CN113773083B - Bismuth telluride-based material with high strength and high thermoelectric property and preparation method thereof - Google Patents
Bismuth telluride-based material with high strength and high thermoelectric property and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 35
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000010453 quartz Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000713 high-energy ball milling Methods 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000012856 weighed raw material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000002490 spark plasma sintering Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000004098 selected area electron diffraction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention discloses a bismuth telluride-based material with high strength and high thermoelectric property and a preparation method thereof, and relates to a bismuth telluride-based material and a preparation method thereof. The invention aims to solve the problems of poor mechanical property and difficult cutting processing of the existing bismuth telluride-based material due to the special layered structure. The chemical general formula of the bismuth telluride-based material with high strength and high thermoelectric property is Bi 0.4 Sb 1.6 Te 3‑x (ii) a The method comprises the following steps: 1. weighing; 2. preparing an ingot; 3. grinding; 4. and (4) sintering. The bismuth telluride-based material is used for preparing the bismuth telluride-based material with high strength and high thermoelectric performance.
Description
Technical Field
The invention relates to a bismuth telluride based material and a preparation method thereof.
Background
In the last 20 years, the thermoelectric performance of the bismuth telluride-based alloy is rapidly improved through microstructure regulation and energy band engineering, and large-scale commercial application in the field of solid-state refrigeration is successfully realized. Particularly, in recent years, thermoelectric devices have attracted attention in terms of micro refrigeration and functions because of their advantages such as no vibration, no noise, no need for auxiliary components, and long service life, and thus are expected to be applied to the fields of electronics, medicine, and the like. However, the special layered structure of the bismuth telluride-based material causes the bismuth telluride-based material to have poor mechanical properties and difficult cutting and processing, and is difficult to process into micron-sized or even submicron-sized materials required by micro devices, thereby limiting the further development of the micro thermoelectric devices. Therefore, the mechanical property of the bismuth telluride alloy is improved while the high thermoelectric property is obtained.
Disclosure of Invention
The invention provides a bismuth telluride-based material with high strength and high thermoelectric property and a preparation method thereof, aiming at solving the problems that the existing bismuth telluride-based material is poor in mechanical property and difficult to cut due to a special layered structure.
Bismuth telluride base with high strength and high thermoelectric performanceThe chemical general formula of the material, namely the bismuth telluride-based material with high strength and high thermoelectric property is Bi 0.4 Sb 1.6 Te 3-x ，0.01≤x≤0.03。
A preparation method of a bismuth telluride-based material with high strength and high thermoelectric performance is carried out according to the following steps:
1. weighing:
in a glove box in an argon protective atmosphere, the chemical formula is Bi 0.4 Sb 1.6 Te 3-x Weighing Bi, sb and Te according to the stoichiometric ratio, placing the weighed raw materials into a quartz tube, and vacuumizing the quartz tube to 10 DEG C -2 Sealing under Pa to obtain a sealed quartz tube; wherein x is more than or equal to 0.01 and less than or equal to 0.03;
2. preparing an ingot:
placing the sealed quartz tube in a box-type resistance furnace, heating the sealed quartz tube to 1073K-1123K within 4 h-5 h, then preserving heat for 8 h-10 h under the condition of 1073K-1123K, and finally slowly cooling along with the furnace to obtain an initial ingot;
3. grinding:
smashing the initial cast ingot, placing the smashed initial cast ingot in a stainless steel ball milling tank, and carrying out high-energy ball milling for 2-4 h under the condition of argon atmosphere to obtain nanoscale powder;
4. and (3) sintering:
sintering for 4-8 min by using a discharge plasma sintering furnace under the conditions that the temperature is 650-700K and the pressure is 60-80 MPa to obtain the bismuth telluride-based material with high strength and high thermoelectric performance.
