CN102051513B - Metal selenide thermoelectric material for intermediate temperate and preparation process thereof - Google Patents

Metal selenide thermoelectric material for intermediate temperate and preparation process thereof Download PDF

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CN102051513B
CN102051513B CN2010105390994A CN201010539099A CN102051513B CN 102051513 B CN102051513 B CN 102051513B CN 2010105390994 A CN2010105390994 A CN 2010105390994A CN 201010539099 A CN201010539099 A CN 201010539099A CN 102051513 B CN102051513 B CN 102051513B
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temperature
sintering
thermoelectric material
metal selenide
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崔教林
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Ningbo University of Technology
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Abstract

The invention provides a metal selenide thermoelectric material for intermediate temperate and a preparation process thereof, which relates to the field of thermoelectric materials. The design point is as follows: the chemical formula of the thermoelectric material is InxAgySe3, wherein x + y=2, 0.05<= y <=0.25. The preparation process comprises the following steps: putting elemental In, Ag and Se into a vacuum quartz tube; synthesizing for 20-28 hours at the temperature of 1000-1100 DEG C; cooling the InxAgySe3 cast ingot in a furnace to 600-650 DEG C, and then, immediately quenching in water; crushing and ball-milling the quenched InxAgySe3 cast ingot; carrying out spark plasma sintering to prepare a block, wherein the sintering temperature is 550-650 DEG C, the sintering pressure is 40-60Mpa, and the holding time is 8-12 minutes; coating a sodium silicate concentrated solution on the surface of the sintered block material; drying; and then, annealing for 20-28 hours in the vacuum quartz tube, wherein the annealing temperature is 180-200 DEG C. The material provided by the invention is prepared by using a conventional powder metallurgy method, thus the process is simple; the transition metal element Ag is used for replacing the In element in the In2Se3 thermoelectric alloy in an equimolar mode, thus the cost is lower; and the material has environment-friendly characteristics and does not have noise, thus the material is suitable for being used as an environment-friendly energy material.

Description

Middle temperature is with metal selenide thermoelectric material and preparation technology
Technical field
The present invention relates to thermoelectric material, is that a kind of middle temperature is with metal selenide thermoelectric material and preparation technology.
Background technology
Thermoelectric material is a kind of through current carrier, comprises the motion realization electric energy in electronics or hole and the novel semi-conductor functional materials that heat energy is directly changed each other.Generating and the refrigeration plant made by thermoelectric material have advantages such as volume is little, pollution-free, noiselessness, no wearing and tearing, good reliability, life-span length.In civil area, potential range of application: home freezer, refrigerator, superconductive electronic device cooling and cogeneration, the small-sized electric supply installation of used heat utilization power supply and side area etc.
The over-all properties of thermoelectric material is described by non-dimensional thermoelectric figure of merit ZT, ZT=T σ α 2/ κ, wherein α is that Seebeck coefficient, σ are that specific conductivity, κ are that thermal conductivity, T are T.Therefore, the performance of thermoelectric material and temperature have confidential relation.Up to now, the homogeneous thermoelectric material of being found, its highest thermoelectric figure of merit (ZT) are only just obtained peak under some temperature values.At present, mainly be the basic and serial alloy of metal silicide of Pb-Te of the exploitation fifties by the middle temperature of using among a small circle with the thermoelectric power generation material, the former its maximum thermoelectric figure of merit is about 1.5, but the Pb environmental pollution is bigger, and human body is also had injury.The latter's thermoelectricity capability is lower, its thermoelectric figure of merit generally about 0.3, maximum thermoelectric figure of merit ZT≤0.6.The principal feature of metal selenide thermoelectric material is an anisotropy, and inside has bidimensional synusia structure.Therefore, adopt methods such as doping, alloy solid solution method and designing material preparation technology can improve its thermoelectricity capability.
