CN104555950A - Bismuth telluride material with excellent thermoelectric properties at medium temperature zone and method for preparing bismuth telluride material with excellent thermoelectric properties at medium temperature zone - Google Patents

Bismuth telluride material with excellent thermoelectric properties at medium temperature zone and method for preparing bismuth telluride material with excellent thermoelectric properties at medium temperature zone Download PDF

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CN104555950A
CN104555950A CN201510051468.8A CN201510051468A CN104555950A CN 104555950 A CN104555950 A CN 104555950A CN 201510051468 A CN201510051468 A CN 201510051468A CN 104555950 A CN104555950 A CN 104555950A
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tellurobismuthite
sintering
preparation
bismuth telluride
temperature zone
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CN104555950B (en
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史迅
郝峰
陈立东
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • C01B19/00—Selenium; Tellurium; Compounds thereof

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Abstract

The invention relates to a bismuth telluride material with excellent thermoelectric properties at the medium temperature zone and a method for preparing the bismuth telluride material with excellent thermoelectric properties at the medium temperature zone. The formula of the bismuth telluride material is CuxBi0.3Sb1.7-xTe3, wherein x is greater than or equal to 0.005 and less than or equal to 0.02. The carrier concentration of the bismuth telluride material disclosed by the invention is effectively improved through self doping and Cu doping so that the electric properties of the material are greatly optimized and simultaneously the intrinsic excitation is restrained; and the optimized material has remarkably-improved thermoelectric properties at the 550K neighboring temperature zone.