The beneficial effects of the invention are:
the invention reduces Bi 0.4 Sb 1.6 Te 3 And the proportion of the Te is combined with high-energy ball milling to grind the smelting cast ingot into powder with the size of 20 nm-50 nm. At the moment, a large amount of residual stress exists in the powder, the secondary grain boundary annealing in the subsequent discharge plasma sintering process is driven, high-density nanometer twin crystals are constructed, and the material compression strength is improved from 188MPa to 264MPa. Meanwhile, the average zT value of the material at 30-250 ℃ is also improved from 0.86 to 1.07, and the synchronization of thermoelectric property and mechanical property is realizedThe improvement of mechanical property can solve the problems of poor mechanical property and difficult cutting processing of the existing bismuth telluride-based material due to the special layered structure.
The invention is used for the bismuth telluride-based material with high strength and high thermoelectric property and the preparation method thereof.
Drawings
FIG. 1 is a transmission electron micrograph of (a) Bi prepared by a comparative experiment 0.4 Sb 1.6 Te 3 (b) Bi prepared in example III 0.4 Sb 1.6 Te 2.97 ；
FIG. 2 is a selected area electron diffraction pattern, (c) a selected area electron diffraction pattern near the interface of the two layered structure in FIG. 1 (b), (d) a selected area electron diffraction pattern inside the single layered structure in FIG. 1 (b);
FIG. 3 shows Bi 0.4 Sb 1.6 Te 3-x Graph of the variation of the conductivity of the alloy with temperature, 1 is Bi prepared in example one 0.4 Sb 1.6 Te 2.99 And 2 is Bi prepared in example two 0.4 Sb 1.6 Te 2.98 And 3 is Bi prepared in example III 0.4 Sb 1.6 Te 2.97 And 4 is Bi prepared by comparative experiment 0.4 Sb 1.6 Te 3 ；
FIG. 4 shows Bi 0.4 Sb 1.6 Te 3-x The Seebeck coefficient of the alloy varies with temperature, 1 is Bi prepared in the first embodiment 0.4 Sb 1.6 Te 2.99 And 2 is Bi prepared in example two 0.4 Sb 1.6 Te 2.98 3 is Bi prepared in example III 0.4 Sb 1.6 Te 2.97 And 4 is Bi prepared by comparative experiment 0.4 Sb 1.6 Te 3 ；
FIG. 5 shows Bi 0.4 Sb 1.6 Te 3-x The variation of the alloy thermal conductivity with the temperature is shown in the graph; bi prepared in example one 0.4 Sb 1.6 Te 2.99 2 is Bi prepared in example two 0.4 Sb 1.6 Te 2.98 And 3 is Bi prepared in example III 0.4 Sb 1.6 Te 2.97 And 4 is Bi prepared by a comparative experiment 0.4 Sb 1.6 Te 3 ；
FIG. 6 shows Bi 0.4 Sb 1.6 Te 3-x The thermoelectric figure of merit of the alloy is plotted with the change of temperature;
FIG. 7 shows Bi 0.4 Sb 1.6 Te 3-x The average thermoelectric merit figure of the alloy in the range of 30-250 ℃;
FIG. 8 shows Bi 0.4 Sb 1.6 Te 3-x Stress-strain curve at room temperature for the alloy.
Detailed Description
The technical solution of the present invention is not limited to the embodiments listed below, and includes any combination of the embodiments.