At In 2Se 3Mixing in the binary alloy is the comparatively common means of improving its performance.Adulterated purpose mainly is at In 2Se 3Introduce impurity level between inner bidimensional synusia structure, thereby change its energy band structure, reduce energy gap, finally coordinate semiconductor material inner electronic transport and heat transport.Based on the difference of doped chemical or compound, will form two kinds of semi-conducting materials of p-type and n-type.The many sons of P-N-type semiconductorN are the hole, and the many sons of n-N-type semiconductorN are electronics.But up to the present, for In 2Se 3The pyroelectric behavior report of matrix body material is very few, does not also have detailed relevant In at present 2Se 3The comprehensive thermoelectricity capability of matrix body material is the report of non-dimensional thermoelectric figure of merit (ZT).
Material preparation method is very big to the property relationship of material.Because In 2Se 3Sill is anisotropy, and therefore through changing preparation technology, example adopts its graceful method of boolean, zone melting method, hot extrusion method all to obtain tangible anisotropic material, but industrial scale is restricted.Preparation In 2Se 3Base film and nano wire not only equipment requirements are high, and productivity is low, and its application difficulty of obtained material is bigger, thus low-dimensional materials and device thereof be manufactured with bigger limitation.Selenium at high temperature is than being easier to the evaporable element, also volatilization at high temperature easily of selenide equally.For stoping the volatilization of components such as selenide, apply the water glass strong solution at sample surfaces, treat to carry out again behind the airing thermal treatments such as follow-up vacuum annealing of entire sample.
Summary of the invention
The present invention selects transition element Ag as In 2Se 3The doping agent that electrothermal alloy is inner improves the thermo-electric conversion performance, and being intended to provides warm with metal selenide thermoelectric material and preparation technology in a kind of to this area.Its objective is and realize through following technical scheme.
Temperature use the metal selenide thermoelectric material in a kind of, and warm in this is through at In with the metal selenide thermoelectric material 2Se 3Doping Ag element in the electrothermal alloy, its main points are that temperature is In with the metal selenide thermoelectric material in this 2Se 3Part In element in the electrothermal alloy replaces with Ag element, In 2Se 3The mole number of In element is 0.05～0.25 in the electrothermal alloy, and said middle temperature uses the chemical formula of metal selenide thermoelectric material to be In xAg ySe 3, x+y=2 wherein, 0.05≤y≤0.25.
Should in temperature be divided into five with preparation technology of metal selenide thermoelectric material and go on foot and carry out.The first step: melting is synthetic.Middle temperature is placed the synthetic In of melting in the vitreosil pipe with simple substance element In, Ag, the Se of metal selenide thermoelectric material xAg ySe 3, synthesis temperature is 1000～1100 ℃, generated time is 24 hours.Second step: slowly cooling.With melting synthetic In in the vitreosil pipe xAg ySe 3Ingot casting cools to 600～650 ℃ with the furnace.The 3rd step: quench.With the In in the vitreosil pipe xAg ySe 3After being cooled to 600～650 ℃, ingot casting, can form steady I n so immediately at quenching-in water 2Se 3Phase.The 4th step: sintering.To pass through the In after the quenching xAg ySe 3Ingot casting is pulverized, ball milling, and the powder behind the ball milling is processed block through plasma discharging spark sintering (SPS), and sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.Like optimal sintering temperature is 600 ℃, sintering pressure 50MPa, and soaking time is 10 minutes under sintering temperature.The 5th step: the block materials surface-coated water glass strong solution behind the sintering, in the vitreosil pipe, annealed 180～200 ℃ of annealing temperatures 20～28 hours.Like 190 ℃ of optimum annealing temperatures, soaking time 24 hours.Before the performance test, temperature in this is polished with fine sandpaper with the surface that thermopair, electrode contacts with the metal selenide thermoelectric material gently, remove in this warm with metal selenide thermoelectric material surface coating layer, confession performance test usefulness.
