CN105002384A - High-temperature thermal-electric material in n-type In-Sn-Li-Se based semi-conductor and preparation technology thereof - Google Patents
High-temperature thermal-electric material in n-type In-Sn-Li-Se based semi-conductor and preparation technology thereof Download PDFInfo
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- CN105002384A CN105002384A CN201510305817.4A CN201510305817A CN105002384A CN 105002384 A CN105002384 A CN 105002384A CN 201510305817 A CN201510305817 A CN 201510305817A CN 105002384 A CN105002384 A CN 105002384A
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Abstract
The invention relates to a high-temperature thermal-electric material in an n-type In-Sn-Li-Se based semi-conductor and a preparation technology thereof. The high-temperature thermal-electric material is characterized in that Sn with the mole fraction of 0.0495 and Li with the mole fraction of 0.0495 are added into an InSe alloy to form a quaternary thermal-electric material, and the chemical formula of the thermal-electric material is InSn0.01Li0.01Se; according to the preparation technology, In, Sn, Li and Se of the corresponding amount are weighed according to the chemical formula, and are smelted for 24 hours in a vacuum mode at the temperature of 950 DEG C-1050 DEG C; a smelted cast ingot is crushed and machined in a ball-milling mode, powder machined in the ball-milling mode is sintered and formed through discharging plasma sparks, the sintering temperature is 550 DEG C, the sintering pressure is 50 Mpa, time for heat preservation is 10 minutes, and the InSn0.01Li0.01Se thermal-electric material is obtained through preparation; when the thermal-electric material is at 813 K, the Seebeck coefficient a is equal to -350.21(MuV/K), the electrical conductivity s is equal to 8.93'103W-1.m-1, the heat conductivity k is equal to 0.88(W.K-1.m-1), and the maximum thermo-electricity merit figure is equal to 1.01. The material has the advantages of being free from pollution and noise, capable of being used for manufacturing medium and high temperature generating components, reliable in operation, and long in service life, and the preparation technology is simple.
Description
Technical field
The present invention relates to field of new, is high-temperature thermoelectric material and preparation technology thereof in a kind of n-type In-Sn-Li-Se base semiconductor.
Background technology
Thermoelectric semiconductor material is a kind of by current carrier, and the motion comprising electronics or hole realizes the novel semi-conductor functional materials that electric energy and heat energy are directly changed mutually.The generating made by thermoelectric material and refrigeration plant have the advantages such as volume is little, pollution-free, noiselessness, nothing wearing and tearing, good reliability, life-span length.In civil area, potential range of application: home freezer, refrigerator, superconductive electronic device cooling and cogeneration, Waste Heat Reuse are powered and side area small-scale power-plant device etc.
The over-all properties of thermoelectric material is by zero dimension thermoelectric figure of merit
zTdescribe,
zT=
tsa 2/
k, wherein
abe Seebeck coefficient,
sbe specific conductivity,
kbe thermal conductivity,
tabsolute temperature.Therefore, performance and the temperature of thermoelectric material have close relationship, the highest thermoelectric figure of merit of material (
zT) only under some temperature values, just obtain maximum value.At present, by the series alloy such as Pb-Te base, metal silicide of the mainly exploitation fifties of high temperature thermoelectric generating material in applying among a small circle; The maximum thermoelectric figure of merit of both is about 1.5, but Pb environmental pollution is comparatively large, also has injury to human body; Another shortcoming is that the best use temperature of these materials is generally 500
obelow C, therefore use temperature restriction is larger.In intrinsic situation, the thermoelectricity capability of InSe semi-conductor is not high, is difficult to make generating thermo-electric device; Its major cause is that the carrier concentration of this kind of material internal is not high, and material electric conductivity is too low.But it is higher that the advantage of this kind of semiconductor material is use temperature, and there is very high Seebeck coefficient; Although specific conductivity is lower in intrinsic situation, suitable element impurity can change its carrier concentration, thus significantly improves its specific conductivity.
Summary of the invention
For overcoming the deficiency of eigen I nSe semi-conductor, the present invention is intended to high-temperature thermoelectric material and preparation technology thereof in the n-type In-Sn-Li-Se base semiconductor providing a kind of performance higher to this area, makes it solve the technical problem that existing same type of material thermoelectricity capability is not good enough and use temperature is lower.Its objective is and to be achieved through the following technical solutions.
In this n-type In-Sn-Li-Se base semiconductor, high-temperature thermoelectric material is that in InSe alloy, add molar fraction be the Sn element of 0.00495 and the Li element of 0.00495, and form quaternary thermoelectric material, the chemical formula of this quaternary thermoelectric material is InSn
0.01li
0.01se.Above-mentioned thermoelectric material adopts powder metallurgic method to be prepared from, and its preparation technology is as follows: according to Formula I nSn
0.01li
0.01se is proportioning four kinds of elements in high-vacuum gloves case, after be placed directly in the interior paraffin sealing of silica tube and take out.Then rapid will containing the silica tube Vacuum Package of four kinds of elements, after melting synthesis again.Synthesis temperature is 950 ~ 1050 DEG C, generated time 20 ~ 28 hours.Then the quad alloy in vitreosil pipe is cooled to the furnace 700 ~ 80 DEG C immediately at quenching-in water, by the ingot casting pulverizing after quenching, ball milling, Ball-milling Time 10 hours.The dried powder of ball milling is prepared through discharge plasma sintering, and sintering temperature is 500 ~ 600 DEG C, and sintering pressure 40 ~ 60MPa, prepares InSn
0.01li
0.01se thermoelectric material.