Description

A kind of middle warm area Tellurobismuthite material with excellent heat electrical property and preparation method thereof
Technical field
The invention belongs to thermoelectric material field, relate to the P type Tellurobismuthite material after a kind of optimization and preparation method, this material warm area near 550K has excellent thermoelectricity capability, meets the service requirements of Tellurobismuthite power generating device well.
Background technology
Thermoelectric generation technology can utilize thermoelectric material to realize the mutual conversion of heat energy and electric energy.Utilize Seebeck effect, inferior industrial waste heat can be converted to the electric energy of high-quality, and there is green non-pollution, advantage that reliability is high.The efficiency of conversion of thermoelectric material all has relation with the temperature of high/low temperature end during work and material itself, and wherein the thermoelectricity capability thermoelectric figure of merit ZT of material evaluates, and is defined as ZT=S 2σ T/k, wherein S is Seebeck coefficient, and σ is specific conductivity, and T is absolute temperature, and k represents thermal conductivity.The ZT value of material is higher, and its thermoelectricity capability is also higher.
Tellurobismuthite is a kind of conventional thermoelectric material, and commercialization degree is higher, and P type Tellurobismuthite material conventional is at present Bi 2te 3with Sb 2te 3solid solution compound, prepare mainly through preparation methods such as zone melting method, descent method, powder metallurgy.Wherein utilize zone melting method and descent method can prepare the Tellurobismuthite monocrystal material having and take tropism by force, and along the direction of growth, there is best thermoelectricity capability, but due to easy cleavage, the waste of material in the course of processing, can be caused.In addition, powder metallurgy is also a kind of important preparation method, the method is simple, and can significantly improve mechanics of materials intensity, there is better processing characteristics, but in sintering process, material can produce certain orientation under the inducing action of pressure, therefore the thermoelectricity that need carry out evaluating material according to sintering pressure direction transports performance.
Bi 0.5sb 1.5te 3be composition comparatively conventional at present, at room temperature have excellent thermoelectricity capability, be therefore often used as the thermoelectric cooling device of near room temperature, the technology matched with it is also comparatively complete.But the working temperature of Thermoelectric Generator temperature end is at about 550K, be in middle temperature warm area, and traditional Tellurobismuthite material B i 0.5sb 1.5te 3intrinsic excitation occurs near 550K causes material property sharply to worsen, and cannot meet the service requirements of Tellurobismuthite power generating device.But intrinsic excitation suppresses by the carrier concentration increasing material, the content of Sb can be increased on the one hand, utilize auto-doping to improve carrier concentration, Cu also can be used on the other hand to adulterate and improve carrier concentration.Also lack the research work being optimized warm area performance in Tellurobismuthite by comprehensive utilization auto-doping and Cu doping at present.It should be noted that the Tellurobismuthite material usually adopting pressure sintering mode to prepare has good thermoelectricity capability perpendicular to sintering pressure direction in addition, but cut in the direction and easily make material generation cleavage, cause waste, thus increase production cost.Therefore, improve the thermoelectricity capability that Tellurobismuthite is parallel to sintering pressure direction, can be effectively cost-saving, have broad application prospects.
Summary of the invention
The present invention is intended to overcome the defect of existing Tellurobismuthite material in thermoelectricity capability and preparation method, the invention provides a kind of middle warm area Tellurobismuthite material with excellent heat electrical property and preparation method thereof.
The invention provides the Tellurobismuthite material that a kind of middle warm area has excellent heat electrical property, the composition general formula of described Tellurobismuthite material is Cu xbi 0.3sb 1.7-xte 3, wherein 0.005≤x≤0.02.
Preferably, described Tellurobismuthite material is P type, is better than the thermoelectricity capability perpendicular to sintering pressure direction at the thermoelectricity capability being parallel to sintering pressure direction.
Preferably, when 550K, described Tellurobismuthite material is being parallel to the thermoelectric figure of merit in sintering pressure direction between 1.0-1.3.
Again, the invention provides a kind of preparation method of above-mentioned Tellurobismuthite material, comprising:
1) stoichiometrically take the simple substance of described Tellurobismuthite material component, encapsulate in a vacuum or inert atmosphere after mixing;
2) by the above-mentioned simple substance of encapsulation first melting treatment at 1000-1150 DEG C, then quenching and 350-450 DEG C of anneal, again the material that above-mentioned simple substance is formed through melting, anneal is ground to form powder, 400-450 DEG C, pressure sintering under 50-65MPa, obtain described Tellurobismuthite material.
