sintering mold, then placing the mold into a sintering furnace, pressurizing to a set pressure of 30-100MPa by utilizing a spark plasma sintering technology, vacuumizing to 1-5Pa, then heating by adding current, heating to a sintering temperature of 723-800K, keeping the sintering temperature for a period of time, then reducing the current, cooling to room temperature, finishing sintering to obtain the p-type cubic phase GeSeA2xB3xA thermoelectric material.
5. The method for producing a Ge-Se-based thermoelectric material according to claim 4, characterized in that: in the step (1), the rotation speed of ball milling and mixing is 200-600rpm, preferably 450rpm, and the time of ball milling and mixing is 8-24h, preferably 12 h.
6. The method for producing a Ge-Se-based thermoelectric material according to claim 4, characterized in that: in the step (2), the melting temperature is 973K-1273K, the preferable temperature is 1073K, and the reaction time is 1h-12h, and the preferable time is 2 h.
7. The method for producing a Ge-Se-based thermoelectric material according to claim 4, characterized in that: in the step (3), the set pressure is 50 MPa.
8. The method for producing a Ge-Se-based thermoelectric material according to claim 4, characterized in that: in the step (3), the sintering temperature is 743K, the sintering temperature holding time is 1-30min, and the preferable time is 5 min.
9. The method for producing a Ge-Se-based thermoelectric material according to claim 4, characterized in that: in the step (3), the sintering furnace is a discharge plasma sintering instrument.
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| CN114249304A (en) * | 2020-09-25 | 2022-03-29 | 中国科学院大连化学物理研究所 | High-performance BiTe-based composite thermoelectric material and preparation method thereof |
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