CN115196965B - N-type bismuth telluride thermoelectric material and preparation method thereof - Google Patents
N-type bismuth telluride thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN115196965B CN115196965B CN202210879540.6A CN202210879540A CN115196965B CN 115196965 B CN115196965 B CN 115196965B CN 202210879540 A CN202210879540 A CN 202210879540A CN 115196965 B CN115196965 B CN 115196965B
- Authority
- CN
- China
- Prior art keywords
- sintering
- ball milling
- bismuth telluride
- thermoelectric material
- type bismuth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/62615—High energy or reactive ball milling
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses an n-type bismuth telluride thermoelectric material and a preparation method thereof, wherein the chemical formula of the n-type bismuth telluride thermoelectric material is Bi 2 Te 3‑x Se x +y％SbI 3 Wherein x is<0.5，0＜y<0.3. The preparation method comprises the following steps: (1) Ball milling mechanical alloying is carried out on each component material according to the stoichiometric ratio of the n-type bismuth telluride thermoelectric material; and (2) carrying out step-by-step hot-pressed sintering on the ball-milled material. The invention is realized by doping SbI 3 And carrying out mechanical ball milling alloying for a long time to obtain stable and moderate carrier concentration, wherein the mechanical strength and the thermoelectric performance of the n-type bismuth telluride thermoelectric material obtained through reducing sintering meet the preparation requirements of miniature thermoelectric refrigerating devices.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to an n-type bismuth telluride thermoelectric material and a preparation method thereof.
Background
The thermoelectric material is a green environment-friendly energy conversion material capable of realizing direct conversion between heat energy and electric energy, and can rapidly refrigerate by utilizing the Peltier effect, thereby being capable of providing low-temperature environments with different temperature requirements for the fields of medical devices, low-temperature instruments, scientific research cameras, THz communication technology, infrared detection and the like. The refrigerating efficiency of the thermoelectric material is mainly achieved by a dimensionless thermoelectric figure of merit zt=s 2 Sigma T/kappa, where S is the Seebeck coefficient (V.K -1 ) Sigma is the conductivity (S.m -1 ) Kappa is the thermal conductivity (W.m -1 ·K -1 ) T is Kelvin temperature (K). Bismuth telluride is the only thermoelectric material currently commercialized, and researchers developed p-Bi in the last 60 th century 2-x Sb x Te 3 And n-Bi 2 Te 3-x Se x Formulation, on the basis of which it is possible to obtainA commercial thermoelectric material with p-type zt=0.8-1.2 and n-type zt=0.8-1.1 is obtained. Se content of n-type bismuth telluride in commercial formulations for enhanced electron concentration>10%, the forbidden bandwidth of the material is improved, and the temperature range with the optimal performance is shifted to high temperature. At present, bismuth telluride thermoelectric materials for low-temperature efficient refrigeration and temperature control are quite rare, and the development of the bismuth telluride thermoelectric materials with high performance at room temperature and below has important scientific and industrial significance. On the other hand, the development of miniaturized devices brings higher requirements on the mechanical properties of materials, the common zone-melting crystal bar cannot meet the practical requirements, and new formulas and processes are required to be developed to synthesize the high-strength and high-efficiency thermoelectric materials.
The development of high-performance bismuth telluride thermoelectric materials below room temperature requires on the one hand to reduce the forbidden bandwidth of the material and on the other hand to properly reduce the carrier concentration of the material. According to ACS appl. Mater. Interfaces 2020,12,31619-31627, the n-type bismuth telluride carrier concentration is very sensitive to the synthesis process, while there is Bi providing holes Te Inversion defect, and V providing electrons Te Vacancies, i.e. donor-like effects. In the smelting ingot casting process, inversion defects are dominant, the p-type performance is displayed, and the inversion defects are restrained by high-doped Se, so that the conversion of the performance p-n is realized; smelting and ball milling nanocrystallization process to generate high-concentration dislocation so as to lead the donor-like effect to be dominant, thus Bi 2-x Sb x Te 3 Can obtain n-type performance, as disclosed in patent CN113421959A as Se-free n-type Bi 2-x Sb x Te 3 The thermoelectric material has high thermoelectric performance near room temperature. Other bismuth telluride thermoelectric material patents have focused on the development of new methods such as: CN106571422a discloses a method for preparing high-performance n-type bismuth telluride thermoelectric material by zone-melting monocrystal method by adding small amount of Sb based on commercial formula; based on a commercial formula, the patents CN112201743A and CN1039286004A utilize self-propagating reaction and combine conventional annealing, plasma spark sintering and hot forging treatment to obtain an n-type bismuth telluride thermoelectric material; patent CN113328031A discloses a method for rapidly preparing a tellurium without cutting by utilizing the modes of accelerating falling of molten liquid drops, rapid cooling, directional solidification and lamellar accumulation on the basis of commercial formulaBismuth thermoelectric material; patent CN110002412a discloses a bismuth telluride thermoelectric material with high texture and thermal strength obtained by hot extrusion of a molten ingot on the basis of a commercial formulation.