Preferably, described encapsulation adopts plasma or flame gun packaged type to be enclosed in silica tube by above-mentioned simple substance.
Preferably, melting treatment 10-14 hour at 1000-1150 DEG C, temperature rise rate is 1-3 DEG C/min.
Preferably, at 350-450 DEG C of anneal 3-5 days.
Preferably, described pressure sintering is discharge plasma sintering, and the time of discharge plasma sintering is 8-12 minute, and temperature rise rate is 30-50 DEG C/min.
Beneficial effect of the present invention:
In the present invention, Tellurobismuthite material effectively improves the carrier concentration of material by auto-doping and Cu doping, and material electrical property is significantly optimized, and intrinsic excitation is suppressed simultaneously.Material after optimization thermoelectricity capability of warm area near 550K is increased dramatically.
Accompanying drawing explanation
Fig. 1 illustrates the preparation method of P type Tellurobismuthite in one embodiment of the present invention;
Fig. 2 shows the Bi of preparation in comparative example 1 0.3sb 1.7te 3correlated performance curve, wherein, a is Bi 0.3sb 1.7te 3the temperature variant curve of thermal conductivity, b is Bi 0.3sb 1.7te 3the temperature variant curve of specific conductivity, c is Bi 0.3sb 1.7te 3the temperature variant curve of Seebeck coefficient, d is Bi 0.3sb 1.7te 3the temperature variant curve of thermoelectric figure of merit ZT;
Fig. 3 shows the Cu of preparation in embodiment 1 0.005bi 0.3sb 1.695te 3correlated performance curve, wherein, a is Cu 0.005bi 0.3sb 1.695te 3the temperature variant curve of thermal conductivity, b is Cu 0.005bi 0.3sb 1.695te 3the temperature variant curve of specific conductivity, c is Cu 0.005bi 0.3sb 1.695te 3the temperature variant curve of Seebeck coefficient, d is Cu 0.005bi 0.3sb 1.695te 3the temperature variant curve of thermoelectric figure of merit ZT;
Fig. 4 shows the Cu of preparation in embodiment 2 0.01bi 0.3sb 1.69te 3correlated performance curve, wherein, a is Cu 0.01bi 0.3sb 1.69te 3the temperature variant curve of thermal conductivity, b is Cu 0.01bi 0.3sb 1.69te 3the temperature variant curve of specific conductivity, c is Cu 0.01bi 0.3sb 1.69te 3the temperature variant curve of Seebeck coefficient, d is Cu 0.01bi 0.3sb 1.69te 3the temperature variant curve of thermoelectric figure of merit ZT;
In Fig. 2 ~ Fig. 4, //press represents and is parallel to sintering pressure direction, and ⊥ press represents perpendicular to sintering pressure direction.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention provides the P type Tellurobismuthite material after a kind of optimization, it consists of Cu xbi 0.3sb 1.7-xte 3(0.005≤x≤0.02).This composition effectively improves the carrier concentration of material by auto-doping and Cu doping, and material electrical property is significantly optimized, and intrinsic excitation is suppressed simultaneously.
As x=0.005, for composition Cu xbi 0.3sb 1.7-xte 3, this material ZT value when to have maximum ZT value be 1.24,550K to 500K is still 1.2.Because Tellurobismuthite power generating device operation temperature area is in 350K to 550K warm area, in this warm area, this material (Cu xbi 0.3sb 1.7-xte 3) average ZT also reaches 1.2, mean that effciency of energy transfer is 7.6%, meet the service requirements of power generating device, contribute to improving efficiency of conversion, there is fabulous prospects for commercial application.
Because this material can have certain orientation under the effect of the pressure in sintering process, the thermoelectricity capability being parallel and perpendicular to pressure direction is caused to there are differences, after tested, material involved in the present invention has better thermoelectricity capability being parallel to pressure direction, consider the feature of the easy cleavage of Tellurobismuthite, and this direction has good workability, waste effectively can be avoided, cost-saving.
This material comparatively has better thermoelectricity capability perpendicular to pressure direction being parallel to sintering pressure direction, is not only convenient to processing cutting, and near 550K in warm area thermoelectricity capability excellent.Material after optimization thermoelectricity capability of warm area near 550K is increased dramatically.
Preparation of the present invention is realized by the technique of Vacuum Package, melting, quenching, annealing.Accompanying drawing 1 is preparation technology's schema, and preparation method comprises the following steps:
1) the present invention with the high-purity element simple substance of Cu, Bi, Sb, Te for initial feed, according to x:0.3:(1.7-x): the molar ratio weighing of 3, and be encapsulated in silica tube;
2) being encapsulated in the glove box being full of argon gas atmosphere of silica tube is carried out, and using plasma or flame gun mode encapsulate, and encapsulation process silica tube vacuumizes;
3) melting process carries out in vertical melting furnace.Be raised to 1000 ~ 1150 DEG C (such as about 1100 DEG C) from room temperature with the temperature rise rate of 1.5 DEG C/min, constant temperature melting 10 ~ 14 hours (such as 12 hours), then frozen water quenchings;
4) annealing process completed in tube furnace, 350 ~ 450 DEG C (such as 400 DEG C) annealing 3 ~ 5 days;
