CN103172379B - Rare-earth sulfide thermoelectric material and preparation method thereof - Google Patents
Rare-earth sulfide thermoelectric material and preparation method thereof Download PDFInfo
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- CN103172379B CN103172379B CN201310138721.4A CN201310138721A CN103172379B CN 103172379 B CN103172379 B CN 103172379B CN 201310138721 A CN201310138721 A CN 201310138721A CN 103172379 B CN103172379 B CN 103172379B
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Abstract
The invention discloses a kind of Rare-earth sulfide thermoelectric material and preparation method thereof, the chemical constitution formula of this Rare-earth sulfide thermoelectric material is A
xla
yce
2-x-ys
3, wherein A is at least one element in alkaline earth element Ca, Sr, Ba; X, y are respectively the molar percentage coefficient shared by alkaline earth element and La, 0≤x≤1,0≤y≤1.Its preparation process is: by chemical constitution formula raw materials weighing, and after porphyrize mixing, in vulcanized gas, under 800 ~ 1300 DEG C of conditions, sulfuration 1 ~ 3 hour, obtains powdered material; Then through porphyrize, shaping, at 1100 ~ 1600 DEG C, the vacuum under pressure sintering of 30 ~ 150Mpa 5 ~ 30 minutes, obtains bulk thermoelectric material.Thermoelectric material of the present invention has good thermoelectricity capability, and preparation method is simple, can be widely used in the waste heat of middle and high warm area, waste-heat power generation field.
Description
Technical field
The invention belongs to semi-conductor thermoelectric material preparing technical field, be specifically related to a kind of Rare-earth sulfide thermoelectric material and preparation method thereof.
Background technology
Along with the development of process of industrialization, the fossil feedstock such as a large amount of coals, oil are used to generating and heating, caused global energy and environment problem, and these problems are more and more serious.Heat energy and electric energy are most important energy forms in our actual life, electric energy be in the various form energy transmission and use at most, the most a kind of.According to relevant data display, only having an appointment in existing heat energy 35% obtains utilization, and most of heat energy is then discharge with used heat form, is not well utilized.Thermoelectric material is a kind of functional materials that directly heat energy and electric energy can be carried out conversion mutually, compared with other energy transformation, thermoelectric material have lightweight, volume is little, pollution-free, noiselessness, safe and reliable, the feature such as can work in the presence of a harsh environment, therefore have broad application prospects in generating and refrigeration.It can utilize low grade heat energy to generate electricity, and generates electricity as utilized thermal power plant, the waste heat of Nuclear power plants and the using waste heat from tail gas of automobile and aircraft etc.If use thermoelectric material to be made full use of by low grade heat energy, a large amount of fossil oil can be saved, and to alleviating day by day serious energy and environment problem, adapt to the aspects such as low-carbon economy requirement and producing great function.
The thermoelectricity capability thermoelectric figure of merit Z of material characterizes: Z=S
2σ/κ.Wherein S is Seebeck coefficient, and σ is specific conductivity, and κ is thermal conductivity.High performance thermoelectric material will have large Z value, that is, and large Seebeck coefficient, high specific conductivity and low thermal conductivity.The Seebeck coefficient of thermoelectric material, specific conductivity and thermal conductivity depend on the carrier concentration of material, reasonably control the carrier concentration of material, can prepare high performance thermoelectric material.Document [S.M. Taher, et al., Mat. Res. Bull. 16 (1981) 1407] is reported, rare-earth sulfide has good thermoelectricity capability, particularly Th
3p
4the γ phase sesquialter rare-earth sulfide of the cubic crystal structure of type has superior thermoelectricity capability especially.Document [T. Takeshta, et al., J. Appl. Phys. 57 (1985) 4633] is reported, by the carrier concentration regulating the proportioning of rare earth metal and sulphur can regulate Rare-earth sulfide thermoelectric material, obtains good thermoelectricity capability.Because rare earth metal has very strong activity, be very easily oxidized in atmosphere, therefore the method prepare Rare-earth sulfide thermoelectric material to equipment and requirement for experiment condition very harsh, be unfavorable for applying of Rare-earth sulfide thermoelectric material.Document [M. Ohta, et al., J. Alloys. Compd. 418 (2006) 209] is reported, by pyroprocessing, make sulphur partial loss, thus change the proportioning of rare earth metal and sulphur, reach the control to rare-earth sulfide carrier concentration.But the method needs high treatment temp, and carrier concentration is wayward.For improving the thermoelectricity capability of rare-earth sulfide further, to need better, more practical method.
Summary of the invention
The object of the present invention is to provide a kind of high performance Rare-earth sulfide thermoelectric material and preparation method thereof, by alkaline earth element, the part of rare earth element is replaced, to improve the carrier concentration of material; Simultaneously by the mutual replacement of La and Ce element, produce lattice imperfection, reduce the thermal conductivity of material, thus improve A
x la
y ce
2-
x-
y s
3the thermoelectric figure of merit Z of thermoelectric material, realizes the raising of conducting material thermoelectricity performance.