Advantage of the present invention: when the institute adulterated Ag element at In xAg ySe 3In mole number be 0.2, sample after surface-coated is handled, at 884K promptly 611 ℃ the time, Seebeck alpha=-186.0 of material (μ V/K), conductivity=1.02 * 10 4Ω -1.m -1, thermal conductivity κ=0.31 (W.K -1.m -1), maximum thermoelectric figure of merit ZT=1.1; Should middle temperature adopt conventional powder metallurgic method preparation with the metal selenide thermoelectric material, technology is simple; Adopt transition metal Ag substitute I n 2Se 3The In element of the medium mole number of electrothermal alloy, cost is lower; The thermoelectric conversion element noiselessness that this material is processed, pollution-free, be a kind of ep-type material.
Description of drawings
Fig. 1 is the present invention and other material property contrast synoptic diagram.Ordinate zou among the figure is thermoelectric figure of merit ZT; X-coordinate is temperature T/K; Curve 1 expression In 1.95Ag 0.05Se 3/ curve 2 expression In 2Se 3/ curve 3 expression In 1.75Ag 0.25Se 3/ curve 4 expression In 1.85Ag 0.15Se 3/ curve 5 expression In 1.8Ag 0.2Se 3The In of/curve 6 expression Coated (surface-coated) 1.8Ag 0.2Se 3
Embodiment
Below in conjunction with embodiment the present invention is further described:
The binary alloy In of Ag does not mix 2Se 3, when its Seebeck coefficient earlier near-129.0 (μ V.K the room temperature -1) rise to-569.0 (the μ V.K of 663K -1) ,-338.0 (μ V.K when dropping to 884K then -1) time (negative sign representes that material is the n-type), specific conductivity raises with temperature is dull, near 0.13 Ω the room temperature -1.m -1729.0 Ω when being increased to 884K -1.m -1, the total heat conductance is from 0.87 (WK -1m -1) drop to 0.28 (WK -1m -1).In behind the doping Ag element xAg ySe 3In temperature with metal selenide thermoelectric material (x+y=2,0.05≤y≤0.25), when the y value is incremented to 0.2 from 0.05, promptly the mole number of Ag element increases at 0.2 o'clock, In by 0.05 xAg ySe 3The Seebeck coefficient increase with the content of Ag and descend, when the mole number of Ag was incremented to 0.25 by 0.2, the Seebeck coefficient increased with the content of Ag and rises.In xAg ySe 3Conductivity variations just in time opposite with the variation of Seebeck coefficient, when the mole number of Ag reached 0.2, specific conductivity reached peak.Should in temperature reach at 0.2 o'clock and obtain peak with the comprehensive electric property of metal selenide thermoelectric material at the mole number of Ag, the total heat conductance increases along with the content of Ag and descends.
Comprehensive Seebeck coefficient, specific conductivity and these three factors of thermal conductivity are summarised as In xAg ySe 3The content of middle Ag has an optimum value, at this optimum value, In xAg ySe 3Comprehensive thermoelectricity capability ZT value be mxm..Among the present invention, this best Ag content is that mole number is 0.2.Sample is under the temperature 884K of mxm. reaching comprehensive thermoelectricity capability ZT value after surface-coated is handled, In xAg ySe 3Specific conductivity be 1.02 * 10 4Ω -1m -1, be the In of Ag of not mixing under the uniform temp 2Se 3Alloy specific conductivity 0.7 * 10 3Ω -1m -1About 15 times; The Seebeck coefficient is-186.0 (μ V.K -1), the total heat conductance is 0.31 (WK -1m -1), non-dimensional thermoelectric figure of merit ZT is 1.1.
Embodiment 1:
According to Formula I n 2Se 3Weighing purity also places respectively in the vitreosil pipe greater than In and Se two elements of 99.999wt.%.The melting synthesis temperature is 1000～1100 ℃, and the melting generated time is 24 hours.Between smelting period, whenever jolted pipe, guarantee that reaction evenly at a distance from 1 hour.The synthetic back of melting slowly is cooled to 600～650 ℃ earlier in stove, then at quenching-in water.Ingot casting after the quenching is through pulverizing, ball milling, and the ball milling time was controlled at 5 hours, and the powder behind the ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.In vacuum environment, annealed 20～28 hours through the block materials behind the sintering, annealing temperature is 180～200 ℃.