Disclosure of Invention
Aiming at the problem of wide band gap of the current n-type multi-Se and Sb bismuth telluride thermoelectric material, the invention adopts the method of doping SbI 3 The carrier concentration is regulated, meanwhile, the Se content is reduced, and the narrow band gap n-type bismuth telluride thermoelectric material with less Se and Sb and the preparation method thereof are provided, so that the thermoelectric material with high thermoelectric performance and bending strength near 300K can be obtained, and the preparation requirements of low-temperature high-strength high-efficiency thermoelectric refrigerating devices are met.
In one aspect of the present invention, an n-type bismuth telluride thermoelectric material having a chemical formula Bi is provided 2 Te 3-x Se x +y％SbI 3 Wherein x is<0.5，0＜y<0.3。
In the technical scheme of the invention, bi 2 Te 3-x Se x +y％SbI 3 Wherein y% is mass percent, which means SbI 3 Is Bi by mass 2 Te 3-x Se x Y% of the mass.
Preferably, x=0.3.
Preferably, 0.03.ltoreq.y.ltoreq.0.07.
In certain embodiments, the n-type bismuth telluride thermoelectric material has the formula Bi 2 Te 2.7 Se 0.3 +0.03％SbI 3 、Bi 2 Te 2.7 Se 0.3 +0.06％SbI 3 Or Bi 2 Te 2.7 Se 0.3 +0.07％SbI 3 。
In another aspect of the present invention, there is provided a method for preparing an n-type bismuth telluride thermoelectric material, comprising the steps of:
(1) Ball milling mechanical alloying is carried out on each component material according to the stoichiometric ratio of the n-type bismuth telluride thermoelectric material;
(2) Step-by-step hot-pressing sintering is carried out on the ball-milled material;
wherein the chemical formula of the n-type bismuth telluride thermoelectric material is Bi 2 Te 3-x Se x +y％SbI 3 Wherein x is<0.5，0＜y<0.3。
As a preferred embodiment, the component materials are high-purity raw materials.
As a preferred embodiment, the ball milling is performed under a protective atmosphere;
preferably, the rotation speed of the ball milling is 800-1700 r/min, and the time of the ball milling is 3-10 hours;
preferably, the ball milling is batch ball milling, and the ratio of the ball milling time to the rest time of the batch ball milling is 1-10: 2, wherein the single ball milling time is 5-30 minutes, and the accumulated ball milling time is not shorter than 3 hours;
preferably, the ball-milled medium is 3mm in diameter: 5mm:8mm:10mm: the number ratio of 15mm is 1-15: 1 to 10:0 to 5:1 to 4: and (3) proportioning the materials.
As a preferred embodiment, the step hot press sintering comprises two sintering.
As a preferred embodiment, the temperature of the first sintering of the two sintering is 350-550 ℃ and the pressure is 30-80 MPa;
preferably, the temperature of the first sintering of the two sintering is 450 ℃ and the pressure is 40-50 MPa.
As a preferable embodiment, the temperature of the second sintering in the two sintering is 450-550 ℃ and the pressure is 30-80 MPa;
preferably, the temperature of the second sintering in the two sintering is 500-550 ℃ and the pressure is 40-50 MPa.
As a preferable implementation mode, the step-by-step hot-press sintering is reducing hot-press sintering performed step by step, and the reducing hot-press sintering is adopted to flatten the product of the first sintering, so that the orientation degree of the in-layer direction is improved;
in some specific embodiments, the diameter-variable hot-press sintering is realized by using different hot-press dies, and when the conventional cylindrical hot-press die is used for sintering, the diameter of the hot-press die used for the second sintering is larger than that of the first sintering, preferably 1.5-2 times of that of the first sintering, and the cross section area of the former is 2.25-4 times of that of the latter; in some examples, the hot press die for the first sintering has a diameter of 10 to 25mm.
