CN107010609B - A kind of p-type Cu4Ga6Te11Base medium temperature thermoelectric semiconductor - Google Patents
A kind of p-type Cu4Ga6Te11Base medium temperature thermoelectric semiconductor Download PDFInfo
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- CN107010609B CN107010609B CN201710144261.4A CN201710144261A CN107010609B CN 107010609 B CN107010609 B CN 107010609B CN 201710144261 A CN201710144261 A CN 201710144261A CN 107010609 B CN107010609 B CN 107010609B
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Abstract
The present invention relates to a kind of p-type Cu4Ga6Te11Base medium temperature thermoelectric semiconductor, which is in Cu4Ga6Te11It uses molar fraction to replace Cu element for 0.024 Sb equimolar in alloy, constitutes quaternary thermoelectric semiconductor, chemical formula Cu3.5Ga6Sb0.5Te11；Its synthesis technology are as follows: tetra- kinds of elements of Cu, Ga, Sb, Te of corresponding amount, vacuum melting 120 hours at 1050~1150 DEG C are weighed according to chemical formula.After melting in liquid nitrogen chilling, then take out ingot casting and crush ball milling, the powder after ball milling is shaped through plasma discharging spark sintering, and sintering time 10 minutes, sintering temperature was 550~650 DEG C, and sintering pressure is 55~65MPa.It anneals 65~75 hours in 390 DEG C of vacuum tube after sintering, Cu is prepared3.5Ga6Sb0.5Te11Thermoelectric semiconductor.The advantages that it is noiseless with pollution-free, is applied to medium temperature power generating component and makes, reliable for operation, and the service life is long, and preparation process is simple.
Description
Technical field
The present invention relates to field of new materials, the key components use suitable for the medium temperature power generation that thermal energy and electric energy are directly converted
Material is a kind of p-type Cu4Ga6Te11Base medium temperature thermoelectric semiconductor.
Background technique
Thermoelectric semiconductor material is a kind of by carrier, and the movement including electronics or hole realizes that electric energy and thermal energy are direct
The novel semi-conductor functional material mutually converted.By thermoelectric material production power generation and refrigerating plant have it is small in size, pollution-free,
The advantages that noiseless, without abrasion, good reliability, long service life.In civil field, potential application range: domestic refrigerator, cold
Cabinet, superconductive electronic device be cooling and cogeneration, Waste Heat Reuse power supply and outlying district small-scale power-plant device etc..
The comprehensive performance of thermoelectric material is described by dimensionless thermoelectric figure of merit ZT, ZT=T σ α2/ κ, wherein α is Seebeck system
It is thermal conductivity, T is absolute temperature that number, σ, which are conductivity, κ,.Therefore, the performance Yu temperature of thermoelectric material have close relationship, material
Highest thermoelectric figure of merit (ZT) only under some temperature value just obtain maximum value.Currently, the power generation applied by small range is used
Thermoelectric generating material is mainly Pb-Te base, metal silicide, skutterudites and the clathrates etc. of the exploitation fifties
Series alloy.The maximum thermoelectric figure of merit of these materials is 1.5 or so, but Pb environmental pollution is larger, also harmful to human body.Separately
One the disadvantage is that the stability of these materials also up for further confirming that.Cu under normal conditions4Ga6Te11Thermoelectricity is partly led
The preparation difficulty of body is larger, it is difficult to obtain pure Cu4Ga6Te11Phase.Therefore a kind of synthesis technology need to be explored, to obtain
Cu4Ga6Te11Pure phase.Simultaneously as the thermoelectricity capability of the ternary material is not high in intrinsic situation, it is difficult to production power generation heat
Electrical part.The main reason is that the thermal conductivity of this kind of material is too big, carrier concentration is not also high, therefore conductivity is relatively low.But
The advantages of this kind of semiconductor material is that band gap width is moderate, and has Seebeck coefficient required for excellent thermoelectric material.Although
Thermal conductivity is too high in intrinsic situation, conductivity is lower, but suitable element impurity can change its band structure, introduce impurity energy
Grade, so that high carrier concentration is obtained, to significantly improve its conductivity.Simultaneously as being dissolved impurity in intracell
After element, scattering of the phonon at lattice defect increases, and so as to reduce lattice thermal conductivity, improves conducting material thermoelectricity performance.