5) block after annealing adopts discharge plasma sintering technique (SPS) to prepare compact block material after pulverizing.Employing diameter is that the graphite jig of Φ 12.7mm carries out pressure sintering, sintering temperature is between 400 DEG C to 450 DEG C, temperature rise rate is about 40 DEG C/min, and pressure is 50 ~ 65Mpa, and the time is 8 ~ 12 minutes (such as at sintering temperature heat-insulation pressure keeping about 10min).
Described Vacuum Package also can be carried out under inert protective gas.
Described pressure sintering adopts discharge plasma sintering mode.
This material has been prepared by melting, quenching, annealing, discharge plasma sintering technique (SPS), first high-purity element simple substance is weighed according to stoichiometric ratio, and vacuum encloses silica tube, technique through the high-temperature fusion of 1000 ~ 1150 DEG C, quenching and 350 ~ 450 DEG C of annealing obtains the ingot casting of uniform composition, then pulverize, and adopt SPS sintering technology to be prepared into compact block, wherein SPS sintering temperature is 400 ~ 450 DEG C, sintering pressure is 50 ~ 65Mpa, and the heat-insulation pressure keeping time is 8 ~ 12min.Utilize this technique to carry out high-volume producing this material on a large scale, find that thermoelectricity capability is good, there is good repeatability, the requirement of industrial mass manufacture can be met.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Comparative example 1:
According to chemical formula Bi 0.3sb 1.7te 3take high-purity element simple substance and load silica tube, in the glove box being full of argon inert atmosphere, adopt plasma gun to encapsulate, packaged silica tube is placed in vertical melting furnace and carries out melting, be raised to 1000 DEG C with the temperature rise rate of 1.5 DEG C/min, and carry out quenching after being incubated 12 hours at such a temperature.The silica tube filling sample through quenching directly is put into annealing furnace and is annealed, and annealing temperature is 400 DEG C, is incubated 5 days at such a temperature.Finally the Tellurobismuthite block grind into powder obtained is prepared into compact block by discharge plasma sintering (SPS).Sintering temperature is between 400 DEG C to 450 DEG C, and sintering pressure is 50Mpa, and at this temperature and pressure heat-insulation pressure keeping 10min.Thermoelectricity capability is measured sample parallel after sintering and is characterized respectively perpendicular to sintering pressure direction.Data presentation comparatively takes tropism by force because material has, there is lower thermal conductance being parallel to pressure direction, thus make material have good thermoelectricity capability in this direction, having maximum ZT value at 400K is 1.1, when 550K, ZT value is only about 0.78, and comparatively significantly decline during 400K (as Fig. 2).
Embodiment 1:
According to chemical formula Cu 0.005bi 0.3sb 1.695te 3take high-purity element simple substance and load silica tube, in the glove box being full of argon inert atmosphere, adopt plasma gun to encapsulate, packaged silica tube is placed in vertical melting furnace and carries out melting, be raised to 1100 DEG C with the temperature rise rate of 1.5 DEG C/min, and carry out quenching after being incubated 12 hours at such a temperature.The silica tube filling sample through quenching directly is put into annealing furnace and is annealed, and annealing temperature is 400 DEG C, is incubated 5 days at such a temperature.Finally the Tellurobismuthite block grind into powder obtained is prepared into compact block by discharge plasma sintering (SPS).Sintering temperature is between 400 DEG C to 450 DEG C, and sintering pressure is 50Mpa, and at this temperature and pressure heat-insulation pressure keeping 10min.Thermoelectricity capability test shows that this material has better thermoelectricity capability being parallel to sintering pressure direction, and the specific conductivity of this material is compared to Bi 0.3sb 1.7te 3had and significantly promoted, lattice thermal conductance but significantly reduces, and this makes material C u 0.005bi 0.3sb 1.695te 3material thermoelectric figure of merit can reach 1.24 when 500K, still 1.2 are maintained when 550K, in Tellurobismuthite power generating device operating temperature range, (350K ~ 550K) average ZT can reach 1.2, can meet the service requirements (as Fig. 3) of Tellurobismuthite power generating device.
Embodiment 2:
According to chemical formula Cu 0.01bi 0.3sb 1.69te 3take high-purity element simple substance and load silica tube, in the glove box being full of argon inert atmosphere, adopt plasma gun to encapsulate, packaged silica tube is placed in vertical melting furnace and carries out melting, be raised to 1100 DEG C with the temperature rise rate of 1.5 DEG C/min, and carry out quenching after being incubated 12 hours at such a temperature.The silica tube filling sample through quenching directly is put into annealing furnace and is annealed, and annealing temperature is 400 DEG C, is incubated 5 days at such a temperature.Finally the Tellurobismuthite block grind into powder obtained is prepared into compact block by discharge plasma sintering (SPS).Sintering temperature is between 400 DEG C to 450 DEG C, and sintering pressure is 50Mpa, and at this temperature and pressure heat-insulation pressure keeping 10min.Thermoelectricity capability test shows, the thermoelectric figure of merit of this material reaches 1.05 when 500K, causes performance will lower than Cu due to the too high off-target carrier concentration of carrier concentration 0.005bi 0.3sb 1.695te 3(as Fig. 4).