According to the technical scheme disclosed by the application, a person skilled in the art has an incentive to adjust the carrier concentration by selecting the values of x and y, adjusting the ball milling ball size, the number of ball milling media with different sizes and the ball milling time and doping a small amount of Sb at the Bi position according to the actual production requirement so as to achieve the ideal technical effect.
The technical scheme has the following advantages or beneficial effects:
the invention provides an n-type bismuth telluride thermoelectric material with a narrow forbidden band width by adopting a ball milling process and a step hot-pressing sintering process, and the optimal performance temperature interval is near room temperature, thereby being beneficial to developing low-temperature thermoelectric refrigeration devices. In addition, the ball milling process is favorable for improving the overall uniformity and mechanical property of the material and is favorable for developing a low-temperature micro refrigeration device. In addition, ball milling generally enhances the donor-like effect of bismuth telluride materials, thereby increasing the carrier concentration, and therefore, the invention is realized by doping SbI 3 And mechanical ball milling alloying for a long time, and stable and moderate carrier concentration can be obtained.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of the mechanically alloyed powder of examples 1-3 of the invention.
Fig. 2 is a graph showing the results of conductivity testing of the n-type bismuth telluride thermoelectric materials in examples 1-3 of the present invention.
Fig. 3 is a graph showing the seebeck coefficient test results of the n-type bismuth telluride thermoelectric material in examples 1 to 3 of the present invention.
Fig. 4 is a graph showing the results of thermal conductivity testing of the n-type bismuth telluride thermoelectric materials in examples 1-3 of the present invention.
Fig. 5 is a graph of the results of thermoelectric figure of merit zT performance tests for the n-type bismuth telluride thermoelectric materials of examples 1-3 of the present invention.
Fig. 6 is a graph showing the results of testing the bending resistance of the n-type bismuth telluride thermoelectric materials according to examples 1-3 of the present invention.
FIG. 7 is a graph showing the results of conductivity testing of thermoelectric materials in comparative examples 1 to 3 according to the present invention.
FIG. 8 is a graph showing the Seebeck coefficient test results of thermoelectric materials in comparative examples 1 to 3 of the present invention.
FIG. 9 is a graph showing the results of thermal conductivity testing of thermoelectric materials in comparative examples 1 to 3 of the present invention.
FIG. 10 is a graph showing the results of the thermoelectric figure of merit zT performance test of the thermoelectric materials of comparative examples 1 to 3 of the present invention.
Detailed Description
The invention provides an n-type bismuth telluride thermoelectric material and a preparation method thereof, and aims to more specifically and clearly describe the purpose, technical scheme and effect of the invention, and the following detailed description of the invention is to be understood that the following embodiments are only some embodiments of the invention, but not all embodiments. Accordingly, the examples of the present invention provided below are only for the present invention and are not intended to limit the present invention.
In the following examples, the electrical property test equipment is Japanese ZEM-3, and the thermal diffusivity D test equipment is German relaxation-resistant laser thermal conductivity meter LFA-450; thermal conductivity is through κ=c p The density rho is obtained by calculating the Drho and the density rho is obtained by testing by an Archimedes method, and the specific heat C p Calculated by a Du Long-Peltier formula.
Example 1
According to chemical formula Bi 2 Te 2.7 Se 0.3 +0.03wt％SbI 3 In the stoichiometric ratio of the high-purity simple substance Sb, te, bi, se and the compound SbI 3 Weighing; placing the weighed materials and 10 zirconia ball-milling beads with the diameter of 3mm, 5 zirconia ball-milling beads with the diameter of 5mm and 2 zirconia ball-milling beads with the diameter of 10mm into a 70mL zirconia ball-milling tank, and filling Ar gas into the ball-milling tank and sealing; intermittent ball milling is carried out at a rotating speed of 1200r/min, and the ball milling/rest time ratio is 1:1, the single ball milling time is 10min, and the accumulated ball milling time is 6h; placing the obtained high-purity mechanical alloying powder into a cylindrical hot-pressing graphite mold with the diameter of 10mm, vacuumizing to below 10Pa, heating to 450 ℃ at the heating rate of 50 ℃/min, and then pressurizing to 50MPa for primary hot-pressing sintering, wherein the sintering time is 20min; cooling to room temperature after sintering for 15 min; placing the primary hot pressed sintered sample in a straight lineAnd (3) performing secondary hot-pressing sintering in a cylindrical hot-pressing graphite die with the diameter of 20mm, wherein the sintering temperature is 550 ℃, the sintering pressure is 50MPa, the sintering time is 20min, and the temperature rise and the vacuum degree are the same as those of the primary sintering.