The first specific implementation way is as follows: the chemical general formula of the bismuth telluride-based material with high strength and high thermoelectric property is Bi 0.4 Sb 1.6 Te 3-x ，0.01≤x≤0.03。
The beneficial effects of the embodiment are as follows: this embodiment reduces Bi 0.4 Sb 1.6 Te 3 And the proportion of the Te is combined with high-energy ball milling to grind the smelting cast ingot into powder with the size of 20 nm-50 nm. At the moment, a large amount of residual stress exists in the powder, the secondary grain boundary annealing in the subsequent discharge plasma sintering process is driven, high-density nanometer twin crystals are constructed, and the material compression strength is improved from 188MPa to 264MPa. Meanwhile, the average zT value of the material at 30-250 ℃ is also improved from 0.86 to 1.07, the synchronous improvement of thermoelectric property and mechanical property is realized, and the improvement of mechanical property can solve the problems of poor mechanical property and difficult cutting processing of the existing bismuth telluride-based material due to the special layered structure.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: x is more than or equal to 0.02 and less than or equal to 0.03. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: x =0.03. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the preparation method of the bismuth telluride-based material with high strength and high thermoelectric property is carried out according to the following steps:
1. weighing:
in a glove box in an argon protective atmosphere, the chemical formula is Bi 0.4 Sb 1.6 Te 3-x Weighing Bi, sb and Te according to the stoichiometric ratio, placing the weighed raw materials into a quartz tube, and vacuumizing the quartz tube to 10 DEG C -2 Sealing under Pa to obtain a sealed quartz tube; wherein x is more than or equal to 0.01 and less than or equal to 0.03;
2. preparing an ingot:
placing the sealed quartz tube in a box-type resistance furnace, heating the sealed quartz tube to 1073K-1123K within 4 h-5 h, then preserving heat for 8 h-10 h under the condition of 1073K-1123K, and finally slowly cooling along with the furnace to obtain an initial ingot;
3. grinding:
smashing the initial cast ingot, placing the smashed initial cast ingot in a stainless steel ball milling tank, and carrying out high-energy ball milling for 2-4 h under the condition of argon atmosphere to obtain nanoscale powder;
4. and (3) sintering:
sintering for 4-8 min by using a discharge plasma sintering furnace under the conditions that the temperature is 650-700K and the pressure is 60-80 MPa to obtain the bismuth telluride-based material with high strength and high thermoelectric performance.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: in the first step, x is more than or equal to 0.02 and less than or equal to 0.03. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the present embodiment is different from the fourth or fifth embodiment in that: and in the second step, the sealed quartz tube is heated to 1073K in 4h, and then the temperature is kept for 8 h-10 h under the condition of 1073K. The other is the same as the fourth or fifth embodiment.
The seventh concrete implementation mode: this embodiment differs from one of the fourth to sixth embodiments in that: the particle size of the nano-grade powder in the third step is 20 nm-50 nm. The other is the same as one of the fourth to sixth embodiments.
The specific implementation mode is eight: this embodiment is different from one of the fourth to seventh embodiments in that: and in the third step, a SPEX-8000M high-energy ball mill is used for high-energy ball milling for 2 to 4 hours under the condition of argon atmosphere. The rest is the same as the fourth to seventh embodiments.
The specific implementation method nine: this embodiment is different from the fourth to eighth embodiment in that: and in the fourth step, a discharge plasma sintering furnace is used for sintering for 5-8 min under the conditions that the temperature is 650-700K and the pressure is 70-80 MPa. The others are the same as the fourth to eighth embodiments.
The detailed implementation mode is ten: this embodiment is different from one of the fourth to ninth embodiments in that: and in the fourth step, a discharge plasma sintering furnace is used for sintering for 5min under the conditions that the temperature is 673K and the pressure is 80 MPa. The rest is the same as the fourth to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the chemical general formula of the bismuth telluride-based material with high strength and high thermoelectric property is Bi 0.4 Sb 1.6 Te 3-x X =0.01, i.e. of the general formula Bi 0.4 Sb 1.6 Te 2.99 ；
The preparation method of the bismuth telluride-based material with high strength and high thermoelectric property comprises the following steps:
1. weighing:
in a glove box in an argon protective atmosphere, the chemical formula is Bi 0.4 Sb 1.6 Te 3-x Weighing Bi, sb and Te according to the stoichiometric ratio, placing the weighed raw materials in a quartz tube, connecting the quartz tube with a vacuum mechanical pump, and vacuumizing the quartz tube to 10 DEG C -2 Sealing the quartz tube by using high-temperature flame under Pa to obtain a sealed quartz tube; x =0.01;
2. preparing an ingot:
placing the sealed quartz tube in a box-type resistance furnace, heating the sealed quartz tube to 1073K within 4h, then preserving the heat for 10h under the condition of 1073K, and finally slowly cooling along with the furnace to obtain an initial ingot;
3. grinding:
smashing the initial cast ingot, placing the smashed initial cast ingot in a stainless steel ball milling tank, and carrying out high-energy ball milling for 2 hours by using a SPEX-8000M high-energy ball mill under the condition of argon atmosphere to obtain nanoscale powder;
4. and (3) sintering:
sintering for 5min by using a discharge plasma sintering furnace under the conditions of 673K temperature and 80MPa pressure to obtain the bismuth telluride-based material with high strength and high thermoelectric property.