In above-mentioned preparation technology, described InSn
0.01li
0.01the preferentially synthesis temperature of Se thermoelectric material is 1000 DEG C, and preferentially sintering temperature is 550 DEG C, preferentially sintering pressure 50MPa, is incubated 10 minutes at a sintering temperature.
Advantage of the present invention: to adopt in above-mentioned preparation technology this n-type preparation-obtained high-temperature thermoelectric material when 813K, the Seebeck coefficient of material
a=-350.21 (mV/K), specific conductivity
s=8.93 ' 10
3w
-1m
-1, thermal conductivity
k=0.88 (WK
-1m
-1), maximum thermoelectric figure of merit
zT=1.01, be thermoelectricity capability preferably material in the InSe base alloy reported at present.This material adopts conventional powder metallurgic method preparation, and technique is simple; Adopt a small amount of Sn and Li, cost is lower; Can be applicable to middle high-temperature power generation components and parts make, the thermoelectric conversion element made has noiselessness, pollution-free, reliable, the feature that the life-span is long.Be suitable as environment-friendly type thermoelectric material to use.
Accompanying drawing explanation
Fig. 1 is that the present invention contrasts schematic diagram with other material parallel in the thermoelectricity capability of pressing direction.
Fig. 2 is that the present invention contrasts schematic diagram with other material vertical in the thermoelectricity capability of pressing direction.
Ordinate zou in above figure is thermoelectric figure of merit
zT; X-coordinate is temperature
t/ K; And the relation of its Chemical Composition and embodiment is indicated with different marks.
Embodiment
Below in conjunction with accompanying drawing, with specific embodiment, the invention will be further described.
InSn
0.01li
0.01the Seebeck coefficient of Se is from-738.47 (mV/K of near room temperature
-1)-350.21 (mVK when being reduced to 813K gradually
-1).Specific conductivity raises, from the 7.92W of near room temperature with temperature dullness
-1m
-1be increased to 8.93 ' 10 during 813K
3w
-1m
-1.Total heat conductance is from 1.76 (WK
-1m
-1) monotonic decreasing is to 0.88 (WK during 813K
-1m
-1).In this, the Thermal Synthetic electrical property of high-temperature thermoelectric material exists
tobtain maximum value during=813K, maximum thermoelectric figure of merit reaches
zT=1.01.
Embodiment 1:
According to Formula I nSn
0.01li
0.01se weigh purity be greater than 99.999wt.% In, Sn, Li, Se tetra-element particle prepare burden in high-vacuum gloves case, be directly positioned over paraffin sealing in silica tube afterwards, rapid vacuum encapsulation after taking out.Then melting 24 hours at 1000 DEG C.After melting synthesis, when slowly cooling to about 750 DEG C in stove, be put into quenching-in water rapidly.By the ingot casting pulverizing after quenching, ball milling, Ball-milling Time controls at 5 hours, and the powder after ball milling is shaped through plasma discharging spark sintering, and sintering temperature is 550 DEG C, sintering pressure 50MPa, and sintering time is 10 minutes.Prepare InSn
0.01li
0.01se quaternary thermoelectric material.
Embodiment 2:
According to Formula I nSe weigh purity be greater than 99.999wt.% In, Se two element particle Vacuum Package in silica tube.Then melting 24 hours at 1000 DEG C.After melting synthesis, when slowly cooling to about 750 DEG C in stove, be put into quenching-in water rapidly.By the ingot casting pulverizing after quenching, ball milling, Ball-milling Time controls at 5 hours, and the powder after ball milling is shaped through plasma discharging spark sintering, and sintering temperature is 550 DEG C, sintering pressure 50MPa, and sintering time is 10 minutes.Prepare InSe binary electrothermal material.
Embodiment 3:
According to Formula I nSn
0.005li
0.005se weigh purity be greater than 99.999wt.% In, Sn, Li, Se tetra-element particle prepare burden in high-vacuum gloves case, be directly positioned over paraffin sealing in silica tube afterwards, rapid vacuum encapsulation after taking out.Then melting 24 hours at 1000 DEG C.After melting synthesis, when slowly cooling to about 750 DEG C in stove, be put into quenching-in water rapidly.By the ingot casting pulverizing after quenching, ball milling, Ball-milling Time controls at 5 hours, and the powder after ball milling is shaped through plasma discharging spark sintering, and sintering temperature is 550 DEG C, sintering pressure 50MPa, and sintering time is 10 minutes.Prepare InSn
0.005li
0.005se quaternary thermoelectric material.