Example 2
According to chemical formula Bi 2 Te 2.7 Se 0.3 +0.05wt％SbI 3 Stoichiometric ratio of Te, bi and SbI 3 Weighing, namely placing 10 weighed materials and zirconia ball-milling beads with the diameter of 3mm, 5 zirconia ball-milling beads with the diameter of 5mm and 2 zirconia ball-milling beads with the diameter of 10mm into a 70mL zirconia ball-milling tank, and filling Ar gas into the ball-milling tank and sealing; intermittent ball milling is carried out at a rotating speed of 1200r/min, and the ball milling/rest time ratio is 1:1, the single ball milling time is 10min, and the accumulated ball milling time is 6h; placing the obtained high-purity mechanical alloying powder into a cylindrical hot-pressing graphite mold with the diameter of 10mm, vacuumizing to below 10Pa, heating to 450 ℃ at the heating rate of 50 ℃/min, and then pressurizing to 50MPa for primary hot-pressing sintering, wherein the sintering time is 20min; cooling to room temperature after sintering for 15 min; and placing the primary hot-pressed sintering sample into a cylindrical hot-pressed graphite die with the diameter of 20mm for secondary hot-pressed sintering, wherein the sintering temperature is 550 ℃, the sintering pressure is 50MPa, the sintering time is 20min, and the temperature rising speed and the vacuum degree are the same as those of the primary sintering.
Example 3
According to chemical formula Bi 2 Te 2.7 Se 0.3 +0.07wt％SbI 3 Stoichiometric ratio of the high-purity simple substances Sb, te, bi and compound SbI 3 Weighing; placing the weighed materials and 10 zirconia ball-milling beads with the diameter of 3mm, 5 zirconia ball-milling beads with the diameter of 5mm and 2 zirconia ball-milling beads with the diameter of 10mm into a 70mL zirconia ball-milling tank, and filling Ar gas into the ball-milling tank and sealing; intermittent ball milling is carried out at a rotating speed of 1200r/min, and the ball milling/rest time ratio is 1:1, the single ball milling time is 10min, and the accumulated ball milling time is 6h; placing the obtained high-purity mechanical alloying powder into a cylindrical hot-pressing graphite mold with the diameter of 10mm, vacuumizing to below 10Pa, heating to 450 ℃ at the heating rate of 50 ℃/min, and then pressurizing to 50 DEG CCarrying out primary hot-pressing sintering under the pressure of MPa, wherein the sintering time is 20min; cooling to room temperature after sintering for 15 min; and placing the primary hot-pressed sintering sample into a cylindrical hot-pressed graphite die with the diameter of 20mm for secondary hot-pressed sintering, wherein the sintering temperature is 550 ℃, the sintering pressure is 50MPa, the sintering time is 20min, and the temperature rising speed and the vacuum degree are the same as those of the primary sintering.
FIG. 1 is a powder X-ray diffraction pattern of the mechanically alloyed powder prepared in examples 1-3 of the invention, from which it can be seen that the high purity target product was obtained by a ball milling reaction for 6 hours.
Comparative example 1
The thermoelectric material in this comparative example was Bi 2 Te 2.7 Se 0.3 The preparation method is prepared through the process flows of ball milling and thermal deformation, and comprises the following specific preparation processes:
according to chemical formula Bi 2 Te 2.7 Se 0.3 Weighing high-purity simple substances Te, bi and Se according to the stoichiometric ratio, placing 10 weighed materials and zirconia ball-milling beads with the diameter of 3mm, 5 zirconia ball-milling beads with the diameter of 5mm and 2 zirconia ball-milling beads with the diameter of 10mm into a 70mL zirconia ball-milling tank, and filling Ar gas into the ball-milling tank and sealing; intermittent ball milling is carried out at a rotating speed of 1200r/min, and the ball milling/rest time ratio is 1:1, the single ball milling time is 10min, and the accumulated ball milling time is 6h; placing the submerged high-purity mechanical alloying powder in a cylindrical hot-pressing graphite mold with the diameter of 10mm, vacuumizing to below 10Pa, heating to 450 ℃ at the heating rate of 50 ℃/min, pressurizing to 50MPa, performing primary hot-pressing sintering for 20min, and cooling to room temperature after sintering is finished for 15 min; and placing the primary hot-pressed sintering sample into a cylindrical hot-pressed graphite die with the diameter of 20mm for secondary hot-pressed sintering, wherein the sintering temperature is 550 ℃, the sintering pressure is 50MPa, the sintering time is 20min, and the temperature rising rate and the vacuum degree are the same as those of the primary sintering.