The following technical scheme of employing of the present invention:
A kind of Rare-earth sulfide thermoelectric material, the chemical constitution formula of this Rare-earth sulfide thermoelectric material is A
x la
y ce
2-
x-
y s
3, wherein A is at least one element in alkaline earth element Ca, Sr, Ba;
x,
ybe respectively the molar percentage coefficient shared by alkaline earth element and La, 0≤
x≤ 1,0≤
y≤ 1.
A preparation method for Rare-earth sulfide thermoelectric material, comprises the following steps:
(1) by chemical constitution formula A
x la
y ce
2-
x-
y s
3prepare burden, obtain original mixture;
(2), after being mixed by said mixture porphyrize, at 800 ~ 1300 DEG C, sulfuration in 1 ~ 3 hour in vulcanized gas, is carried out;
(3) powdered material is obtained after cooling;
(4) the powdered material porphyrize, shaping will obtained, at 1100 ~ 1600 DEG C, the vacuum under pressure sintering of 30 ~ 150Mpa 5 ~ 30 minutes;
(5) Rare-earth sulfide thermoelectric material is obtained after cooling.
As preferably, in described step (1), with the raw material that at least one in the oxide compound of A, carbonate, nitrate is element A, with at least one in the oxide compound of La, carbonate, nitrate for the raw material of La element, with at least one in the oxide compound of Ce, carbonate, nitrate for the raw material of Ce element.
As preferably, the reaction atmosphere of vulcanized gas for being provided by the mixture of one or both in dithiocarbonic anhydride, hydrogen sulfide described in step (2).
As preferably, the vacuum sintering described in step (4) is vacuum heating-press sintering or vacuum discharge plasma agglomeration.
As preferably, the carbonate of described A is: the oxide compound of described A is: the mixture of one or more in calcium oxide, strontium oxide, barium oxide.
As preferably, the carbonate of described A is: the mixture of one or more in calcium carbonate, Strontium carbonate powder, barium carbonate.
As preferably, the nitrate of described A is: the mixture of one or more in nitrocalcite, strontium nitrate, nitrate of baryta.
The beneficial effect that the present invention has is:
The present invention is replaced the part of rare earth element by alkaline earth element, improves the carrier concentration of material, by the mutual replacement of La and Ce element, produces lattice imperfection, reduces the thermal conductivity of material.The present invention substantially increases the thermoelectric figure of merit Z of Rare-earth sulfide thermoelectric material, realizes the raising of conducting material thermoelectricity performance.Present invention process is simple, and efficiency is high, and production cost is low, has good industrial applications prospect, can be widely used in the waste heat of middle and high warm area, waste-heat power generation field.
Accompanying drawing explanation
Fig. 1 is Ca in embodiment 1
0.02la
0.8ce
1.18s
3the X-ray diffractogram of powdered sample;
Fig. 2 is Ca in embodiment 1
0.02la
0.8ce
1.18s
3the X-ray diffractogram of sintered sample;
Fig. 3 is Ca in embodiment 2
0.03la
0.5ce
1.47s
3the X-ray diffractogram of powdered sample;
Fig. 4 is Ca in embodiment 1
0.04la
0.4ce
1.56s
3the X-ray diffractogram of powdered sample.
Embodiment
Embodiment 1
By raw material (calcium oxide, lanthanum trioxide, cerium oxide) by chemical constitution formula Ca
0.02la
0.8ce
1.18s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1000 DEG C, in hydrogen sulfide atmosphere, sulfuration 3 hours, obtains powdered material after cooling.The X-ray diffractogram of powdered sample is shown in Fig. 1.To obtain powdered material porphyrize, shaping, at 1400 DEG C, the vacuum under pressure hot pressed sintering of 50Mpa 10 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.The X-ray diffractogram of sintered sample is shown in Fig. 2.
