CN103172379A - 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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- CN103172379A CN103172379A CN2013101387214A CN201310138721A CN103172379A CN 103172379 A CN103172379 A CN 103172379A CN 2013101387214 A CN2013101387214 A CN 2013101387214A CN 201310138721 A CN201310138721 A CN 201310138721A CN 103172379 A CN103172379 A CN 103172379A
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Abstract
The invention discloses a rare-earth sulfide thermoelectric material and a preparation method thereof. The chemical constitution formula of the rare-earth sulfide thermoelectric material is AxLayCe2-x-yS3, wherein A is at least one of alkaline earth elements Ca, Sr and Ba; x and y are respectively molar percentage coefficients of the alkaline earth elements and La; x is smaller than or equal to 1 and greater than or equal to 0; and y is smaller than or equal to 1 and greater than or equal to 0. The preparation method comprises the preparation steps of weighing the materials according to the chemical constitution formula, grinding and mixing the materials, vulcanizing for 1-3 hours under the condition of 800-1300 DEG C in sulfide atmosphere to obtain powder material; and vacuum sintering for 5-30 minutes at 1100-1600 DEG C under the pressure of 30-150 Mpa after grinding and molding, so as to obtain the massive thermoelectric material. The thermoelectric material disclosed by the invention has good thermoelectric properties and simple preparation method, and can be widely applied to the fields of afterheat and waste-heat power generation of medium and high temperature zones.
Description
Technical field
The invention belongs to the 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.Show according to relevant data, only having an appointment in existing heat energy 35% has obtained utilization, and most of heat energy is to discharge with the used heat form, is not well utilized.Thermoelectric material is a kind ofly can be directly heat energy and electric energy be carried out the functional materials of conversion mutually, compare with other energy transformation, that thermoelectric material has is lightweight, volume is little, pollution-free, noiselessness, safe and reliable, the characteristics such as can work under severe environment, is therefore having broad application prospects aspect generating and refrigeration.It can utilize the low grade heat energy generating, as utilizes the waste heat of thermal power plant, Nuclear power plants and the using waste heat from tail gas of automobile and aircraft etc. to generate electricity.If use thermoelectric material that low grade heat energy is taken full advantage of, can save a large amount of fossil oils, to alleviating day by day serious energy and environment problem, adapt to the aspect generation great functions such as low-carbon economy requirement.
The thermoelectricity capability of material characterizes with thermoelectric figure of merit Z: Z=S
2σ/κ.Wherein S is the Seebeck coefficient, and σ is specific conductivity, and κ is thermal conductivity.High performance thermoelectric material will have large Z value, that is to say, 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] report, 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] report, the carrier concentration by the proportioning of regulating rare earth metal and sulphur can be regulated the rare-earth sulfide thermoelectric material obtains good thermoelectricity capability.Because rare earth metal has very strong activity, very easily oxidation in air, so the method to prepare the rare-earth sulfide thermoelectric material very harsh to equipment and requirement for experiment condition, be unfavorable for applying of rare-earth sulfide thermoelectric material.Document [M. Ohta, et al., J. Alloys. Compd. 418 (2006) 209] report can pass through pyroprocessing, makes the sulphur partial loss, thereby changes the proportioning of rare earth metal and sulphur, reaches the control to the rare-earth sulfide carrier concentration.But the method needs high treatment temp, and carrier concentration is wayward.Be further to improve the thermoelectricity capability of rare-earth sulfide, need to have 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; By the mutual replacement of La and Ce element, produce lattice imperfection simultaneously, reduce the thermal conductivity of material, thereby 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 are A
x La
y Ce
2-
x-
y S
3, wherein A is at least a element in alkaline earth element Ca, Sr, Ba;
x,
yBe respectively the shared molar percentage coefficient of alkaline earth element and La, 0≤
x≤ 1,0≤
y≤ 1.
A kind of preparation method of rare-earth sulfide thermoelectric material comprises the following steps:
(1) press chemical constitution formula A
x La
y Ce
2-
x-
y S
3Prepare burden, obtain original mixture;
(2) with after the mixing of said mixture porphyrize, under 800～1300 ℃, carry out sulfuration in 1～3 hour in vulcanized gas;
(3) obtain powdered material after cooling;
(4) with the powdered material porphyrize, the moulding that obtain, at 1100～1600 ℃, the vacuum under pressure sintering of 30～150Mpa 5～30 minutes;
(5) obtain the rare-earth sulfide thermoelectric material after cooling.
