CN114408874A - Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof - Google Patents

Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof Download PDF

Info

Publication number
CN114408874A
CN114408874A CN202210033342.8A CN202210033342A CN114408874A CN 114408874 A CN114408874 A CN 114408874A CN 202210033342 A CN202210033342 A CN 202210033342A CN 114408874 A CN114408874 A CN 114408874A
Authority
CN
China
Prior art keywords
entropy
thermoelectric material
sintering
bismuth telluride
simple substance
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.)
Granted
Application number
CN202210033342.8A
Other languages
Chinese (zh)
Other versions
CN114408874B (en
Inventor
何佳清
朱彬
王江舵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Thermoelectricity New Energy Technology Co ltd
Original Assignee
Shenzhen Thermoelectricity New Energy Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen Thermoelectricity New Energy Technology Co ltd filed Critical Shenzhen Thermoelectricity New Energy Technology Co ltd
Priority to CN202210033342.8A priority Critical patent/CN114408874B/en
Publication of CN114408874A publication Critical patent/CN114408874A/en
Application granted granted Critical
Publication of CN114408874B publication Critical patent/CN114408874B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • 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
    • C04B35/64—Burning or sintering processes
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention provides a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof, wherein the chemical formula of the bismuth telluride thermoelectric material is Bi2‑x‑zQzSbxTe3‑ySey(ii) a Wherein Q comprises any one or the combination of at least two of Ag, Cu or Cr; x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1. The bismuth telluride thermoelectric material of the invention is prepared into the high-performance room temperature thermoelectric material through entropy engineering, and on one hand, the doping of Q elementOn the other hand, due to the large amount of solid solution of various elements, the configuration entropy of the material is obviously increased, the material becomes more stable, a single-phase material is obtained, the increase of the configuration entropy obviously enhances the dissonance, and thus the lattice thermal conductivity is greatly reduced; as the electric and thermal transport characteristics are synchronously optimized, the thermoelectric performance of the bismuth telluride thermoelectric material is obviously improved.

Description

Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof
Technical Field
The invention belongs to the technical field of energy materials, relates to a thermoelectric material and a preparation method thereof, and particularly relates to a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof.
Background
The thermoelectric material is a new energy material capable of directly realizing the interconversion of heat energy and electric energy, and the mechanism is established on the three thermoelectric conversion effects of the seebeck effect, the peltier effect and the thomson effect. Over the past few decades, the research of thermoelectric materials has thus entered a new stage due to the increasing attention on energy problems. The thermoelectric refrigeration and power generation device can be manufactured by connecting two semiconductor thermoelectric materials of a P type and an N type in series. The thermoelectric device has the advantages of no pollution, no noise, no moving parts, no vibration and the like. The conversion efficiency of thermoelectric devices depends mainly on the dimensionless thermoelectric figure of merit of the material: ZT ═ α (α)2σ/κ) T, where α is the seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the thermodynamic temperature. Obviously, an ideal thermoelectric material should have high electrical performance and low thermal conductivity, but the ZT value is challenging to improve due to the interdependence of these physical parameters.
High performance thermoelectric devices require that the thermoelectric performance and the service temperature range of P-type and N-type materials match each other as much as possible. Bismuth telluride is a thermoelectric material with the best performance near room temperature and the widest commercial application at present. The ZT value of the existing P-type bismuth telluride alloy and N-type bismuth telluride alloy reaches about 1.4, but the performance of the existing P-type bismuth telluride alloy and N-type bismuth telluride alloy still cannot meet the increasingly vigorous market, and the commercial application of the existing P-type bismuth telluride alloy and N-type bismuth telluride alloy is severely limited.
CN112500164A discloses a bismuth telluride thermoelectric material and a preparation method thereof, wherein the preparation method comprises the following steps: step one, according to a chemical formula X of the N-type bismuth telluride materialw/Bi2Te2.7-wSe0.3Weighing Bi, Te and Se simple substance powder as raw materials, or according to the chemical formula X of the P-type bismuth telluride materialw/Bi0.5-wSb1.5Te3Weighing Bi, Sb and Te elementary substance powderIs taken as a raw material, X is a doping element, w is the stoichiometric ratio of the doping element X, and the range of w is more than or equal to 0 and less than or equal to 0.1; step two, uniformly mixing the raw materials, and then placing the mixture into a ball milling tank provided with a plasma generator for high-energy ball milling; and step three, transferring the powder in the tank body after ball milling to a sintering mold under inert gas for sintering, wherein the sintering is carried out twice, and cooling to obtain the bismuth telluride thermoelectric material. The invention combines the plasma ball milling and the spark plasma sintering technology for the first time to prepare the high-performance bismuth telluride material, and the method has the advantages of high speed, controllable powder components, low energy consumption and suitability for mass production.
CN110752285A discloses a manufacturing method for improving the performance of an N-type Bi-Sb-Te-Se-based thermoelectric material, which comprises the following steps: according to the formula Bi2-xSbxTe3-ySey+ zwt% of Te, weighing metal particles as raw materials according to the stoichiometric ratio, mixing and smelting to obtain a master alloy, wherein x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 3, and z is more than or equal to 0 and less than or equal to 30; the master alloy is put into a vacuum ball mill to be ball milled into nano-scale powder, and the nano-scale powder comprises Bi2-xSbxTe3-ySeyA multiphase material with Te; sintering the nanoscale powder into a bulk by means of a spark plasma sintering technique to obtain an N-type Bi-Sb-Te-Se-based thermoelectric material, wherein the sintering temperature in the spark plasma sintering technique is higher than the melting point of the Te phase and lower than Bi2-xSbxTe3-ySeyThe melting point of (2). According to the manufacturing method for improving the performance of the N-type Bi-Sb-Te-Se-based thermoelectric material, the mother alloy is ball-milled through a ball milling process, and the thermoelectric performance of the N-type Bi-Sb-Te-Se-based thermoelectric material is improved by sintering nanoscale powder obtained after ball milling through a liquid phase sintering technology.
At present, researchers have combined entropy engineering with thermoelectric materials and desired to develop high performance thermoelectric materials. The concept of "high-entropy alloy" was proposed in 2004, and Cantor et al prepared a single-phase multi-component alloy with stable configuration entropy for the first time, and thereafter, high-entropy engineering was widely studied in the field of alloys. Until 2015, entropy stable oxides (Mg)0.2Zn0.2Co0.2Cu0.2Zn0.2) After O is reported, the high entropy concept is stepped into the ceramic collarA domain. The method not only proves the driving force of entropy, but also opens up a new idea for the research of high-entropy non-metallic materials. High entropy systems typically have four large high entropy effects: thermodynamically high entropy effects; the diffusion effect is delayed in dynamics; the structure is lattice distortion effect; the effect is a cocktail in performance. By reasonable formula design, the high-entropy material with high strength, high hardness, huge dielectric constant, high-temperature oxidation resistance and low thermal conductivity can be obtained. Unlike high entropy alloys, high entropy ceramics are typically semiconductors or insulators with band gaps, which make them potentially functional materials. For example, a high entropy copper-based compound can be a good thermoelectric material due to its large seebeck coefficient and low thermal conductivity.
In summary, the invention provides a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof, wherein the chemical formula of the bismuth telluride thermoelectric material is Bi2-x-zQzSbxTe3-ySey(ii) a Wherein Q comprises any one or the combination of at least two of Ag, Cu or Cr; x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1. According to the bismuth telluride thermoelectric material, the high-performance room-temperature thermoelectric material is obtained through entropy engineering, on one hand, doping of Q element provides electrons and optimizes the electric conductivity, on the other hand, due to a large amount of solid solution of various elements, the configuration entropy of the material is obviously increased, on the contrary, the material becomes more stable, a single-phase material is obtained, the increase of the configuration entropy obviously enhances the non-harmonicity, and thus the lattice thermal conductivity is greatly reduced; because the electric and thermal transport characteristics are synchronously optimized, the thermoelectric performance of the bismuth telluride thermoelectric material is obviously improved; the preparation method provided by the invention is simple in process, only comprises smelting, grinding and sintering, and is convenient for large-scale popularization.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide bismuth telluride based on entropy engineeringThe thermoelectric material is characterized in that the chemical formula of the entropy engineering-based bismuth telluride thermoelectric material is as follows: bi2-x-zQzSbxTe3-ySey；
Wherein Q comprises any one or the combination of at least two of Ag, Cu or Cr; x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1.
According to the bismuth telluride thermoelectric material, the high-performance room-temperature thermoelectric material is obtained through entropy engineering, on one hand, doping of Q element provides electrons and optimizes the electric conductivity, on the other hand, due to a large amount of solid solution of various elements, the configuration entropy of the material is obviously increased, on the contrary, the material becomes more stable, a single-phase material is obtained, the increase of the configuration entropy obviously enhances the non-harmonicity, and thus the lattice thermal conductivity is greatly reduced; as the electric and thermal transport characteristics are synchronously optimized, the thermoelectric performance of the bismuth telluride thermoelectric material is obviously improved.
The bismuth telluride thermoelectric material based on entropy engineering obtains a high-performance room-temperature thermoelectric material through entropy engineering, and greatly reduces lattice thermal conductivity by increasing the entropy value on the basis of maintaining better electric transmission, so that the high-performance room-temperature thermoelectric material is obtained, and a new way is provided for refrigeration and power generation application of the thermoelectric material near room temperature.
Aiming at the problem that the performance of the traditional room temperature thermoelectric material bismuth telluride alloy is low, the stable high-entropy single-phase room temperature thermoelectric material is obtained by an entropy increasing method, so that the non-harmonicity is greatly increased, the lattice thermal conductivity is reduced, and meanwhile, the high-performance room temperature thermoelectric material is obtained by doping external atoms to optimize the carrier concentration.
It is to be noted that the chemical formula of the bismuth telluride thermoelectric material based on entropy engineering according to the present invention satisfies 0 < x < 2, such as 0.1, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.4, or 1.7, etc., but is not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
It is to be noted that the chemical formula of the bismuth telluride thermoelectric material based on entropy engineering according to the present invention, wherein y satisfies 0 < y < 3, such as 0.1, 0.5, 0.8, 0.9, 1, 1.3, 1.6, 1.7, 2, 2.2, 2.4, 2.5, 2.7 or 2.9, is not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
It is to be noted that the chemical formula of the bismuth telluride thermoelectric material based on entropy engineering according to the present invention, wherein z satisfies 0 < z ≦ 0.1, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1, etc., but is not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
The second purpose of the invention is to provide a preparation method of the bismuth telluride thermoelectric material based on entropy engineering, which comprises the following steps:
(1) according to the chemical formula Bi2-x-zQzSbxTe3-ySeyWeighing a Bi simple substance, a Q simple substance, a Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio; wherein, Q comprises any one or the combination of at least two of Ag, Cu or Cr, x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1; uniformly mixing the weighed raw materials, and sequentially smelting and cooling to obtain a master alloy;
(2) grinding the master alloy obtained in the step (1) to obtain sample powder;
(3) and (3) sintering the sample powder obtained in the step (2) to obtain the bismuth telluride thermoelectric material based on entropy engineering.
The preparation method only comprises smelting, grinding and sintering, and has the advantages of simple process, strong practicability, convenience for large-scale popularization and the like.
It is worth noting that the purity of each raw material in the preparation method of the invention is more than 99.99 wt%.
In the preferred embodiment of the present invention, in the step (1), the weighed raw materials are put into a quartz tube, sealed and mixed uniformly, put into a muffle furnace for melting, and cooled to obtain the master alloy.
As a preferable technical scheme of the invention, the vacuum degree of the sealed quartz tube is controlled to be (5-9) multiplied by 10- 4Pa, e.g. 5X 10-4Pa、5.5×10-4Pa、6×10-4Pa、6.5×10-4Pa、7×10-4Pa、7.5×10-4Pa、8×10- 4Pa、8.5×10-4Pa or 9X 10-4Pa, etc., but are not limited to the recited values, and other values not recited within the above numerical range are also applicable.
As a preferable embodiment of the present invention, the temperature increase rate of the melting in the step (1) is 2 to 5 ℃/min, for example, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.8 ℃/min, 4 ℃/min, 4.2 ℃/min, 4.7 ℃/min, or 5 ℃/min, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
It is worth mentioning that in the process of smelting the weighed raw materials to obtain the master alloy, if the temperature rise speed is too low and is lower than 2 ℃/min, the texture structure of the final material is coarse, and the performance of the thermoelectric material is affected; if the temperature rise rate is too high and is higher than 5 ℃/min, raw material particles are heated unevenly in the muffle furnace, so that the particles are not smelted sufficiently, and the obtained master alloy may contain impurity phases which can influence the performance of the thermoelectric material. The preparation method controls the temperature rise speed within the range of [2 ℃/min, 5 ℃/min ], can ensure that particles are fully smelted, and can avoid coarse structures.
Preferably, the temperature for the smelting in step (1) is 850-.
It is worth mentioning that in the process of smelting the weighed raw materials to obtain the master alloy, if the smelting temperature is too low and is lower than 850 ℃, the smelting of the raw material particles is insufficient, the obtained master alloy may contain impurity phases, and the impurity phases may affect the performance of the thermoelectric material; if the melting temperature is too high, above 1050 ℃, explosion may occur during melting of each raw material particle. The preparation method controls the smelting temperature within the range of 850 ℃ and 1050 ℃, so that raw material particles can be fully smelted, and the problem of explosion in the smelting process can be avoided.
Preferably, the holding time for the smelting in step (1) is 2-10h, such as 2h, 2.5h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the above range are also applicable.
It is worth mentioning that in the process of smelting each weighed raw material to obtain a master alloy, if the heat preservation time is too short and is shorter than 2 hours, insufficient smelting of particles can be caused, and the obtained master alloy may contain impurity phases which can affect the performance of the thermoelectric material; if the holding time is too long, longer than 10 hours, explosion may occur during the process of smelting the particles. The preparation method controls the heat preservation time of the smelting within the range of [2h, 10h ], so that the particles can be fully smelted, and the problem of explosion in the smelting process can be avoided.
In step (2), the master alloy obtained in step (1) is put into a milling pot and manually milled.
Preferably, the milling jar comprises an agate milling jar or a stainless steel milling jar.
In a preferred embodiment of the present invention, the polishing time in step (2) is 0.5 to 5 hours, for example, 0.5 hour, 0.55 hour, 0.6 hour, 0.64 hour, 0.72 hour, 0.77 hour, 0.8 hour, 0.86 hour, 0.93 hour, 0.99 hour, 1 hour, 2 hours, 2.5 hours, 3 hours, or 5 hours, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
It is worth noting that in the process of grinding the master alloy to obtain the sample powder, if the grinding time is too short, which is shorter than 0.5h, the particle size of the obtained sample powder is too large; if the grinding time is too long and longer than 5 hours, the possibility of redox generation of the master alloy is increased, and the obtained sample powder may be doped with a hetero-phase, which affects the performance of the thermoelectric material. The preparation method controls the grinding time within the range of [0.5h, 5h ], so that the mother alloy can be fully ground, and the impurity phase doped in the sample powder obtained by grinding can be avoided.
Preferably, the sample powder in step (2) has a particle size range of 300-400 μm, i.e. the sample powder after sieving has a particle size range of 300-400 μm, such as 300 μm, 310 μm, 320 μm, 325 μm, 338 μm, 350.9 μm, 364 μm, 370 μm, 380 μm, 390 μm or 400 μm, but not limited to the values listed, and other values not listed in the above range are also applicable.
It is to be noted that, in the process of grinding the master alloy to obtain the sample powder, the particle size range of the sample powder obtained by sieving is limited to [300 μm, 400 μm ], and the sample powder does not have metallic luster, so that whether the sample powder is within [300 μm, 400 μm ] can be roughly judged by observing whether the surface of the sample powder obtained after grinding has metallic luster.
As a preferable technical scheme of the invention, the sintering in the step (3) is spark plasma sintering or hot-pressing sintering.
As a preferred embodiment of the present invention, the sintering temperature in the step (3) is 400-480 ℃, for example, 400 ℃, 425 ℃, 450 ℃, 453 ℃, 455 ℃, 458 ℃, 460.2 ℃, 464 ℃, 470 ℃, 475 ℃, 478.6 ℃ or 480 ℃, but is not limited to the values listed above, and other values not listed above within the above range are also applicable.
It is worth to say that the preparation method of the invention controls the sintering temperature to be [400, 480 ℃), which not only can obtain compact products, avoid the influence on thermoelectric materials, but also can prevent explosion in the sintering process.
Preferably, the pressure of the sintering in step (3) is 40-60MPa, such as 40MPa, 43MPa, 45Pa, 46Pa, 49Pa, 50Pa, 52.5Pa, 55.3MPa, 55Pa, 57Pa, 58MPa, or 60MPa, but is not limited to the recited values, and other values not recited in the above range of values are equally applicable.
It is worth to be noted that, in the process of sintering the sample powder, if the sintering pressure is too low and is lower than 40MPa, the powder binding degree is not high, and the performance of the thermoelectric material is affected; if the sintering pressure is too high, above 60MPa, explosion may occur during sintering. The preparation method controls the sintering pressure to be 40MPa or 60MPa, can improve the powder bonding degree, and can avoid explosion in the sintering process.
Preferably, the sintering time in step (3) is 3-8min, such as 3min, 3.5min, 4min, 4.2min, 4.5min, 4.9min, 5min, 5.3min, 5.6min, 5.8min, 6min, 6.1min, 6.7min, 7min, 7.2min, 7.4min, 7.75min or 8min, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
It is worth to be noted that, in the process of sintering the sample powder, if the sintering time is too short and is shorter than 3min, the sintering is insufficient, and the performance of the thermoelectric material is affected; if the sintering time is too long, which is longer than 8min, the crystal grains will be too large, and the performance of the thermoelectric material will be reduced. The preparation method controls the sintering time within the range of [3min, 8min ], so that the powder can be fully sintered, and the performance of the thermoelectric material cannot be influenced by overlarge sintered grains.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) according to the chemical formula Bi2-x-zQzSbxTe3-ySeyWeighing a Bi simple substance, a Q simple substance, a Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio; wherein, Q comprises any one or the combination of at least two of Ag, Cu or Cr, x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1; putting the weighed raw materials into a quartz tube, sealing and uniformly mixing, putting into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be (5-9) multiplied by 10-4Pa; controlling the temperature rise speed of the smelting to be 2-5 ℃/min, the temperature to be 850-;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 0.5-5h, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) and (3) performing discharge plasma sintering or hot-pressing sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 400-480 ℃, the pressure to be 40-60MPa and the time to be 3-8min, and obtaining the bismuth telluride thermoelectric material based on entropy engineering.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the bismuth telluride thermoelectric material, the high-performance room-temperature thermoelectric material is obtained through entropy engineering, on one hand, doping of Q element provides electrons and optimizes the electric conductivity, on the other hand, due to a large amount of solid solution of various elements, the configuration entropy of the material is obviously increased, on the contrary, the material becomes more stable, a single-phase material is obtained, the increase of the configuration entropy obviously enhances the non-harmonicity, and thus the lattice thermal conductivity is greatly reduced;
(2) because the electric and thermal transport characteristics are synchronously optimized, the thermoelectric performance of the bismuth telluride thermoelectric material is obviously improved;
(3) the preparation method provided by the invention is simple in process, only comprises smelting, grinding and sintering, and is convenient for large-scale popularization.
Drawings
FIG. 1 is a graph showing thermoelectric figure of merit ZT versus temperature curves of thermoelectric materials obtained in examples 1-3 of the present invention and comparative examples 1-2.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) according to the chemical formula Bi0.97Ag0.03SbTe2Weighing a Bi simple substance, an Ag simple substance, an Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio of Se; wherein, Q is Ag, x is 1, y is 1, and z is 0.03; the weighed raw materials are put into a quartz tube to be sealed and mixed evenlyUniformly mixing, putting into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be 7 multiplied by 10-4Pa; controlling the heating rate of the smelting to be 5 ℃/min, the temperature to be 1050 ℃ and the heat preservation time to be 6 h;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 2 hours, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) and (3) performing discharge plasma sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 400 ℃, the pressure to be 40MPa and the time to be 8min, and obtaining the bismuth telluride thermoelectric material based on entropy engineering.
Example 2
The embodiment provides a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) according to the chemical formula Bi0.95Ag0.05SbTe2Weighing a Bi simple substance, an Ag simple substance, an Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio of Se; wherein, Q is Ag, x is 1, y is 1, and z is 0.05; putting the weighed raw materials into a quartz tube, sealing and uniformly mixing, putting into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be 7 multiplied by 10-4Pa; controlling the heating rate of the smelting to be 3 ℃/min, the temperature to be 950 ℃ and the heat preservation time to be 6 h;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 3 hours, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) and (3) performing discharge plasma sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 450 ℃, the pressure to be 50MPa and the time to be 5min, and obtaining the bismuth telluride thermoelectric material based on entropy engineering.
Example 3
The embodiment provides a bismuth telluride thermoelectric material based on entropy engineering and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) according to the chemical formula Bi0.94Ag0.06SbTe2Weighing a Bi simple substance, an Ag simple substance, an Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio of Se; wherein, Q is Ag, x is 1, y is 1, and z is 0.06; putting the weighed raw materials into a quartz tube, sealing and uniformly mixing, putting into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be 7 multiplied by 10-4Pa; controlling the heating rate of the smelting to be 2 ℃/min, the temperature to be 850 ℃ and the heat preservation time to be 6 h;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 2 hours, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) and (3) performing discharge plasma sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 480 ℃, the pressure to be 60MPa and the time to be 4min, and obtaining the bismuth telluride thermoelectric material based on entropy engineering.
Comparative example 1
This comparative example provides a P-type Bi2Te3A thermoelectric material and a method for preparing the same, the method comprising the steps of:
(1) according to the chemical formula Bi2Te3Weighing a Bi simple substance and a Te simple substance according to the stoichiometric ratio, putting the weighed raw materials into a quartz tube, sealing and uniformly mixing, putting the quartz tube into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be 7 multiplied by 10-4Pa; controlling the heating rate of the smelting to be 3 ℃/min, the temperature to be 950 ℃ and the heat preservation time to be 6 h;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 3 hours, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) performing discharge plasma sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 450 ℃, the pressure to be 50MPa and the time to be 5min,obtaining P-type Bi2Te3A thermoelectric material.
Comparative example 2
The present comparative example provides a bismuth telluride thermoelectric material and a preparation method thereof, based on the preparation method described in example 2, the differences are only that: step (1) omits Q (i.e., Ag), which is represented by the formula BiSbTe2Se, i.e., x ═ 1, y ═ 1; the preparation method comprises the following steps:
(1) according to the chemical formula BiSbTe2Weighing a Bi simple substance, a Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio of Se; putting the weighed raw materials into a quartz tube, sealing and uniformly mixing, putting into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be 7 multiplied by 10-4Pa; controlling the heating rate of the smelting to be 3 ℃/min, the temperature to be 950 ℃ and the heat preservation time to be 6 h;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 3 hours, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) and (3) performing discharge plasma sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 450 ℃, the pressure to be 50MPa and the time to be 5min, and obtaining the bismuth telluride thermoelectric material based on entropy engineering.
FIG. 1 is a graph showing thermoelectric figure of merit ZT versus temperature of thermoelectric materials obtained in examples 1 to 3 and comparative examples 1 to 2, as can be seen from FIG. 1:
(1) the thermoelectric figure of merit ZT of the entropy engineering-based bismuth telluride thermoelectric material obtained in example 2 is greater than 1.2 at a temperature of [350K, 500K ], and reaches a maximum value of 1.7 at a temperature of 425K;
(2) compared with example 2, although thermoelectric figure of merit ZT of the entropy engineering-based bismuth telluride thermoelectric materials obtained in examples 1 and 3 is slightly reduced, thermoelectric performance is still high when the temperature is [350K, 500K ];
(3) p-type Bi obtained in comparative example 12Te3The thermoelectric figure of merit ZT maximum of the thermoelectric material is only 0.9,the maximum value of the thermoelectric figure of merit ZT of 1.7 in example 1 is improved by 89% compared with the maximum value of the thermoelectric figure of merit ZT of 0.9 in comparative example 1;
(4) the bismuth telluride thermoelectric material obtained in the comparative example 2 omits the doping of Q element, so that the maximum value of thermoelectric figure of merit ZT is only 0.5, and the thermoelectric performance is greatly reduced.
In conclusion, the bismuth telluride thermoelectric material obtains the high-performance room-temperature thermoelectric material through entropy engineering, on one hand, doping of Q element provides electrons and optimizes electric conductivity, on the other hand, due to a large amount of solid solution of various elements, the configuration entropy of the material is obviously increased, on the contrary, the material becomes more stable, a single-phase material is obtained, the increase of the configuration entropy obviously enhances the dissonance, and thus the lattice thermal conductivity is greatly reduced; because the electric and thermal transport characteristics are synchronously optimized, the thermoelectric performance of the bismuth telluride thermoelectric material is obviously improved; the preparation method provided by the invention is simple in process, only comprises smelting, grinding and sintering, and is convenient for large-scale popularization.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. The bismuth telluride thermoelectric material based on entropy engineering is characterized in that the chemical formula of the bismuth telluride thermoelectric material based on entropy engineering is as follows: bi2-x-zQzSbxTe3-ySey；
Wherein Q comprises any one or the combination of at least two of Ag, Cu or Cr; x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1.
2. A method for preparing a bismuth telluride thermoelectric material based on entropy engineering as claimed in claim 1, wherein the method comprises the following steps:
(1) according to the chemical formula Bi2-x-zQzSbxTe3-ySeyWeighing a Bi simple substance, a Q simple substance, a Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio; wherein, Q comprises any one or the combination of at least two of Ag, Cu or Cr, x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1; uniformly mixing the weighed raw materials, and sequentially smelting and cooling to obtain a master alloy;
(2) grinding the master alloy obtained in the step (1) to obtain sample powder;
(3) and (3) sintering the sample powder obtained in the step (2) to obtain the bismuth telluride thermoelectric material based on entropy engineering.
3. The production method according to claim 2, wherein in the step (1), the weighed raw materials are put into a quartz tube, sealed and mixed uniformly, put into a muffle furnace for smelting, and cooled to obtain the master alloy.
4. The production method according to claim 3, wherein the degree of vacuum of the sealed quartz tube is controlled to be (5-9) x 10-4Pa。
5. The production method according to any one of claims 2 to 4, wherein the temperature rise rate of the melting in step (1) is 2 to 5 ℃/min;
preferably, the temperature of the smelting in the step (1) is 850-1050 ℃;
preferably, the heat preservation time of the smelting in the step (1) is 2-10 h.
6. The production method according to any one of claims 2 to 5, wherein in the step (2), the master alloy obtained in the step (1) is put into a milling pot to be manually milled;
preferably, the milling jar comprises an agate milling jar or a stainless steel milling jar.
7. The method according to any one of claims 2 to 6, wherein the time for the grinding in step (2) is 0.5 to 5 hours;
preferably, the particle size of the sample powder in step (2) is in the range of 300-400 μm.
8. The production method according to any one of claims 2 to 7, wherein the sintering in step (3) is spark plasma sintering or hot press sintering.
9. The method according to any one of claims 2-8, wherein the sintering temperature in step (3) is 400-480 ℃;
preferably, the pressure of the sintering in the step (3) is 40-60 MPa;
preferably, the sintering time in the step (3) is 3-8 min.
10. The method of any one of claims 2 to 9, comprising the steps of:
(1) according to the chemical formula Bi2-x-zQzSbxTe3-ySeyWeighing a Bi simple substance, a Q simple substance, a Sb simple substance, a Te simple substance and a Se simple substance according to the stoichiometric ratio;wherein, Q comprises any one or the combination of at least two of Ag, Cu or Cr, x is more than 0 and less than 2, y is more than 0 and less than 3, and z is more than 0 and less than or equal to 0.1; putting the weighed raw materials into a quartz tube, sealing and uniformly mixing, putting into a muffle furnace for smelting, and cooling to obtain the master alloy;
wherein the vacuum degree of the sealed quartz tube is controlled to be (5-9) multiplied by 10-4Pa; controlling the temperature rise speed of the smelting to be 2-5 ℃/min, the temperature to be 850-;
(2) putting the master alloy obtained in the step (1) into an agate grinding tank or a stainless steel grinding tank, manually grinding for 0.5-5h, and sieving to obtain sample powder with the particle size range of 300-400 mu m;
(3) and (3) performing discharge plasma sintering or hot-pressing sintering on the sample powder obtained in the step (2), controlling the sintering temperature to be 400-480 ℃, the pressure to be 40-60MPa and the time to be 3-8min, and obtaining the bismuth telluride thermoelectric material based on entropy engineering.
CN202210033342.8A 2022-01-12 2022-01-12 Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof Active CN114408874B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210033342.8A CN114408874B (en) 2022-01-12 2022-01-12 Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210033342.8A CN114408874B (en) 2022-01-12 2022-01-12 Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114408874A true CN114408874A (en) 2022-04-29
CN114408874B CN114408874B (en) 2023-07-18

Family

ID=81273889

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210033342.8A Active CN114408874B (en) 2022-01-12 2022-01-12 Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114408874B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116281881A (en) * 2023-03-24 2023-06-23 西安交通大学 Bismuth telluride-based thermoelectric material, preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1757774A (en) * 2005-11-17 2006-04-12 钢铁研究总院 Preparation method of bismuth-tollurium base thromoelectric alloy
CN102257648A (en) * 2008-12-19 2011-11-23 开利公司 Bulk-processed, enhanced figure-of-merit thermoelectric materials
KR20160125132A (en) * 2015-04-21 2016-10-31 희성금속 주식회사 Method for Bi-Te-based thermoelectric materials using Resistance Heat
KR20160146188A (en) * 2015-06-12 2016-12-21 한국전기연구원 Thermoelectric telluride materials formed complex-crystalline structure by interstitial doping
CN108231991A (en) * 2017-11-24 2018-06-29 浙江大学 A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat
CN110752285A (en) * 2019-11-05 2020-02-04 南方科技大学 Manufacturing method for improving performance of N-type Bi-Sb-Te-Se-based thermoelectric material
CN112645710A (en) * 2020-12-11 2021-04-13 哈尔滨石油学院 Method for improving thermoelectric performance of bismuth telluride-based pseudo-ternary thermoelectric material by co-doping Er and Ag
CN113774492A (en) * 2021-09-13 2021-12-10 哈尔滨工业大学 Preparation method of high-textured nanocrystalline bismuth telluride

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1757774A (en) * 2005-11-17 2006-04-12 钢铁研究总院 Preparation method of bismuth-tollurium base thromoelectric alloy
CN102257648A (en) * 2008-12-19 2011-11-23 开利公司 Bulk-processed, enhanced figure-of-merit thermoelectric materials
KR20160125132A (en) * 2015-04-21 2016-10-31 희성금속 주식회사 Method for Bi-Te-based thermoelectric materials using Resistance Heat
KR20160146188A (en) * 2015-06-12 2016-12-21 한국전기연구원 Thermoelectric telluride materials formed complex-crystalline structure by interstitial doping
CN108231991A (en) * 2017-11-24 2018-06-29 浙江大学 A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat
CN110752285A (en) * 2019-11-05 2020-02-04 南方科技大学 Manufacturing method for improving performance of N-type Bi-Sb-Te-Se-based thermoelectric material
CN112645710A (en) * 2020-12-11 2021-04-13 哈尔滨石油学院 Method for improving thermoelectric performance of bismuth telluride-based pseudo-ternary thermoelectric material by co-doping Er and Ag
CN113774492A (en) * 2021-09-13 2021-12-10 哈尔滨工业大学 Preparation method of high-textured nanocrystalline bismuth telluride

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116281881A (en) * 2023-03-24 2023-06-23 西安交通大学 Bismuth telluride-based thermoelectric material, preparation method and application thereof
CN116281881B (en) * 2023-03-24 2024-04-05 西安交通大学 Bismuth telluride-based thermoelectric material, preparation method and application thereof

Also Published As

Publication number Publication date
CN114408874B (en) 2023-07-18

Similar Documents

Publication Publication Date Title
CN101080506B (en) Production method of thermoelectric semiconductor alloy, thermoelectric conversion module and thermoelectric power generating device
US6069312A (en) Thermoelectric materials with filled skutterudite structure for thermoelectric devices
KR101364895B1 (en) Doped lead tellurides for thermoelectric applications
WO2017041634A1 (en) Bisbtese-based thermoelectric material
WO2019169970A1 (en) N-type mg-sb-based room temperature thermoelectric material and preparation method therefor
CN102339946B (en) High-performance thermoelectric composite material and preparation method thereof
US7732704B2 (en) Conductive paste for connecting thermoelectric conversion material
CN112531097B (en) n-type bismuth telluride-based thermoelectric material and preparation method thereof
CN108238796B (en) Copper seleno solid solution thermoelectric material and preparation method thereof
US20170125658A1 (en) Thermoelectric Conversion Element and Thermoelectric Conversion Module
CN101220513B (en) Thermal treatment method for improving type N polycrystal Bi2Te3thermoelectricity capability
CN112028632A (en) Non-stoichiometric bismuth telluride-based thermoelectric material and preparation method thereof
CN111490148B (en) Preparation method of polycrystalline SnSe-based thermoelectric material
CN101101954A (en) A cadmium-stibium-based p type thermal electrical material and its making method
CN107235477A (en) A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof
CN106904972A (en) A kind of environmentally friendly telluride tinbase thermoelectric material and preparation method thereof
CN108511589B (en) High-configuration entropy thermoelectric compound and design method and preparation method thereof
CN110752285A (en) Manufacturing method for improving performance of N-type Bi-Sb-Te-Se-based thermoelectric material
CN114408874B (en) Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof
CN108950278A (en) A kind of method that microwave heating prepares BiCuSeO thermoelectric block body material
CN1786229A (en) Preparation method of CoSb3 pyroelectric material having nanometer/micron composite crystal structure
CN110760933B (en) Preparation method of rare earth telluride based high-temperature thermoelectric material
CN103290249A (en) Method and apparatus for producing thermoelectric conversion material, and sputtering target production method
CN111048658A (en) SnI2Doped CsGeI3Perovskite thermoelectric material and preparation method thereof
US20230329115A1 (en) Thermoelectric Material, Method for Producing Same, and Thermoelectric Power Generation Element

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