Claims (8)

1. in, warm area has a Tellurobismuthite material for excellent heat electrical property, it is characterized in that, the composition general formula of described Tellurobismuthite material is Cu xbi 0.3sb 1.7-xte 3, wherein 0.005≤x≤0.02.
2. Tellurobismuthite material according to claim 1, is characterized in that, described Tellurobismuthite material is P type, is better than the thermoelectricity capability perpendicular to sintering pressure direction at the thermoelectricity capability being parallel to sintering pressure direction.
3. Tellurobismuthite material according to claim 1 and 2, is characterized in that, when 550K, described Tellurobismuthite material is being parallel to the thermoelectric figure of merit in sintering pressure direction between 1.0-1.3.
4. the preparation method of arbitrary described Tellurobismuthite material in claim 1-3, is characterized in that, comprising:
1) stoichiometrically take the simple substance of described Tellurobismuthite material component, encapsulate in a vacuum or inert atmosphere after mixing;
2) by the above-mentioned simple substance of encapsulation first melting treatment at 1000-1150 DEG C, then quenching and 350-450 DEG C of anneal, again the material that above-mentioned simple substance is formed through melting, anneal is ground to form powder, 400-450 DEG C, pressure sintering under 50-65MPa, obtain described Tellurobismuthite material.
5. preparation method according to claim 4, is characterized in that, described encapsulation adopts plasma or flame gun packaged type to be enclosed in silica tube by above-mentioned simple substance.
6. the preparation method according to claim 4 or 5, is characterized in that, melting treatment 10-14 hour at 1000-1150 DEG C, and temperature rise rate is 1-3 DEG C/min.
7., according to described preparation method arbitrary in claim 4-6, it is characterized in that, at 350-450 DEG C of anneal 3-5 days.
8., according to described preparation method arbitrary in claim 4-7, it is characterized in that, described pressure sintering is discharge plasma sintering, and the time of discharge plasma sintering is 8-12 minute, and temperature rise rate is 30-50 DEG C/min.
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CN112397634A (en) * 2020-11-16 2021-02-23 昆明理工大学 Method for improving performance of Bi-Sb-Te-based thermoelectric material
CN112694070A (en) * 2019-10-23 2021-04-23 中国科学院宁波材料技术与工程研究所 Composite thermoelectric material and preparation method thereof
CN113004045A (en) * 2019-12-18 2021-06-22 中国科学院上海硅酸盐研究所 High-content heavy element doped beta-FeSi2Base thermoelectric material and preparation method thereof
CN114249304A (en) * 2020-09-25 2022-03-29 中国科学院大连化学物理研究所 High-performance BiTe-based composite thermoelectric material and preparation method thereof
CN114408872A (en) * 2021-11-30 2022-04-29 慈溪市香格电器有限公司 Preparation method of bismuth telluride refrigeration material and application of bismuth telluride refrigeration material in water ion generator
CN115216846A (en) * 2022-05-26 2022-10-21 杭州大和热磁电子有限公司 P-type bismuth telluride alloy material, preparation method and application thereof
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CN106986315A (en) * 2016-01-21 2017-07-28 中国科学院上海硅酸盐研究所 A kind of p-type bismuth telluride thermoelectric material and preparation method suitable for low-temperature electricity-generating
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CN112694070A (en) * 2019-10-23 2021-04-23 中国科学院宁波材料技术与工程研究所 Composite thermoelectric material and preparation method thereof
CN113004045A (en) * 2019-12-18 2021-06-22 中国科学院上海硅酸盐研究所 High-content heavy element doped beta-FeSi2Base thermoelectric material and preparation method thereof
CN114249304A (en) * 2020-09-25 2022-03-29 中国科学院大连化学物理研究所 High-performance BiTe-based composite thermoelectric material and preparation method thereof
CN112397634A (en) * 2020-11-16 2021-02-23 昆明理工大学 Method for improving performance of Bi-Sb-Te-based thermoelectric material
CN112397634B (en) * 2020-11-16 2023-02-28 昆明理工大学 Method for improving performance of Bi-Sb-Te-based thermoelectric material
CN114408872A (en) * 2021-11-30 2022-04-29 慈溪市香格电器有限公司 Preparation method of bismuth telluride refrigeration material and application of bismuth telluride refrigeration material in water ion generator
CN115216846A (en) * 2022-05-26 2022-10-21 杭州大和热磁电子有限公司 P-type bismuth telluride alloy material, preparation method and application thereof
CN115216846B (en) * 2022-05-26 2023-11-24 杭州大和热磁电子有限公司 P-type bismuth telluride alloy material, preparation method and application thereof
CN116693292A (en) * 2023-06-06 2023-09-05 西安交通大学 p-type Bi 2 Te 3 Method for preparing base thermoelectric material

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