As preferably, in described step (1), at least a raw material as the A element in the oxide compound of A, carbonate, the nitrate, at least a raw material as the La element in the oxide compound of La, carbonate, the nitrate, at least a raw material as the Ce element in the oxide compound of Ce, carbonate, the nitrate.
As preferably, the reaction atmosphere of the described vulcanized gas of step (2) for being provided by one or both the mixture in dithiocarbonic anhydride, hydrogen sulfide.
As preferably, the described vacuum sintering of 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 replaces the part of rare earth element by alkaline earth element, has improved the carrier concentration of material, by the mutual replacement of La and Ce element, produces lattice imperfection, has reduced the thermal conductivity of material.The present invention has improved the thermoelectric figure of merit Z of rare-earth sulfide thermoelectric material greatly, realizes the raising of conducting material thermoelectricity performance.Technique of the present invention is simple, and efficient is high, and production cost is low, has good industrial applications prospect, can be widely used in waste heat, the waste-heat power generation field of middle and high warm area.
Description of drawings
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
Raw material (calcium oxide, lanthanum trioxide, cerium oxide) is pressed chemical constitution formula Ca
0.02La
0.8Ce
1.18S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1000 ℃, in hydrogen sulfide atmosphere, sulfuration was 3 hours, obtained powdered material after cooling.The X-ray diffractogram of powdered sample is seen Fig. 1.To obtain powdered material porphyrize, moulding, at 1400 ℃, 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 seen Fig. 2.
Embodiment 2
Raw material (calcium carbonate, Phosbloc, cerous carbonate) is pressed chemical constitution formula Ca
0.03La
0.5Ce
1.47S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1200 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 2 hours, obtained powdered material after cooling.The X-ray diffractogram of powdered sample is seen Fig. 3.To obtain powdered material porphyrize, moulding, at 1500 ℃, the vacuum under pressure discharge plasma sintering of 30Mpa 20 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 3
Raw material (nitrocalcite, lanthanum nitrate, cerous nitrate) is pressed chemical constitution formula Ca
0.04La
0.4Ce
1.56S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1300 ℃, in hydrogen sulfide atmosphere, sulfuration was 2 hours, obtained powdered material after cooling.The X-ray diffractogram of powdered sample is seen Fig. 4.To obtain powdered material porphyrize, moulding, at 1600 ℃, the vacuum under pressure hot pressed sintering of 80Mpa 30 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 4
Raw material (strontium oxide, lanthanum trioxide, cerium oxide) is pressed chemical constitution formula Sr
0.4La
0.7Ce
0.9S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1200 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 1 hour, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1500 ℃, the vacuum under pressure discharge plasma sintering of 100Mpa 5 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 5
Raw material (Strontium carbonate powder, Phosbloc, cerous carbonate) is pressed chemical constitution formula Sr
0.6La
0.2Ce
1.2S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1100 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 3 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1400 ℃, the vacuum under pressure discharge plasma sintering of 40Mpa 30 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 6
Raw material (strontium nitrate, lanthanum nitrate, cerous nitrate) is pressed chemical constitution formula Sr
0.05La
0.4Ce
1.55S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1300 ℃, in hydrogen sulfide atmosphere, sulfuration was 3 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1600 ℃, the vacuum under pressure discharge plasma sintering of 50Mpa 10 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 7
Raw material (barium oxide, lanthanum trioxide, cerium oxide) is pressed chemical constitution formula Ba
0.25La
0.5Ce
1.25S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1300 ℃, in hydrogen sulfide atmosphere, sulfuration was 2 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1400 ℃, the vacuum under pressure hot pressed sintering of 80Mpa 20 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 8
Raw material (barium carbonate, Phosbloc, cerous carbonate) is pressed chemical constitution formula Ba
0.45La
0.4Ce
1.15S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1100 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 2 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1300 ℃, the vacuum under pressure hot pressed sintering of 120Mpa 30 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 9
Raw material (nitrate of baryta, lanthanum nitrate, cerous nitrate) is pressed chemical constitution formula Ba
0.55La
0.2Ce
1.25S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1300 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 1 hour, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1600 ℃, the vacuum under pressure discharge plasma sintering of 50Mpa 5 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 10
Raw material (calcium carbonate, nitrate of baryta, lanthanum trioxide, cerium oxide) is pressed chemical constitution formula Ca
0.45Ba
0.15Ce
1.4S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1200 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 2 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1500 ℃, the vacuum under pressure discharge plasma sintering of 50Mpa 10 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 11
Raw material (calcium oxide, strontium nitrate, barium carbonate, Phosbloc, cerous nitrate) is pressed chemical constitution formula Ca
0.15Sr
0.15Ba
0.05LaCe
0.65S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1250 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 3 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1400 ℃, the vacuum under pressure hot pressed sintering of 30Mpa 20 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 12
Raw material (lanthanum trioxide, Phosbloc, cerous nitrate, cerium oxide) is pressed chemical constitution formula La
0.6Ce
1.4S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1300 ℃, in dithiocarbonic anhydride atmosphere, sulfuration was 2 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1450 ℃, the vacuum under pressure hot pressed sintering of 45Mpa 25 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Embodiment 13
Raw material (nitrocalcite, Phosbloc, cerium oxide) is pressed chemical constitution formula CaLa
0.25Ce
0.75S
3Obtain original mixture after calculating weighing.After the original mixture porphyrize was mixed, at 1300 ℃, in hydrogen sulfide atmosphere, sulfuration was 3 hours, obtained powdered material after cooling.To obtain powdered material porphyrize, moulding, at 1500 ℃, the vacuum under pressure discharge plasma sintering of 30Mpa 15 minutes obtains the bulk thermoelectric material of pure isometric system after cooling.