Embodiment 4:
According to Formula I nSn
0.02li
0.02se weigh purity be greater than 99.999wt.% In, Sn, Li, Se tetra-element particle prepare burden in high-vacuum gloves case, be directly positioned over paraffin sealing in silica tube afterwards, rapid vacuum encapsulation after taking out.Then melting 24 hours at 1000 DEG C.After melting synthesis, when slowly cooling to about 750 DEG C in stove, be put into quenching-in water rapidly.By the ingot casting pulverizing after quenching, ball milling, Ball-milling Time controls at 5 hours, and the powder after ball milling is shaped through plasma discharging spark sintering, and sintering temperature is 550 DEG C, sintering pressure 50MPa, and sintering time is 10 minutes.Prepare InSn
0.02li
0.02se quaternary thermoelectric material.
Seebeck coefficient (the mV/K of the various embodiments described above resulting materials
-1), specific conductivity (W
-1m
-1), thermal conductivity (WK
-1m
-1), thermoelectric figure of merit (
zT) see the following form one:
Table one
From above-mentioned table one, in n-type In-Sn-Li-Se base semiconductor of the present invention, high-temperature thermoelectric material (embodiment 3) has best thermoelectricity capability, and preparation technology is simple, and cost is lower, is a kind of middle high-temperature thermoelectric material with actual application value.
Claims (4)
1. high-temperature thermoelectric material in a n-type In-Sn-Li-Se base semiconductor, it is characterized in that Sn and the Li element being respectively 0.00495 in InSe alloy containing molar fraction, form high-temperature thermoelectric material in quaternary, in this quaternary, the chemical formula of high-temperature thermoelectric material is InSn
0.01li
0.01se.
2. the preparation technology of high-temperature thermoelectric material in n-type In-Sn-Li-Se base semiconductor, is characterized in that this preparation technology is according to Formula I nSn
0.01li
0.01in, Sn, Li, Se tetra-kinds of elements are placed on vacuum melting synthesis in silica tube by Se, melting synthesis temperature is 950 ~ 1050 DEG C, generated time 20 ~ 28 hours, then immediately at quenching-in water after cooling to the quaternary compound in vitreosil pipe with the furnace 700 ~ 800 DEG C, by the ingot casting pulverizing after quenching, ball milling, the powder after ball milling is prepared through discharge plasma sintering, and sintering temperature is 500 ~ 600 DEG C, sintering pressure 40 ~ 60MPa, prepares InSn
0.01li
0.01se thermoelectric material.
3. the preparation technology of high-temperature thermoelectric material in n-type In-Sn-Li-Se base semiconductor according to claim 2, is characterized in that described InSn
0.01li
0.01the preferentially synthesis temperature of Se thermoelectric material is 1000 DEG C, and preferentially sintering temperature is 550 DEG C, preferentially sintering pressure 50MPa, is incubated 10 minutes at a sintering temperature.
4. the preparation technology of high-temperature thermoelectric material in n-type In-Sn-Li-Se base semiconductor according to claim 2, described four kinds of elements are it is characterized in that first to prepare burden in high-vacuum gloves case, directly be placed on paraffin sealing in silica tube afterwards, rapid vacuum encapsulation after taking out.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105750557A (en) * | 2016-03-03 | 2016-07-13 | 宁波工程学院 | N-shaped In6Se7-based thermoelectric semiconductor and preparation process thereof |
| CN105800569A (en) * | 2016-03-03 | 2016-07-27 | 宁波工程学院 | N-type CuIn3Se5-based medium-high temperature thermoelectric semiconductor and unbalanced preparation technology thereof |
-
2015
- 2015-06-05 CN CN201510305817.4A patent/CN105002384A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| A.A.A. DARWISH等: "Structural and electrical studies on nanostructured InSe thin films", 《APPLIED SURFACE SCIENCE》 * |
| C. JULIEN等: "Electrical characterization of lithium intercalated InSe", 《MATERIALS SCIENCE AND ENGINEERING：B》 * |
| G. MICOCCI等: "Electrical properties of indium selenide single crystals doped with tin", 《SOLAR ENERGY MATERIALS AND SOLAR CELLS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105750557A (en) * | 2016-03-03 | 2016-07-13 | 宁波工程学院 | N-shaped In6Se7-based thermoelectric semiconductor and preparation process thereof |
| CN105800569A (en) * | 2016-03-03 | 2016-07-27 | 宁波工程学院 | N-type CuIn3Se5-based medium-high temperature thermoelectric semiconductor and unbalanced preparation technology thereof |
| CN105800569B (en) * | 2016-03-03 | 2017-12-12 | 宁波工程学院 | N types CuIn3Se5The non-equilibrium preparation technology of base high temperature thermoelectric semiconductor |
| CN105750557B (en) * | 2016-03-03 | 2018-12-07 | 宁波工程学院 | N-type In6Se7The preparation process of base thermoelectric semiconductor |
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Application publication date: 20151028 |
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