Embodiment 2
By raw material (calcium carbonate, Phosbloc, cerous carbonate) by chemical constitution formula Ca
0.03la
0.5ce
1.47s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1200 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 2 hours, obtains powdered material after cooling.The X-ray diffractogram of powdered sample is shown in Fig. 3.To obtain powdered material porphyrize, shaping, at 1500 DEG C, the vacuum under pressure discharge plasma sintering of 30Mpa 20 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 3
By raw material (nitrocalcite, lanthanum nitrate, cerous nitrate) by chemical constitution formula Ca
0.04la
0.4ce
1.56s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1300 DEG C, in hydrogen sulfide atmosphere, sulfuration 2 hours, obtains powdered material after cooling.The X-ray diffractogram of powdered sample is shown in Fig. 4.To obtain powdered material porphyrize, shaping, at 1600 DEG C, the vacuum under pressure hot pressed sintering of 80Mpa 30 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 4
By raw material (strontium oxide, lanthanum trioxide, cerium oxide) by chemical constitution formula Sr
0.4la
0.7ce
0.9s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1200 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 1 hour, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1500 DEG C, the vacuum under pressure discharge plasma sintering of 100Mpa 5 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 5
By raw material (Strontium carbonate powder, Phosbloc, cerous carbonate) by chemical constitution formula Sr
0.6la
0.2ce
1.2s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1100 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 3 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1400 DEG C, the vacuum under pressure discharge plasma sintering of 40Mpa 30 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 6
By raw material (strontium nitrate, lanthanum nitrate, cerous nitrate) by chemical constitution formula Sr
0.05la
0.4ce
1.55s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1300 DEG C, in hydrogen sulfide atmosphere, sulfuration 3 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1600 DEG C, the vacuum under pressure discharge plasma sintering of 50Mpa 10 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 7
By raw material (barium oxide, lanthanum trioxide, cerium oxide) by chemical constitution formula Ba
0.25la
0.5ce
1.25s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1300 DEG C, in hydrogen sulfide atmosphere, sulfuration 2 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1400 DEG C, the vacuum under pressure hot pressed sintering of 80Mpa 20 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 8
By raw material (barium carbonate, Phosbloc, cerous carbonate) by chemical constitution formula Ba
0.45la
0.4ce
1.15s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1100 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 2 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1300 DEG C, the vacuum under pressure hot pressed sintering of 120Mpa 30 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 9
By raw material (nitrate of baryta, lanthanum nitrate, cerous nitrate) by chemical constitution formula Ba
0.55la
0.2ce
1.25s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1300 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 1 hour, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1600 DEG C, the vacuum under pressure discharge plasma sintering of 50Mpa 5 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 10
By raw material (calcium carbonate, nitrate of baryta, lanthanum trioxide, cerium oxide) by chemical constitution formula Ca
0.45ba
0.15ce
1.4s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1200 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 2 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1500 DEG C, the vacuum under pressure discharge plasma sintering of 50Mpa 10 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 11
By raw material (calcium oxide, strontium nitrate, barium carbonate, Phosbloc, cerous nitrate) by chemical constitution formula Ca
0.15sr
0.15ba
0.05laCe
0.65s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1250 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 3 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1400 DEG C, the vacuum under pressure hot pressed sintering of 30Mpa 20 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 12
By raw material (lanthanum trioxide, Phosbloc, cerous nitrate, cerium oxide) by chemical constitution formula La
0.6ce
1.4s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1300 DEG C, in dithiocarbonic anhydride atmosphere, sulfuration 2 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1450 DEG C, the vacuum under pressure hot pressed sintering of 45Mpa 25 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 13
By raw material (nitrocalcite, Phosbloc, cerium oxide) by chemical constitution formula CaLa
0.25ce
0.75s
3calculate after weighing and obtain original mixture.After being mixed by original mixture porphyrize, at 1300 DEG C, in hydrogen sulfide atmosphere, sulfuration 3 hours, obtains powdered material after cooling.To obtain powdered material porphyrize, shaping, at 1500 DEG C, the vacuum under pressure discharge plasma sintering of 30Mpa 15 minutes, obtains the bulk thermoelectric material of pure isometric system after cooling.
Claims (1)
1. a preparation method for the bulk thermoelectric material of pure isometric system, is characterized in that: by material oxidation calcium, lanthanum trioxide and cerium oxide by chemical constitution formula Ca
0.02la
0.8ce
1.18s
3calculate after weighing and obtain original mixture; After being mixed by original mixture porphyrize, under 1000 DEG C of conditions, in hydrogen sulfide atmosphere, sulfuration 3 hours, obtains powdered material after cooling; By the powdered material porphyrize, shaping obtained; At 1400 DEG C, the vacuum under pressure hot pressed sintering of 50Mpa 10 minutes; The bulk thermoelectric material of pure isometric system is obtained after cooling.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863506A (en) * | 2010-02-12 | 2010-10-20 | 长春理工大学 | Rare earth sulfide with network nano structure and preparation method thereof |
| CN102113141A (en) * | 2009-10-22 | 2011-06-29 | 松下电器产业株式会社 | Thermoelectric conversion material and thermoelectric conversion element |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102113141A (en) * | 2009-10-22 | 2011-06-29 | 松下电器产业株式会社 | Thermoelectric conversion material and thermoelectric conversion element |
| CN101863506A (en) * | 2010-02-12 | 2010-10-20 | 长春理工大学 | Rare earth sulfide with network nano structure and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Effects of double filling of La and Ce on thermoelectric properties of compounds by spark plasma sintering;Q.M.Lu.etal.;《Journal of Applied Physics》;20051231;第98卷;106107-1-106107-3 * |
| Phase relation and thermoelectric properties of the ternary lanthanum chalcogenide system La–A–S (A=Ca, Ba);S Katsuyama.etal.;《Journal of Alloys and Compounds》;20011231;第320卷(第1期);126-132 * |
| 邓瑞平等.稀土硫化物的研究进展.《中国科学:化学》.2012,第42卷(第9期),1337-1355. * |
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