Comparative example 2
The thermoelectric material in this comparative example was Bi 2 Te 2.7 Se 0.3 +0.05wt％SbI 3 The preparation method comprises the following steps of smelting cast ingots, ball milling and thermal deformation:
according to chemical formula Bi 2 Te 2.7 Se 0.3 +0.05wt％SbI 3 In the stoichiometric ratio of the high-purity simple substance Sb, te, bi, se and the compound SbI 3 Weighing, placing the weighed materials into a round bottom quartz tube, and vacuumizing to 10 -4 Sealing Pa; placing a quartz tube filled with materials in a muffle furnace, heating to 800 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, and naturally cooling to room temperature; grinding the obtained smelting ingot into powder by hand, placing 10 zirconia ball-milling beads with the same diameter of 3mm, 5 zirconia ball-milling beads with the diameter of 5mm and 2 zirconia ball-milling beads with the diameter of 10mm into a 70mL zirconia ball-milling tank, and filling Ar gas into the ball-milling tank and sealing; intermittent ball milling is carried out at a rotating speed of 1200r/min, and the ball milling/rest time ratio is 1:1, the single ball milling time is 10min, and the accumulated ball milling time is 30min; placing the obtained high-purity mechanical alloying powder into a cylindrical hot-pressing graphite mold with the diameter of 10mm, vacuumizing to below 10Pa, heating to 450 ℃ at the heating rate of 50 ℃/min, pressurizing to 50MPa, performing hot-pressing sintering for 20min, and cooling to room temperature for 15min after sintering is finished; and placing the primary hot-pressed sintering sample into a cylindrical hot-pressed graphite die with the diameter of 20mm for secondary hot-pressed sintering, wherein the sintering temperature is 550 ℃, the sintering pressure is 50MPa, the sintering time is 20min, and the temperature rising speed and the vacuum degree are the same as those of the primary sintering.
Comparative example 3
The thermoelectric material prepared in this comparative example was Bi 2 Te 2.7 Se 0.3 (SbI 3 ) 0.003 The single crystal is prepared by the following steps:
according to chemical formula Bi 2 Te 2.7 Se 0.3 (SbI 3 ) 0.003 Stoichiometric ratio of Te, bi, se and SbI 3 Weighing, placing into a quartz taper tube with a taper angle of 60 degrees, and vacuumizing to 10 degrees -4 Sealing Pa; placing a quartz tube filled with raw materials into a rocking furnace, heating to 800 ℃ for horizontal rocking sintering for 2 hours, vertically placing the rocking furnace after sintering, and naturally cooling to room temperature; then the quartz tube is taken out and placed in a vertical zone melting furnace, and heated to be molten at 20 ℃/minSpot, heat-insulating for 1h, then zone-melting and growing crystal at a speed of 5mm/h, cutting after the crystal growth is finished [100 ]]The performance test was performed on the directional samples.
FIGS. 2 and 7 are graphs showing the results of conductivity tests of thermoelectric materials of examples 1 to 3 and comparative examples 1 to 3, respectively, according to the present invention, from which it can be seen that ball milling and SbI 3 Doping is critical to the regulation of conductivity, is indispensable, and is independently doped with SbI 3 Or ball milling alone does not give suitable conductivity.
FIGS. 3 and 8 are graphs showing Seebeck coefficient test results of thermoelectric materials of examples 1 to 3 and comparative examples 1 to 3, respectively, from which it can be seen that ball milling and SbI 3 Under the combined action of doping, the Seebeck coefficient can be adjusted to a proper range.
FIGS. 4 and 9 are graphs showing the results of thermal conductivity tests of thermoelectric materials of examples 1 to 3 and comparative examples 1 to 3, respectively, according to the present invention, from which it can be seen that ball milling and SbI 3 The doping can effectively reduce the conductivity while optimizing the conductivity and the Seebeck coefficient, and is beneficial to the improvement of the thermoelectric performance of the material.