Summary of the invention
To overcome Cu4Ga6Te11Thermoelectric semiconductor preparation difficulty is big and performance is insufficient problem, the present invention is directed to ability
Domain provides a kind of higher p-type Cu of performance4Ga6Te11Base medium temperature thermoelectric semiconductor makes it solve existing same type of material pyroelectricity
The technical problem that can be not good enough and use temperature lower.The purpose is to what is be achieved through the following technical solutions.
P-type Cu4Ga6Te11Base medium temperature thermoelectric semiconductor is in Cu4Ga6Te11It is middle use molar fraction for 0.024 Sb
Element equimolar replaces Cu element, constitutes quaternary thermoelectric semiconductor, and the chemical formula of the quaternary thermoelectric semiconductor is
Cu3.5Ga6Sb0.5Te11.The synthesis technology that above-mentioned thermoelectric semiconductor uses is as follows: according to chemical formula Cu3.5Ga6Sb0.5Te11By Cu,
Tetra- kinds of elements of Ga, Sb, Te are placed in quartz ampoule vacuum melting and synthesize, and melting synthesis temperature is 1050~1150 DEG C, when synthesis
Between 110~130 hours.Chilling quenches in liquid nitrogen after melting synthesis, quenched ingot casting is crushed, ball milling, Ball-milling Time 5
Hour, the powder after ball milling is dry is shaped through plasma discharging spark sintering, and sintering time is no more than 10 minutes, and sintering temperature is
550~650 DEG C, 55~65MPa of sintering pressure.It anneals 65~75 hours, is prepared in 390 DEG C of vacuum tube after sintering
Cu3.5Ga6Sb0.5Te11Thermoelectric semiconductor.
In above-mentioned synthesis technology, the Cu3.5Ga6Sb0.5Te11The melting synthesis temperature of thermoelectric semiconductor is 1100 DEG C, is burnt
Junction temperature is 600 DEG C, sintering pressure 60MPa, sintering time 10 minutes, is sintered after annealing 70 hours.
In above-mentioned synthesis technology, the first ingredient in high-vacuum gloves case of tetra- kinds of elements of described Cu, Ga, Sb, Te is directly put afterwards
Enter inner surface to be coated in the quartz ampoule of carbon film with paraffin sealing, rapid vacuum encapsulation, vacuum degree 10 after taking-up-5Pa。
Advantages of the present invention: using the obtained P-type thermoelectric semiconductor of above-mentioned synthesis technology in 778K, material
Factor alpha=200.23 Seebeck (μ V/K), conductivityσ=2.49 × 104Ω-1.m-1, thermal conductivity κ=0.71 (W.K-1.m-1),
Maximum thermoelectric figure of merit ZT=1.1 is the Cu reported at present4Ga6Te11Performance preferably material in base medium temperature thermoelectric semiconductor.
The material uses traditional synthesis technology, replaces Cu element using suitable Sb element, and cost is relatively low, can be applied to medium temperature power generation
Component production, manufactured thermoelectric conversion element have noiseless, pollution-free, reliable for operation, the feature of service life length.It is suitable as
Environment-friendly type thermoelectric material uses.
Detailed description of the invention
Fig. 1 is that the present invention with the thermoelectricity capability of other materials compares schematic diagram.
Ordinate in the above figure is thermoelectric figure of merit ZT；Abscissa is temperature T/K；And its chemistry is indicated with different labels
The relationship of composition and embodiment.
Specific embodiment
With reference to the accompanying drawing, with specific embodiment, the invention will be further described.