Embodiment 2:
The employing mole number is 0.05 the alternative In of moles such as elemental metals Ag 2Se 3In the In element.Earlier according to Formula I n 1.95Ag 0.05Se 3Weighing purity also places respectively in the vitreosil pipe greater than In, Ag and the Se element of 99.999wt.%.The melting synthesis temperature is 1000～1100 ℃, and the melting generated time is 24 hours.Between smelting period, whenever jolted pipe, guarantee that reaction evenly at a distance from 1 hour.The synthetic back of melting slowly is cooled to 600～650 ℃ earlier in stove, then at quenching-in water.Ingot casting after the quenching is through pulverizing, ball milling, and the ball milling time was controlled at 5 hours, and the powder behind the ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.In vacuum environment, annealed 20～28 hours through the block materials behind the sintering, annealing temperature is 180～200 ℃.
Embodiment 3:
The employing mole number is 0.15 the alternative In of moles such as elemental metals Ag 2Se 3In the In element.Earlier according to Formula I n 1.85Ag 0.15Se 3Weighing purity also places respectively in the vitreosil pipe greater than In, Ag and the Se element of 99.999wt.%.The melting synthesis temperature is 1000～1100 ℃, and the melting generated time is 24 hours.Between smelting period, whenever jolted pipe, guarantee that reaction evenly at a distance from 1 hour.The synthetic back of melting slowly is cooled to 600～650 ℃ earlier in stove, then at quenching-in water.Ingot casting after the quenching is through pulverizing, ball milling, and the ball milling time was controlled at 5 hours, and the powder behind the ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.In vacuum environment, annealed 20～28 hours through the block materials behind the sintering, annealing temperature is 180～200 ℃.
Embodiment 4:
The employing mole number is 0.2 the alternative In of moles such as elemental metals Ag 2Se 3In the In element.Earlier according to Formula I n 1.8Ag 0.2Se 3Weighing purity also places respectively in the vitreosil pipe greater than In, Ag and the Se element of 99.999wt.%.The melting synthesis temperature is 1000～1100 ℃, and the melting generated time is 24 hours.Between smelting period, whenever jolted pipe, guarantee that reaction evenly at a distance from 1 hour.The synthetic back of melting slowly is cooled to 600～650 ℃ earlier in stove, then at quenching-in water.Ingot casting after the quenching is through pulverizing, ball milling, and the ball milling time was controlled at 5 hours, and the powder behind the ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.In vacuum environment, annealed 20～28 hours through the block materials behind the sintering, annealing temperature is 180～200 ℃.
Embodiment 5:
The employing mole number is 0.25 the alternative In of moles such as elemental metals Ag 2Se 3In the In element.Earlier according to Formula I n 1.75Ag 0.25Se 3Weighing purity also places respectively in the vitreosil pipe greater than In, Ag and the Se element of 99.999wt.%.The melting synthesis temperature is 1000～1100 ℃, and the melting generated time is 24 hours.Between smelting period, whenever jolted pipe, guarantee that reaction evenly at a distance from 1 hour.The synthetic back of melting slowly is cooled to 600～650 ℃ earlier in stove, then at quenching-in water.Ingot casting after the quenching is through pulverizing, ball milling, and the ball milling time was controlled at 5 hours, and the powder behind the ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.In vacuum environment, annealed 20～28 hours through the block materials behind the sintering, annealing temperature is 180～200 ℃.