FIGS. 5 and 10 are graphs showing the results of the thermoelectric figure of merit zT performance tests of thermoelectric materials of examples 1 to 3 and comparative examples 1 to 3, respectively, in which ball milling and SbI are conducted in the present invention 3 The doping combined treatment process can obtain a high thermoelectric figure of merit, and neither doping nor ball milling alone can achieve this goal.
Fig. 6 is a graph showing the results of the bending resistance test of the thermoelectric materials in examples 1 to 3 of the present invention, and it can be seen from the graph that the n-type bismuth telluride thermoelectric material prepared by the present invention has good mechanical properties and is easy to process into micro devices.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (9)
1. An n-type bismuth telluride thermoelectric material, characterized in thatThe chemical formula of the n-type bismuth telluride thermoelectric material is Bi 2 Te 3- x Se x +y％SbI 3 Wherein x is<0.5，0＜y<0.3；
The preparation method of the n-type bismuth telluride thermoelectric material comprises the following steps:
(1) Ball milling mechanical alloying is carried out on each component material according to the stoichiometric ratio of the n-type bismuth telluride thermoelectric material;
(2) Step-by-step hot-pressing sintering is carried out on the ball-milled material;
the rotation speed of the ball milling is 800-1700 r/min, and the ball milling time is 3-10 hours; the ball milling is intermittent ball milling, and the ratio of the ball milling time to the rest time of the intermittent ball milling is 1-10: 2, wherein the single ball milling time is 5-30 minutes, and the accumulated ball milling time is not shorter than 3 hours;
the step-by-step hot-pressed sintering comprises two times of sintering; the temperature of the first sintering in the two sintering is 350-550 ℃ and the pressure is 30-80 MPa; the temperature of the second sintering in the two sintering is 450-550 ℃ and the pressure is 30-80 MPa.
2. The n-type bismuth telluride thermoelectric material of claim 1 wherein x = 0.3;
preferably, 0.03.ltoreq.y.ltoreq.0.07.
3. The preparation method of the n-type bismuth telluride thermoelectric material is characterized by comprising the following steps of:
(1) Ball milling mechanical alloying is carried out on each component material according to the stoichiometric ratio of the n-type bismuth telluride thermoelectric material;
(2) Step-by-step hot-pressing sintering is carried out on the ball-milled material;
the rotation speed of the ball milling is 800-1700 r/min, and the ball milling time is 3-10 hours; the ball milling is intermittent ball milling, and the ratio of the ball milling time to the rest time of the intermittent ball milling is 1-10: 2, wherein the single ball milling time is 5-30 minutes, and the accumulated ball milling time is not shorter than 3 hours;
the step-by-step hot-pressed sintering comprises two times of sintering; the temperature of the first sintering in the two sintering is 350-550 ℃ and the pressure is 30-80 MPa; the temperature of the second sintering in the two sintering is 450-550 ℃ and the pressure is 30-80 MPa;
wherein the chemical formula of the n-type bismuth telluride thermoelectric material is Bi 2 Te 3-x Se x +y％SbI 3 Wherein x is<0.5，0＜y<0.3。
4. A method according to claim 3, wherein the component materials are high purity materials.
5. The method of claim 3, wherein the ball milling is performed under a protective atmosphere.
6. A method according to claim 3, wherein the ball-milled medium is 3mm in diameter: 5mm:8mm:10mm: the number ratio of 15mm is 1-15: 1 to 10:0 to 5:1 to 4: and (3) proportioning the materials.
7. A method according to claim 3, wherein the first sintering of the two sinters is performed at a temperature of 450 ℃ and a pressure of 40 to 50MPa.
8. A method according to claim 3, wherein the second sintering of the two sintering is performed at a temperature of 500 to 550 ℃ and a pressure of 40 to 50MPa.