Claims (8)
1. rare-earth sulfide thermoelectric material, it is characterized in that: 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 a element in alkaline earth element Ca, Sr, Ba;
x,
yBe respectively the shared molar percentage coefficient of alkaline earth element and La, 0≤
x≤ 1,0≤
y≤ 1.
2. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 1, is characterized in that, comprises the following steps:
(1) press chemical constitution formula A
x La
y Ce
2-
x-
y S
3Prepare burden, obtain original mixture;
(2) with after the mixing of said mixture porphyrize, under 800～1300 ℃, carry out sulfuration in 1～3 hour in vulcanized gas;
(3) obtain powdered material after cooling;
(4) with the powdered material porphyrize, the moulding that obtain, at 1100～1600 ℃, the vacuum under pressure sintering of 30～150Mpa 5～30 minutes;
(5) obtain the rare-earth sulfide thermoelectric material after cooling.
3. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 2, it is characterized in that: in described step (1), at least a raw material as the A element in the oxide compound of A, carbonate, the nitrate, at least a raw material as the La element in the oxide compound of La, carbonate, the nitrate, at least a raw material as the Ce element in the oxide compound of Ce, carbonate, the nitrate.
4. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 2 is characterized in that: the reaction atmosphere of the described vulcanized gas of step (2) for being provided by one or both the mixture in dithiocarbonic anhydride, hydrogen sulfide.
5. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 2, it is characterized in that: the described vacuum sintering of step (4) is vacuum heating-press sintering or vacuum discharge plasma agglomeration.
6. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 3, it is characterized in that: the oxide compound of described A is: the mixture of one or more in calcium oxide, strontium oxide, barium oxide.
7. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 3, it is characterized in that: the carbonate of described A is: the mixture of one or more in calcium carbonate, Strontium carbonate powder, barium carbonate.
8. the preparation method of a kind of rare-earth sulfide thermoelectric material according to claim 3, it is characterized in that: the nitrate of described A is: the mixture of one or more in nitrocalcite, strontium nitrate, nitrate of baryta.
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|---|---|---|---|---|
| CN113788677A (en) * | 2021-09-28 | 2021-12-14 | 上海电机学院 | High-entropy sesqui-rare earth sulfide ceramic material and preparation method and application thereof |
Citations (2)
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|---|---|---|---|---|
| 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 (4)
| Title |
|---|
| 《Journal of Alloys and Compounds》 20011231 S Katsuyama.etal. Phase relation and thermoelectric properties of the ternary lanthanum chalcogenide system La-A-S (A=Ca, Ba) 126-132 第320卷, 第1期 * |
| Q.M.LU.ETAL.: "Effects of double filling of La and Ce on thermoelectric properties of compounds by spark plasma sintering", 《JOURNAL OF APPLIED PHYSICS》 * |
| S KATSUYAMA.ETAL.: "Phase relation and thermoelectric properties of the ternary lanthanum chalcogenide system La–A–S (A=Ca, Ba)", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 邓瑞平等: "稀土硫化物的研究进展", 《中国科学：化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788677A (en) * | 2021-09-28 | 2021-12-14 | 上海电机学院 | High-entropy sesqui-rare earth sulfide ceramic material and preparation method and application thereof |
| CN113788677B (en) * | 2021-09-28 | 2022-10-11 | 上海电机学院 | High-entropy sesqui-rare earth sulfide ceramic material and preparation method and application thereof |
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