Cu3.5Ga6Sb0.5Te11Seebeck coefficient from 173.67 (μ V.K of near room temperature-1) when being gradually increased to 591K
248.75 (μ V.K-1), drop to 195.05 (μ V.K when then gradually with temperature being increased to 803K-1).Conductivity is with temperature
It increases, from the 3.53 × 10 of near room temperature3Ω-1.m-1Increase to 2.49 × 10 when 778K4Ω-1.m-1, then increased with temperature
Drop to 2.17 × 10 when 803K4Ω-1.m-1.Total thermal conductivity is from 1.33 (WK-1m-1) monotonic decreasing to 803K when 0.69
(WK-1m-1).The synthesis thermoelectricity capability of the high temperature thermoelectric semiconductor obtains maximum value in T=778K, and maximum thermoelectric figure of merit reaches
To ZT=1.1.
Embodiment 1:
According to chemical formula Cu4Ga6Te11Cu, Ga and Te tri- element particle of the purity greater than 99.999wt.% is weighed in Gao Zhen
Ingredient in empty-handed casing, after be placed directly in inner surface and be coated with paraffin sealing in the quartz ampoule of carbon film, rapid vacuum after taking-up
Encapsulation, vacuum degree 10-5Pa.Then melting synthesizes 120 hours at 1100 DEG C, and chilling is quenched in liquid nitrogen rapidly after melting synthesis
Fire.Quenched ingot casting is crushed, ball milling, Ball-milling Time control was at 5 hours, and the powder after ball milling is dry is in a short time through putting
Electric plasma spark thermal sintering, sintering time 10 minutes, sintering temperature was 600 DEG C, sintering pressure 60MPa.390 after sintering
DEG C vacuum tube in anneal 70 hours, Cu is prepared4Ga6Te11Thermoelectric semiconductor.
Embodiment 2:
According to chemical formula Cu3.8Ga6Sb0.2Te11Weigh tetra- element of Cu, Ga, Sb and Te that purity is greater than 99.999wt.%
Grain ingredient in high-vacuum gloves case, after be placed directly in inner surface and be coated in the quartz ampoule of carbon film with paraffin sealing, after taking-up
Rapid vacuum encapsulation, vacuum degree 10-5Pa.Then melting synthesizes 120 hours at 1100 DEG C, rapidly in liquid nitrogen after melting synthesis
Middle chilling quenching.Quenched ingot casting is crushed, ball milling, Ball-milling Time control was at 5 hours, and the powder after ball milling is dry is in short-term
Interior to shape through plasma discharging spark sintering, sintering time 10 minutes, sintering temperature was 600 DEG C, sintering pressure 60MPa.It burns
It anneals 70 hours in 390 DEG C of vacuum tube after knot, Cu is prepared3.8Ga6Sb0.2Te11Thermoelectric semiconductor.
Embodiment 3:
According to chemical formula Cu3.5Ga6Sb0.5Te11Weigh tetra- element of Cu, Ga, Sb and Te that purity is greater than 99.999wt.%
Grain ingredient in high-vacuum gloves case, after be placed directly in inner surface and be coated in the quartz ampoule of carbon film with paraffin sealing, after taking-up
Rapid vacuum encapsulation, vacuum degree 10-5Pa.Then melting synthesizes 120 hours at 1100 DEG C, rapidly in liquid nitrogen after melting synthesis
Middle chilling quenching.Quenched ingot casting is crushed, ball milling, Ball-milling Time control was at 5 hours, and the powder after ball milling is dry is in short-term
Interior to shape through plasma discharging spark sintering, sintering time 10 minutes, sintering temperature was 600 DEG C, sintering pressure 60MPa.It burns
It anneals 70 hours in 390 DEG C of vacuum tube after knot, Cu is prepared3.5Ga6Sb0.5Te11Thermoelectric semiconductor.