9. The method according to claim 3, wherein the step-by-step hot-press sintering is a reducing hot-press sintering performed in steps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210879540.6A CN115196965B (en) | 2022-07-25 | 2022-07-25 | N-type bismuth telluride thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210879540.6A CN115196965B (en) | 2022-07-25 | 2022-07-25 | N-type bismuth telluride thermoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115196965A CN115196965A (en) | 2022-10-18 |
| CN115196965B true CN115196965B (en) | 2023-07-25 |
Family
ID=83583757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210879540.6A Active CN115196965B (en) | 2022-07-25 | 2022-07-25 | N-type bismuth telluride thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115196965B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200933940A (en) * | 2007-12-28 | 2009-08-01 | Basf Se | Extrusion process for preparing improved thermoelectric materials |
| CN102257648B (en) * | 2008-12-19 | 2018-04-27 | 开利公司 | The thermoelectric material of the shear force detection of body processing |
| KR101528589B1 (en) * | 2013-06-10 | 2015-06-16 | 연세대학교 산학협력단 | Method of manufacturing thermoelectric material and thermoelectric material prepared by the method and thermoelectric generator |
| CN106571422B (en) * | 2016-11-09 | 2022-03-22 | 苏州科技大学 | Bismuth telluride-based N-type thermoelectric material and preparation method thereof |
| CN111477736B (en) * | 2019-01-24 | 2022-09-16 | 中国科学院宁波材料技术与工程研究所 | Bismuth telluride-based thermoelectric material and preparation method thereof |
| CN112531097B (en) * | 2020-11-13 | 2023-10-10 | 深圳热电新能源科技有限公司 | n-type bismuth telluride-based thermoelectric material and preparation method thereof |
| CN112500164B (en) * | 2020-12-14 | 2022-05-27 | 深圳先进电子材料国际创新研究院 | Bismuth telluride thermoelectric material and preparation method thereof |
| CN112670399B (en) * | 2021-01-13 | 2022-01-04 | 武汉理工大学 | Method for eliminating donor-like effect of bismuth telluride-based thermoelectric material |
| CN114713655A (en) * | 2022-04-07 | 2022-07-08 | 深圳先进电子材料国际创新研究院 | Preparation method and extrusion die of bismuth telluride-based thermoelectric material |
-
2022
- 2022-07-25 CN CN202210879540.6A patent/CN115196965B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115196965A (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110002412B (en) | Preparation method of preferred orientation n-type bismuth telluride based polycrystalline bulk thermoelectric material | |
| CN109616568B (en) | N-type antimony trimagneside alloy thermoelectric material with high mobility and preparation method thereof | |
| CN111477736B (en) | Bismuth telluride-based thermoelectric material and preparation method thereof | |
| CN104555950B (en) | 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 | |
| CN106571422B (en) | Bismuth telluride-based N-type thermoelectric material and preparation method thereof | |
| CN111848165B (en) | P-type bismuth telluride thermoelectric material and preparation method thereof | |
| CN113421959B (en) | N-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof | |
| CN110257667B (en) | N-type antimony trimagneside alloy thermoelectric material and preparation thereof | |
| CN106986315B (en) | A kind of p-type bismuth telluride thermoelectric material and preparation method suitable for low-temperature electricity-generating | |
| CN108374198B (en) | A kind of monocrystalline Bi2Te3The preparation method of thermoelectric material | |
| CN108231991A (en) | A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat | |
| CN109671840B (en) | Antimony tellurium selenium matrix alloy construction method for thermoelectric material and antimony tellurium selenium matrix thermoelectric material | |
| CN101217178B (en) | A preparation method for antimonide molybdenum base thermoelectric material | |
| CN108735887B (en) | Antimony-doped high-performance GeTe-PbTe solid solution thermoelectric material and preparation method thereof | |
| CN115196965B (en) | N-type bismuth telluride thermoelectric material and preparation method thereof | |
| CN110760933B (en) | Preparation method of rare earth telluride based high-temperature thermoelectric material | |
| CN105990510A (en) | Copper-selenium based high performance thermoelectric material and preparation method of the same | |
| CN109022863B (en) | Ga-filled skutterudite thermoelectric material and preparation method thereof | |
| CN103290249A (en) | Method and apparatus for producing thermoelectric conversion material, and sputtering target production method | |
| CN106058032A (en) | Element semiconductor thermoelectric material with high thermoelectric performance and preparation method thereof | |
| CN101857929A (en) | Zinc antimony based porous p-type thermoelectric material and preparation method thereof | |
| CN112661122B (en) | Germanium telluride based thermoelectric material with high thermoelectric performance | |
| JP3929880B2 (en) | Thermoelectric material | |
| CN115216846B (en) | P-type bismuth telluride alloy material, preparation method and application thereof | |
| CN112002796A (en) | Rapid preparation of high-performance Bi easy to cut2Te3Method for producing thermoelectric material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |