CN112768594A - Bismuth-tellurium series natural superlattice thermoelectric material and preparation method thereof - Google Patents
Bismuth-tellurium series natural superlattice thermoelectric material and preparation method thereof Download PDFInfo
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- 238000007731 hot pressing Methods 0.000 claims abstract description 26
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- 230000000171 quenching effect Effects 0.000 claims abstract description 24
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- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims description 19
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- 230000001681 protective effect Effects 0.000 claims description 15
- 239000011812 mixed powder Substances 0.000 claims description 11
- 239000002826 coolant Substances 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- -1 bismuth tellurium series Chemical class 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
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- 230000008018 melting Effects 0.000 abstract description 6
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- 238000011031 large-scale manufacturing process Methods 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
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- 229910002899 Bi2Te3 Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 1
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- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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Abstract
The invention provides a bismuth-tellurium natural superlattice thermoelectric material and a preparation method thereof. The bismuth-tellurium natural superlattice thermoelectric material provided by the invention has a structure shown in a formula (1): bi4Te5‑xSexFormula (1); wherein x is more than 0 and less than 5. The invention uses Bi4Te5Based on the fact that a certain amount of Se is doped, the ZT value of the material can be remarkably improved. The preparation method provided by the invention comprises the steps of simple substance powder mixing, high-temperature melting quenching under vacuum condition, grinding, low-temperature annealing under vacuum condition and hot pressing treatment, wherein the simple substance powder is uniformly mixed under the inert gas state, high-temperature melting and quenching are carried out under high vacuum degree to keep a high-temperature phase, then a stable phase of the material at low temperature is obtained through low-temperature annealing, and finally Bi is obtained through hot pressing treatment4Te5‑xSexAnd (5) blocking. Compared with the traditional solid-phase sintering method, the preparation method greatly shortens the preparation periodAnd obviously improves the thermoelectric performance of the material.
Description
Technical Field
The invention relates to the field of thermoelectric materials, in particular to a bismuth-tellurium natural superlattice thermoelectric material and a preparation method thereof.
Background
Under global rapid consumption of fossil energy and large environment of waste increase, waste heat recycling provides new opportunities for relieving energy crisis. The thermoelectric material has an increasingly significant position in the field of energy recycling as a special functional material capable of realizing interconversion between thermal energy and electric energy. To determine heatThe main parameter of the energy conversion efficiency of the electric material is the ZT value of the sample: ZT ═ alpha2σ T/κ. Wherein alpha is the seebeck coefficient of the sample and is defined as the potential difference generated by the material under the unit temperature gradient; σ is the conductivity of the sample; kappa is the thermal conductivity of the sample and consists of two parts of lattice thermal conductivity and electronic thermal conductivity; t is the measured Kelvin temperature of the sample.
Bi4Te5As a novel thermoelectric material in a medium and low temperature region, belongs to (Bi)2)m(Bi2Te3)nHomologues. Its natural superlattice structure is very distinctive, with Bi2Layer and Bi2Te3The basic structural unit is formed by stacking and arranging in the c-axis direction at a ratio of 1: 5. Has excellent chemical structure stability and unique electronic and energy band structure. And the material generally has extremely low intrinsic lattice thermal conductance, and is an ideal thermoelectric material in a medium-low temperature zone. However, the energy conversion efficiency of the above materials is not good, and the current synthesis method is mainly a solid-phase sintering method, which is too cumbersome and takes more than two weeks.
Disclosure of Invention
In view of the above, the present invention provides a bismuth-tellurium-based natural superlattice thermoelectric material and a method for manufacturing the same. The thermoelectric material provided by the invention can obviously replace the thermoelectric property, and meanwhile, the preparation method provided by the invention is simple and feasible, can greatly shorten the preparation period and is convenient for large-scale production.
The invention provides a bismuth-tellurium natural superlattice thermoelectric material, which has a structure shown in a formula (1):
Bi4Te5-xSexformula (1);
wherein x is more than 0 and less than 5.
The invention also provides a preparation method of the bismuth-tellurium natural superlattice thermoelectric material in the technical scheme, which comprises the following steps:
a) under a protective atmosphere, grinding and mixing Bi powder, Te powder and Se powder to obtain mixed powder;
b) carrying out heat treatment on the mixed powder under the vacuum condition to obtain a molten mass;
c) cooling and quenching the molten mass, and then grinding to obtain ground powder;
d) annealing the ground powder under a vacuum condition, and then carrying out hot pressing to obtain the bismuth-tellurium natural superlattice thermoelectric material;
the bismuth tellurium natural superlattice thermoelectric material has a structure shown in a formula (1):
Bi4Te5-xSexformula (1);
wherein x is more than 0 and less than 5.
Preferably, in the step b), the temperature of the heat treatment is 900-1000 ℃ and the time is 6-12 h.
Preferably, in the step b), the vacuum degree of the vacuum condition is 10-5～10-6torr。
Preferably, in the step c), the melt is quenched by cooling with a cooling medium.
Preferably, the temperature of the cooling medium is less than or equal to 0 ℃, and the cooling time is 1-5 min.
Preferably, in the step d), the annealing treatment temperature is 485-500 ℃ and the time is 3-7 days.
Preferably, in the step d), the vacuum degree of the vacuum condition is 10-5～10-6torr。
Preferably, in the step d), the hot pressing temperature is 350-500 ℃, the pressure is 90-100 MPa, and the time is 1-2 h.
Preferably, in said step c), said grinding is carried out under a protective atmosphere; the cooling quenching is carried out under vacuum conditions.
The invention provides a bismuth-tellurium natural superlattice thermoelectric material which has a structure shown in a formula (1) and is formed by Bi4Te5Based on the fact that a certain amount of Se is doped, the ZT value of the material can be remarkably improved. The preparation method provided by the invention comprises the steps of simple substance powder mixing, high-temperature melting quenching under vacuum condition, grinding, low-temperature annealing under vacuum condition and hot pressingThe treatment is to mix the single powder evenly under the inert gas state, to melt and quench at high temperature under high vacuum degree to keep high temperature phase, to obtain stable phase of the material at low temperature by low temperature annealing, and to obtain Bi by hot pressing treatment4Te5-xSexNatural superlattice bulk. Compared with the traditional solid-phase sintering method, the preparation method provided by the invention greatly shortens the preparation period, improves the efficiency, has the advantages of mild and easily controlled conditions, low cost of raw materials and equipment, strong reusability and convenience for large-scale production; in addition, the method adopts Se substitution doping Te to obtain Bi under the condition of not damaging the crystal structure4Te5-xSexThe sample obviously improves the thermoelectric property of the material and has good industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an XRD pattern of a sample obtained in example 1;
FIG. 2 is an SEM photograph of a sample obtained in example 1;
FIG. 3 is an SEM photograph of a sample obtained in example 1;
FIG. 4 is a distribution diagram of Bi elements of a sample obtained in example 1;
FIG. 5 is a graph showing the distribution of Te element in the sample obtained in example 1;
FIG. 6 is an XRD pattern of samples obtained in examples 1 to 6;
FIG. 7 is an SEM photograph of a sample obtained in example 3;
FIG. 8 is an elemental distribution diagram of a sample obtained in example 3;
FIG. 9 is a graph showing the effect of the conductivity σ test on the samples obtained in examples 1 to 6;
FIG. 10 is a graph showing the effect of the Seebeck coefficient α test on samples obtained in examples 1 to 6;
FIG. 11 is a graph showing the effect of the thermal conductivity κ test on the samples obtained in examples 1 to 6;
FIG. 12 is a graph showing the effect of power factor on samples obtained in examples 1 to 6;
FIG. 13 is a graph showing the thermoelectric figure of merit ZT of the samples obtained in examples 1 to 6.
Detailed Description
The invention provides a bismuth-tellurium natural superlattice thermoelectric material, which has a structure shown in a formula (1):
Bi4Te5-xSexformula (1);
wherein x is more than 0 and less than 5; preferably, x is 1, 2, 3 or 4.
The thermoelectric material provided by the invention uses Bi4Te5On the basis, a certain amount of Se is doped to form the specific material shown in the formula (1), so that the ZT value of the material can be obviously improved.
The invention also provides a preparation method of the bismuth-tellurium natural superlattice thermoelectric material in the technical scheme, which comprises the following steps:
a) under a protective atmosphere, grinding and mixing Bi powder, Te powder and Se powder to obtain mixed powder;
b) carrying out heat treatment on the mixed powder under the vacuum condition to obtain a molten mass;
c) cooling and quenching the molten mass, and then grinding to obtain ground powder;
d) annealing the ground powder under a vacuum condition, and then carrying out hot pressing to obtain the bismuth-tellurium natural superlattice thermoelectric material;
the bismuth tellurium natural superlattice thermoelectric material has a structure shown in a formula (1):
Bi4Te5-xSexformula (1);
wherein x is more than 0 and less than 5.
With respect to step a): and grinding and mixing the Bi powder, the Te powder and the Se powder in a protective atmosphere to obtain mixed powder.
In the present invention, the kind of the protective gas providing the protective atmosphere is not particularly limited, and may be a conventional inert gas well known to those skilled in the art, including nitrogen, argon, helium, or the like. In the present invention, the manner of providing the protective atmosphere is not particularly limited and is a matter of routine operation well known to those skilled in the art, such as grinding of the raw material in a glove box filled with a protective gas.
In the invention, the Bi powder, the Te powder and the Se powder are preferably high-purity powders; the purity is preferably above 99.9%, and in some embodiments, 99.99%. In the invention, the dosage of the three elementary substance powders of Bi powder, Te powder and Se powder is preferably stoichiometric ratio, namely Bi powder, Te powder and Se powder are used according to a target product4Te5-xSexThe stoichiometric ratio in (1) is weighed. And grinding and uniformly mixing the three kinds of powder to obtain mixed powder.
In the invention, the grinding mode is not particularly limited, the three elementary substance powders can be respectively ground and then mixed together to be ground and mixed uniformly, or the three elementary substance powders can be directly put together to be ground and mixed to obtain mixed powder.
With respect to step b): and carrying out heat treatment on the mixed powder under the vacuum condition to obtain a molten mass.
In the present invention, the degree of vacuum of the vacuum condition is preferably 10-5～10-6torr. In the present invention, the vacuum condition is preferably provided by: and placing the mixed powder in a quartz tube, vacuumizing the quartz tube to a target vacuum degree, sealing the quartz tube, and performing subsequent treatment.
In the invention, the temperature of the heat treatment is preferably 900-1000 ℃; in some embodiments of the invention, the temperature of the heat treatment is 900 ℃ or 1000 ℃. The time of the heat treatment is preferably 6-12 h; in some embodiments of the invention, the time of the heat treatment is 6h or 12 h. The powder material is melted by heat treatment to obtain a melt.
With respect to step c): and cooling and quenching the molten mass, and then grinding to obtain grinding powder.
In the present invention, the cooling and quenching is preferably performed by cooling and quenching the melt with a cooling medium, that is, by rapidly cooling the melt by putting the melt into the cooling medium. In the present invention, the temperature of the cooling medium is 0 ℃ or less, and in some embodiments, the temperature is 0 ℃. The type of the cooling medium is not particularly limited, and may be, for example, an ice-water mixture at 0 ℃ or liquid nitrogen at less than 0 ℃. In the invention, the cooling time is preferably 1-5 min. The invention firstly melts at high temperature, and then cools and quenches the melt to rapidly cool the melt, so that the sample is not ready to change phase and the high temperature phase of the sample is retained, thereby obtaining the gray black ingot.
In the present invention, the cooling and quenching of the melt are preferably performed under vacuum. Specifically, the vacuum-sealed quartz tube is directly put into a cooling medium for cooling and quenching, and a sample in the quartz tube is always in a vacuum condition.
After the cooling and quenching, grinding; specifically, the sealed quartz tube subjected to the high-temperature treatment is taken out, and the tube is opened to take the material for grinding. In the present invention, the grinding is preferably performed under a protective atmosphere. In the present invention, the kind of the protective gas providing the protective atmosphere is not particularly limited, and may be a conventional inert gas well known to those skilled in the art, including nitrogen, argon, helium, or the like. In the present invention, the manner of providing the protective atmosphere is not particularly limited and is a matter of routine operation well known to those skilled in the art, such as grinding in a glove box filled with a protective gas. By grinding, a uniform portion of ground powder was obtained. The grinding step after cooling quenching cannot be omitted, and the crystallinity of the sample is increased through the grinding, so that the thermoelectric performance of the thermoelectric material is improved.
With respect to step d): and annealing the ground powder under a vacuum condition, and then carrying out hot pressing to obtain the bismuth-tellurium natural superlattice thermoelectric material.
In the present invention, the degree of vacuum of the vacuum condition is preferably 10-5～10-6torr. In the present invention, the vacuum condition is preferably provided by: placing the ground powder in a quartz tube, vacuumizing the quartz tube to a target vacuum degree, sealing the quartz tube, and performingAnd (5) continuing processing.
In the invention, the annealing temperature is preferably 485-500 ℃; in some embodiments of the invention, the temperature of the anneal is 485 deg.C, 490 deg.C, 495 deg.C, or 500 deg.C. The time of the annealing treatment is preferably 3-7 days; in some embodiments of the invention, the annealing treatment is for a period of 3 days, 5 days, or 7 days.
In the present invention, after the annealing treatment, hot pressing is performed. In the invention, the hot pressing temperature is preferably 350-500 ℃, more preferably 350-400 ℃, and the sample density can be effectively improved by hot pressing at the temperature, and the phase change of the sample is avoided. In some embodiments of the invention, the temperature of the hot pressing is 400 ℃ or 500 ℃. In the invention, the pressure of hot pressing is preferably 90-100 MPa; in some embodiments of the invention, the pressure of the hot pressing is 90MPa or 100 MPa. In the invention, the hot pressing time is preferably 1-2 h; in some embodiments of the invention, the time for hot pressing is 1h or 2 h. And hot-pressing to obtain a hot-pressed block sample, namely the bismuth-tellurium series natural superlattice crystal block thermoelectric material.
The preparation method provided by the invention comprises the steps of simple substance powder mixing, high-temperature melting quenching under vacuum condition, grinding, low-temperature annealing under vacuum condition and hot pressing treatment, wherein the simple substance powder is uniformly mixed under the inert gas state, high-temperature melting and quenching are carried out under high vacuum degree to keep a high-temperature phase, then a stable phase of the material at low temperature is obtained through low-temperature annealing, and finally Bi is obtained through hot pressing treatment4Te5-xSexNatural superlattice bulk. Compared with the traditional solid-phase sintering method, the preparation method provided by the invention greatly shortens the preparation period, improves the efficiency, has the advantages of mild and easily controlled conditions, low cost of raw materials and equipment, strong reusability and convenience for large-scale production; in addition, the method adopts Se substitution doping Te to obtain Bi under the condition of not damaging the crystal structure4Te5-xSexThe sample obviously improves the thermoelectric property of the material and has good industrial application prospect.
The experimental result shows that the preparation method can be completed within 1 weekThe preparation, the main reaction is completed in the step of high-temperature melting and quenching, thus greatly shortening the preparation period; meanwhile, the obtained material is at the temperature of 30-400 ℃, compared with pure Bi4Te5Obviously improves the thermoelectric figure of merit, and is a thermoelectric material with wide application prospect in medium and low temperature regions.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, the raw material powders were all high-purity powders, and the purity was 99.99%.
Example 1
S1, grinding the Bi powder and the Te powder uniformly in a stoichiometric ratio of 4: 5 in a glove box filled with nitrogen by using a mortar, and mixing the powder together to form uniform powder.
S2, transferring the obtained powder to a drawer with a weighing paper to 10-5Sealing the quartz tube in high vacuum degree of torr, and then carrying out heat treatment at 900 ℃ for 6h to form a molten mass.
S3, putting the quartz tube filled with the melt into ice water at 0 ℃ for quenching, taking out the quartz tube after 1min, opening the tube, taking out a gray black ingot, and uniformly grinding by using a mortar in a glove box filled with nitrogen to obtain grinding powder.
S4, transferring the powder to suction box 10-5Sealing the quartz tube in high vacuum degree of torr, and annealing at 485 ℃ for 3 days; then opening the tube to take out the powder, and carrying out hot pressing for 1h under the conditions of 400 ℃ and 90MPa to obtain a hot-pressed block sample Bi4Te5。
The obtained sample was subjected to X-ray diffraction measurement, and as a result, referring to fig. 1, fig. 1 is an XRD pattern of the sample obtained in example 1. As can be seen, Bi was obtained4Te5The diffraction pattern of the natural superlattice material is well contrasted with that of a standard card, and the Bi is proved to be obtained4Te5And the purity of the sample is high.
Scanning electron microscope tests and element distribution tests are carried out on the obtained samples, and the results are shown in fig. 2-5, fig. 2 and 3 are SEM images of the samples obtained in example 1, wherein fig. 2 and 3 are SEM images under different magnifications;
fig. 4 and 5 are element distribution test charts of the sample obtained in example 1, in which fig. 4 is a Bi element distribution chart of the sample obtained in example 1, and fig. 5 is a Te element distribution chart of the sample obtained in example 1. As can be seen, Bi was obtained4Te5The samples had a distinct layered structure on the micrometer scale, no surface staining, and very uniform elemental ratios, indicating that the synthesized samples retained well defined crystal structure characteristics.
Example 2
S1, uniformly grinding the Bi powder, the Te powder and the Se powder in a stoichiometric ratio of 4: 1 in a glove box filled with nitrogen by using a mortar, and mixing the powder together to form uniform powder.
S2, transferring the obtained powder to a drawer with a weighing paper to 10-6Sealing the quartz tube in high vacuum degree of torr, and then carrying out heat treatment at 1000 ℃ for 6h to form a molten mass.
S3, putting the quartz tube filled with the melt into ice water at 0 ℃ for quenching, taking out the quartz tube after 2min, opening the tube, taking out a gray black ingot, and uniformly grinding by using a mortar in a glove box filled with nitrogen to obtain grinding powder.
S4, transferring the powder to suction box 10-6Sealing the quartz tube in high vacuum degree of torr, and annealing at 490 ℃ for 3 days; then opening the tube to take out the powder, and carrying out hot pressing for 1h under the conditions of 400 ℃ and 90MPa to obtain a hot-pressed block sample Bi4Te4Se。
Example 3
S1, grinding the Bi powder, the Te powder and the Se powder uniformly by a mortar in a glove box filled with nitrogen according to the stoichiometric ratio of 4: 3: 2, and mixing the powder together to form uniform powder.
S2, transferring the obtained powder to a drawer with a weighing paper to 10-5Sealing the quartz tube in high vacuum degree of torr, and then carrying out heat treatment at 900 ℃ for 12h to form a molten mass.
S3, putting the quartz tube filled with the melt into ice water at 0 ℃ for quenching, taking out the quartz tube after 3min, opening the tube, taking out a gray black ingot, and uniformly grinding by using a mortar in a glove box filled with nitrogen to obtain grinding powder.
S4, transferring the powder to suction box 10-5Sealing the quartz tube in high vacuum degree of torr, and annealing at 495 ℃ for 3 days; then opening the tube to take out the powder, and carrying out hot pressing for 1h under the conditions of 400 ℃ and 90MPa to obtain a hot-pressed block sample Bi4Te3Se2。
Example 4
S1, grinding the Bi powder, the Te powder and the Se powder uniformly by a mortar in a glove box filled with nitrogen according to the stoichiometric ratio of 4: 2: 3, and mixing the powder together to form uniform powder.
S2, transferring the obtained powder to a drawer with a weighing paper to 10-5Sealing the quartz tube in high vacuum degree of torr, and then carrying out heat treatment at 900 ℃ for 6h to form a molten mass.
S3, putting the quartz tube filled with the melt into ice water at 0 ℃ for quenching, taking out the quartz tube after 4min, opening the tube, taking out a gray black ingot, and uniformly grinding by using a mortar in a glove box filled with nitrogen to obtain grinding powder.
S4, transferring the powder to suction box 10-5Sealing the quartz tube in high vacuum degree of torr, and annealing for 7 days at 500 ℃; then opening the tube to take out the powder, and carrying out hot pressing for 1h at 400 ℃ under the pressure of 100MPa to obtain a hot-pressed block sample Bi4Te2Se3。
Example 5
S1, grinding the Bi powder, the Te powder and the Se powder uniformly by a mortar in a glove box filled with nitrogen according to the stoichiometric ratio of 4: 1: 4, and mixing the powder together to form uniform powder.
S2, transferring the obtained powder to a drawer with a weighing paper to 10-5Sealing the quartz tube in high vacuum degree of torr, and then carrying out heat treatment at 900 ℃ for 6h to form a molten mass.
S3, putting the quartz tube filled with the melt into ice water at 0 ℃ for quenching, taking out the quartz tube after 1min, opening the tube, taking out a gray black ingot, and uniformly grinding by using a mortar in a glove box filled with nitrogen to obtain grinding powder.
S4, transferring the powder to suction box 10-5Sealing the quartz tube in high vacuum degree of torr, and annealing at 485 ℃ for 5 days; then opening the tube to take out the powder, and hot-pressing for 1h at 500 ℃ under 100MPa to obtainHot pressed block sample Bi4TeSe4。
Example 6
S1, grinding the Bi powder and the Se powder uniformly in a stoichiometric ratio of 4: 5 in a glove box filled with nitrogen by using a mortar, and mixing the powder together to form uniform powder.
S2, transferring the obtained powder to a drawer with a weighing paper to 10-5Sealing the quartz tube in high vacuum degree of torr, and then carrying out heat treatment at 900 ℃ for 6h to form a molten mass.
S3, putting the quartz tube filled with the melt into ice water at 0 ℃ for quenching, taking out the quartz tube after 5min, opening the tube, taking out a gray black ingot, and uniformly grinding by using a mortar in a glove box filled with nitrogen to obtain grinding powder.
S4, transferring the powder to suction box 10-5Sealing the quartz tube in high vacuum degree of torr, and annealing at 485 ℃ for 7 days; then opening the tube to take out the powder, and carrying out hot pressing for 2h at 500 ℃ and 100MPa to obtain a hot-pressed block sample Bi4Se5。
Example 7
(1) Characterization of
The X-ray diffraction test was performed on the samples obtained in examples 1 to 6, and the results are shown in FIG. 6, in which FIG. 6 is an XRD pattern of the samples obtained in examples 1 to 6. It can be seen that Bi is the same as that in example 14Te5Compared with the samples obtained in examples 2-6, the XRD pattern of the Se-substituted Te-doped sample has no mixed peak, the purity is higher, and the monotonous displacement of the diffraction peak is accompanied, so that the lattice parameter of the sample is changed along with the Se-substituted Te doping, which indicates that the doping of the sample is effective, Se enters into the lattice structure, and the original structure of the material is not damaged.
Bi for the sample obtained in example 34Te3Se2Scanning electron microscope tests and element distribution tests are carried out, and the results are shown in fig. 7 and 8, fig. 7 is an SEM image of the sample obtained in example 3, and fig. 8 is an element distribution diagram of the sample obtained in example 3. It can be seen that the samples after being doped in large quantity still maintain the perfect layered structure, and the element proportion distribution is also very uniform.
(2) Thermoelectric performance testing
The following tests and calculations were performed on the samples obtained in examples 1-6:
testing is as follows: the synthesized block sample is ground into a cube of 3mm × 3mm × 12mm, the cube is placed on a Seebeck measuring instrument, the initial measurement temperature is 30 ℃, the second measurement temperature is 50 ℃, the temperature is measured to 400 ℃ at the point interval of 50 ℃, and the change relation between the electrical conductivity sigma of the block sample and the Seebeck coefficient alpha along with the temperature is measured. Referring to fig. 9 and 10, respectively, fig. 9 is a graph showing the effect of the conductivity σ test on the samples obtained in examples 1 to 6, and fig. 10 is a graph showing the effect of the seebeck coefficient α test on the samples obtained in examples 1 to 6.
Testing is carried out: grinding a block sample into a wafer with the thickness of 2mm multiplied by the diameter of 10mm, measuring the wafer on a laser thermal conductivity meter by adopting a detection standard of measuring the thermal conductivity by adopting a flash method, taking 30 ℃ as an initial measurement temperature and 50 ℃ as a second measurement temperature, measuring the temperature to 400 ℃ at intervals by taking 50 ℃ as a point, heating and cooling the two sides to measure the change relation of the thermal diffusivity of the sample along with the temperature, and finally obtaining the change trend of the thermal conductivity kappa of the sample along with the temperature according to density and specific heat data. Results referring to fig. 11, fig. 11 is a graph showing the effect of the thermal conductivity κ test on the samples obtained in examples 1-6.
Testing (c): by the formula PF ═ alpha2And sigma obtaining the variation relation of the power factor of each sample with the temperature. Results referring to fig. 12, fig. 12 is a graph showing the power factor effect of the samples obtained in examples 1 to 6.
Testing (iv): by the formula ZT ═ alpha2σ T/κ gives the thermoelectric ZT value of each sample as a function of temperature. As a result, referring to FIG. 13, FIG. 13 is a graph showing the effect of the thermoelectric figure of merit ZT of the samples obtained in examples 1 to 6.
The above test results show that Bi is pure sample obtained in example 14Te5Compared with the doped samples obtained in examples 2-6, the conductivity sigma of the doped samples is obviously reduced (see fig. 9), wherein the seebeck coefficient alpha (absolute value) of the doped samples obtained in examples 2-5 is obviously increased, and the seebeck coefficient alpha (absolute value) of the fully-replaced samples obtained in example 6 is reduced (see fig. 10). At the same time, Bi was added to the pure sample Bi obtained in example 14Te5Compared with the fruitThe thermal conductivity κ of the doped samples obtained in examples 2-6 was significantly reduced (see fig. 11), mainly due to the scattering effect of point defects on electrons and phonons caused by doping. The above calculation formula was combined, and the results showed that Bi was pure in the sample obtained in example 14Te5Compared with the samples obtained in the embodiments 2 to 6, the power factor of the doped samples is obviously reduced (see fig. 12), wherein the thermoelectric figure of merit ZT of the doped samples obtained in the embodiments 2 to 5 is obviously improved, and the thermoelectric figure of merit ZT of the fully-replaced samples obtained in the embodiment 6 is reduced. The above results demonstrate that the present invention is in Bi4Te5On the basis, Se is adopted to replace Te, and under the condition of a certain amount of doping replacement, the thermoelectric figure of merit of the obtained sample is obviously improved. Among them, in examples 2 to 5, the sample Bi obtained in example 34Te3Se2The thermoelectric figure of merit of the method is optimized.
The above examples prove that compared with the traditional solid phase method, the preparation method provided by the invention greatly shortens the preparation period, improves the efficiency and is convenient for large-scale production; in addition, the method adopts Se substitution doping Te to obtain Bi under the condition of not damaging the crystal structure4Te5-xSexThe sample obviously improves the thermoelectric property of the material.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A bismuth-tellurium series natural superlattice thermoelectric material is characterized by having a structure shown in formula (1):
Bi4Te5-xSexformula (1);
wherein x is more than 0 and less than 5.
2. The method for preparing the bismuth tellurium series natural superlattice thermoelectric material as claimed in claim 1, is characterized by comprising the following steps of:
a) under a protective atmosphere, grinding and mixing Bi powder, Te powder and Se powder to obtain mixed powder;
b) carrying out heat treatment on the mixed powder under the vacuum condition to obtain a molten mass;
c) cooling and quenching the molten mass, and then grinding to obtain ground powder;
d) annealing the ground powder under a vacuum condition, and then carrying out hot pressing to obtain the bismuth-tellurium natural superlattice thermoelectric material;
the bismuth tellurium natural superlattice thermoelectric material has a structure shown in a formula (1):
Bi4Te5-xSexformula (1);
wherein x is more than 0 and less than 5.
3. The preparation method according to claim 2, wherein in the step b), the temperature of the heat treatment is 900-1000 ℃ and the time is 6-12 h.
4. The method according to claim 2 or 3, wherein the vacuum condition in the step b) has a degree of vacuum of 10-5～10-6torr。
5. The method according to claim 2, wherein the molten mass is quenched by cooling with a cooling medium in step c).
6. The preparation method according to claim 5, wherein the temperature of the cooling medium is less than or equal to 0 ℃ and the cooling time is 1-5 min.
7. The method according to claim 2, wherein the annealing treatment is carried out at 485-500 ℃ for 3-7 days in the step d).
8. The method according to claim 2 or 7, wherein the vacuum condition has a degree of vacuum of 10 in the step d)-5～10-6torr。
9. The preparation method according to claim 2, wherein in the step d), the hot pressing temperature is 350-500 ℃, the pressure is 90-100 MPa, and the time is 1-2 h.
10. The method according to claim 2, wherein in step c), the grinding is carried out under a protective atmosphere;
the cooling quenching is carried out under vacuum conditions.
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