Embodiment 4:
According to chemical formula Cu3Ga6Sb1Te11Weigh tetra- element particle of Cu, Ga, Sb and Te that purity is greater than 99.999wt.%
The ingredient in high-vacuum gloves case, after be placed directly in inner surface and be coated with paraffin sealing in the quartz ampoule of carbon film, it is fast after taking-up
Fast Vacuum Package, vacuum degree 10-5Pa.Then melting synthesizes 120 hours at 1100 DEG C, after melting synthesis rapidly in liquid nitrogen
Chilling quenching.Quenched ingot casting is crushed, ball milling, Ball-milling Time control was at 5 hours, and the powder after ball milling is dry is in the short time
Interior to shape through plasma discharging spark sintering, sintering time 10 minutes, sintering temperature was 600 DEG C, sintering pressure 60MPa.Sintering
It anneals 70 hours in 390 DEG C of vacuum tube afterwards, Cu is prepared3Ga6Sb1Te11Thermoelectric semiconductor.
Embodiment 5:
According to chemical formula Cu2.5Ga6Sb1.5Te11Weigh tetra- element of Cu, Ga, Sb and Te that purity is greater than 99.999wt.%
Grain ingredient in high-vacuum gloves case, after be placed directly in inner surface and be coated in the quartz ampoule of carbon film with paraffin sealing, after taking-up
Rapid vacuum encapsulation, vacuum degree 10-5Pa.Then melting synthesizes 120 hours at 1100 DEG C, rapidly in liquid nitrogen after melting synthesis
Middle chilling quenching.Quenched ingot casting is crushed, ball milling, Ball-milling Time control was at 5 hours, and the powder after ball milling is dry is in short-term
Interior to shape through plasma discharging spark sintering, sintering time 10 minutes, sintering temperature was 600 DEG C, sintering pressure 60MPa.It burns
It anneals 70 hours in 390 DEG C of vacuum tube after knot, Cu is prepared2.5Ga6Sb1.5Te11Thermoelectric semiconductor.
Seebeck coefficient (the μ V.K of the various embodiments described above resulting materials-1), conductivity (Ω-1m-1), thermal conductivity (WK-1m-1), thermoelectric figure of merit (ZT) see the table below one:
Table one
By above-mentioned table one it is found that thermoelectric semiconductor (the Cu that the embodiment of the present invention 3 is prepared3.5Ga6Sb0.5Te11) tool
There is optimal thermoelectricity capability and using traditional synthesis technology and uncomplicated, cost is relatively low, is a kind of to have practical application value
Warm thermoelectric material.
Claims (1)
1. a kind of p-type Cu4Ga6Te11Base medium temperature thermoelectric semiconductor, it is characterised in that in Cu4Ga6Te11In semiconductor using mole
The Sb equimolar that score is 0.024 replaces Cu element, constitutes quaternary thermoelectric semiconductor, and the chemical formula of the quaternary thermoelectric semiconductor is
Cu3.5Ga6Sb0.5Te11。
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| CN108511587B (en) * | 2018-01-24 | 2021-05-18 | 宁波工程学院 | P-type Cu with excessive copper3.9Ga4.2Te8Medium-temperature thermoelectric material and preparation process thereof |
| TWI683910B (en) * | 2018-10-18 | 2020-02-01 | 國立中山大學 | Thermoelectric alloy, method for producing the same and thermoelectric alloy composite |
| CN112310268A (en) * | 2020-10-30 | 2021-02-02 | 中国电子科技集团公司第十八研究所 | Preparation method of novel medium-temperature thermoelectric material |
| CN113998896B (en) * | 2021-10-28 | 2023-03-24 | 杭州光学精密机械研究所 | High-efficiency synthesis method of chalcogenide glass powder |
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| CN102234843A (en) * | 2011-06-24 | 2011-11-09 | 宁波工程学院 | Ga-Te-based thermoelectric semiconductor with superstructure and preparation method thereof |
| CN102887488A (en) * | 2012-09-11 | 2013-01-23 | 宁波工程学院 | Cu-Ga-Sb-Te quaternary thermoelectric semiconductor with chalcopyrite structure, and preparation process for Cu-Ga-Sb-Te quaternary thermoelectric semiconductor |
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