The particle size of the nano-grade powder in the third step is 20 nm-50 nm.
Example two: the difference between the present embodiment and the first embodiment is: x =0.02, i.e. of the general chemical formula Bi 0.4 Sb 1.6 Te 2.98 . The rest is the same as the first embodiment.
Example three: the difference between the present embodiment and the first embodiment is: x =0.03, i.e. of the general chemical formula Bi 0.4 Sb 1.6 Te 2.97 . The rest is the same as in the first embodiment.
Comparative experiment: the difference between the present embodiment and the first embodiment is: x =0, i.e. of the general formula Bi 0.4 Sb 1.6 Te 3 . The rest is the same as the first embodiment.
FIG. 1 is a transmission electron micrograph of (a) Bi prepared in a comparative experiment 0.4 Sb 1.6 Te 3 (b) Bi prepared in example III 0.4 Sb 1.6 Te 2.97 (ii) a As can be seen, some layered structure may appear inside the material grains, and Bi 0.4 Sb 1.6 Te 2.97 The number of the middle laminated structure is far higher than that of Bi 0.4 Sb 1.6 Te 3 。
FIG. 2 is a plot of selected area electron diffraction patterns, (c) selected area electron diffraction patterns near the interface of the two layered structure in FIG. 1 (b), (d) selected area electron diffraction patterns within the single layered structure in FIG. 1 (b); as can be seen, two sets of blobs representing the same structural information appear in the (c) diagram, while only one set appears in the (d) diagram. This shows typical twin diffraction spot characteristics, confirming that the layered structure in fig. 1 is twin, and the occurrence of high-density twin can significantly improve the mechanical properties of the material.
FIG. 3 shows Bi 0.4 Sb 1.6 Te 3-x Graph of the variation of the conductivity of the alloy with temperature, 1 is Bi prepared in example one 0.4 Sb 1.6 Te 2.99 2 is Bi prepared in example two 0.4 Sb 1.6 Te 2.98 3 is Bi prepared in example III 0.4 Sb 1.6 Te 2.97 And 4 is Bi prepared by a comparative experiment 0.4 Sb 1.6 Te 3 . As can be seen, σ for all samples showed a downward trend during the rise of the test temperature, showing typical degenerate semiconductor characteristics. Bi prepared according to standard stoichiometric ratio 0.4 Sb 1.6 Te 3 The alloy has the lowest sigma and is 54.7 multiplied by 10 at room temperature 3 Sm -1 . On the basis, the sigma is gradually increased along with the increase of x, and can reach 135.3 multiplied by 10 at 303K 3 Sm -1 。
FIG. 4 shows Bi 0.4 Sb 1.6 Te 3-x The Seebeck coefficient of the alloy varies with temperature, 1 is Bi prepared in the first embodiment 0.4 Sb 1.6 Te 2.99 2 is Bi prepared in example two 0.4 Sb 1.6 Te 2.98 3 is Bi prepared in example III 0.4 Sb 1.6 Te 2.97 And 4 is Bi prepared by comparative experiment 0.4 Sb 1.6 Te 3 . As can be seen, the Seebeck coefficients of all the alloys are positive values, showing the characteristic p-type conductivity that typical holes dominate. At 30 ℃, the Te content is reduced to ensure that the Seebeck coefficient is from 253.2 mu VK -1 144.8 mu VK reduction -1 And a seebeck coefficient of from 158.1 μ VK at 250 ℃ -1 Increased to 175.6. Mu. VK -1 。
FIG. 5 shows Bi 0.4 Sb 1.6 Te 3-x The variation of alloy thermal conductivity with temperature is shown in the graph; bi prepared in example one 0.4 Sb 1.6 Te 2.99 2 is Bi prepared in example two 0.4 Sb 1.6 Te 2.98 And 3 is Bi prepared in example III 0.4 Sb 1.6 Te 2.97 And 4 is Bi prepared by a comparative experiment 0.4 Sb 1.6 Te 3 . The Te content is reduced to ensure that the room temperature thermal conductivity is from 0.85Wm -1 K -1 Increased to 1.41Wm -1 K -1 (ii) a However, at 250 deg.C, the thermal conductivity is from 1.53Wm by reducing the Te content -1 K -1 Reduced to 1.26Wm -1 K -1 It is stated that Bi can be reduced by reducing the Te content 0.4 Sb 1.6 Te 3 Thermal conductivity of the material in the higher temperature region.