Embodiment 6:
The employing mole number is 0.2 the alternative In of moles such as elemental metals Ag 2Se 3In the In element.Earlier according to Formula I n 1.8Ag 0.2Se 3Weighing purity also places respectively in the vitreosil pipe greater than In, Ag and the Se element of 99.999wt.%.The melting synthesis temperature is 1000～1100 ℃, and the melting generated time is 24 hours.Between smelting period, whenever jolted pipe, guarantee that reaction evenly at a distance from 1 hour.The synthetic back of melting slowly is cooled to 600～650 ℃ earlier in stove, then at quenching-in water.Ingot casting after the quenching is through pulverizing, ball milling, and the ball milling time was controlled at 5 hours, and the powder behind the ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, sintering pressure 40～60MPa, soaking time 8～12 minutes.Block materials surface-coated water glass strong solution behind sintering was annealed in vacuum environment 20～28 hours again, and annealing temperature is 180～200 ℃.
Seebeck coefficient (the μ V.K of above-mentioned each embodiment gained material -1), specific conductivity (Ω -1m -1), thermal conductivity (WK -1m -1), thermoelectric figure of merit ZT sees the following form:
Figure GDA0000086188730000051
Learnt that by last table the material over-all properties among the embodiment 6 is comparatively desirable, promptly adopting mole number is that 0.2 moles such as elemental metals Ag substitute In 2Se 3In the In element time, it is warm with metal selenide thermoelectric material In in resulting that sample is handled the back through surface-coated 1.8Ag 0.2Se 3Over-all properties comparatively desirable.

Claims (4)

1. temperature use the metal selenide thermoelectric material in one kind, it is characterized in that warm in this is In with the metal selenide thermoelectric material 2Se 3Part In element in the electrothermal alloy replaces with the Ag element, and said middle temperature uses the chemical formula of metal selenide thermoelectric material to be In xAg ySe 3, x+y=2 wherein, 0.05≤y≤0.25.
2. according to the preparation technology of the said middle temperature of claim 1, it is characterized in that said In with the metal selenide thermoelectric material xAg ySe 3Be that melting is synthetic in the vitreosil pipe, simple substance element In, Ag, Se are placed in the vitreosil pipe that synthesis temperature is 1000～1100 ℃, generated time is 20～28 hours, then with the In in the vitreosil pipe xAg ySe 3After ingot casting cools to 600～650 ℃ with the furnace immediately at quenching-in water, with the In after quenching xAg ySe 3Ingot casting is pulverized, ball milling; Powder behind the ball milling is processed block through plasma discharging spark sintering, and sintering temperature is 550～650 ℃, sintering pressure 40～60Mpa; Soaking time 8～12 minutes; Block materials surface behind the sintering is with water glass strong solution coating processing, and back to be dried was annealed 180～200 ℃ of annealing temperatures 20～28 hours in the vitreosil pipe.
3. according to the preparation technology of the said middle temperature of claim 2, it is characterized in that said In with the metal selenide thermoelectric material xAg ySe 3The synthesis temperature of melting is 1050 ℃ in the vitreosil pipe, and sintering temperature is 600 ℃, sintering pressure 50MPa, and soaking time is 10 minutes under sintering temperature.
4. according to the preparation technology of the said middle temperature of claim 2, it is characterized in that the block materials behind the said sintering was annealed 24 hours 190 ℃ of annealing temperatures in the vitreosil pipe with the metal selenide thermoelectric material.
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CN103320666B (en) * 2013-05-24 2015-05-20 宁波工程学院 Ag-In-Zn-Se quaternary thermoelectric semiconductor and preparation technology thereof
CN103396122B (en) * 2013-08-09 2015-12-02 中国科学院宁波材料技术与工程研究所 A kind of Cd-Te base thermoelectricity material and preparation method thereof
CN105750557B (en) * 2016-03-03 2018-12-07 宁波工程学院 N-type In6Se7The preparation process of base thermoelectric semiconductor
CN108666045B (en) * 2017-04-01 2020-06-09 中国科学院大连化学物理研究所 Method for preparing iron selenium superconducting material by spark plasma sintering technology
CN110282975B (en) * 2019-07-08 2022-07-01 先导薄膜材料（广东）有限公司 Germanium selenide target material and preparation method thereof
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US20090235969A1 (en) * 2008-01-25 2009-09-24 The Ohio State University Research Foundation Ternary thermoelectric materials and methods of fabrication
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