FIG. 6 shows Bi 0.4 Sb 1.6 Te 3-x The thermoelectric figure of merit of the alloy is plotted with the change of temperature; as can be seen, the ratio is compared with Bi 0.4 Sb 1.6 Te 3 Although the thermoelectric figure of merit of the alloy is not improved after the Te content is reduced, the temperature corresponding to the highest point of the curve is improved from 50 ℃ to more than 100 ℃.
FIG. 7 shows Bi 0.4 Sb 1.6 Te 3-x The average thermoelectric merit figure of the alloy in the range of 30-250 ℃. As can be seen from the graph, the average thermoelectric figure of merit increased by 1.07 and 1.06, respectively, after decreasing by 0.01 and 0.02 Te.
FIG. 8 shows Bi 0.4 Sb 1.6 Te 3-x Room temperature stress-strain curves for the alloys. As can be seen from the figure, the compressive strength of the material is improved from 188MPa to 264MPa, and the compressive strain is correspondingly improved to 5.2%.
Claims (5)
1. A preparation method of a bismuth telluride-based material with high strength and high thermoelectric performance is characterized by comprising the following steps:
1. weighing:
in a glove box in an argon protective atmosphere, bi is represented by the chemical formula 0.4 Sb 1.6 Te 3-x Weighing Bi, sb and Te according to the stoichiometric ratio, placing the weighed raw materials in a quartz tube, and vacuumizing the quartz tube to 10 DEG C -2 Sealing the quartz tube below Pa to obtain a sealed quartz tube; wherein x is more than or equal to 0.01 and less than or equal to 0.03;
2. preparing an ingot:
placing the sealed quartz tube in a box-type resistance furnace, heating the sealed quartz tube to 1073K-1123K within 4 h-5 h, then preserving heat for 8 h-10 h under the condition of 1073K-1123K, and finally slowly cooling along with the furnace to obtain an initial ingot;
3. grinding:
smashing the initial cast ingot, placing the smashed initial cast ingot in a stainless steel ball milling tank, and carrying out high-energy ball milling for 2-4 h by using a SPEX-8000M high-energy ball mill under the condition of argon atmosphere to obtain nanoscale powder; the particle size of the nano-grade powder is 20 nm-50 nm;
4. and (3) sintering:
sintering for 4-8 min by using a discharge plasma sintering furnace under the conditions that the temperature is 650-700K and the pressure is 60-80 MPa to obtain the bismuth telluride-based material with high strength and high thermoelectric performance.
2. The method for preparing the bismuth telluride-based material with high strength and high thermoelectric property as claimed in claim 1, wherein x is 0.02-0.03 in the first step.
3. The method for preparing the bismuth telluride-based material with high strength and high thermoelectric property as claimed in claim 1, wherein in the second step, the sealed quartz tube is heated to 1073K in 4h, and then the temperature is kept at 1073K for 8h to 10h.
4. The preparation method of the bismuth telluride-based material with high strength and high thermoelectric performance as claimed in claim 1, wherein the fourth step is sintering for 5-8 min in a discharge plasma sintering furnace at 650-700K and 70-80 MPa.
5. The method for preparing the bismuth telluride-based material with high strength and high thermoelectric performance as claimed in claim 1, wherein the fourth step is to sinter the bismuth telluride-based material for 5min in a spark plasma sintering furnace at 673K and 80 MPa.
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