CN104409623B - Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material - Google Patents
Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 47
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 44
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000003672 processing method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 title claims abstract description 10
- 230000008859 change Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000009413 insulation Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 10
- 239000011669 selenium Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 238000003825 pressing Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000004857 zone melting Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910002908 (Bi,Sb)2(Te,Se)3 Inorganic materials 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000005680 Thomson effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及热电材料技术领域，尤其涉及一种提高N型碲化铋基粉末烧结块体热电材料性能的加工方法。The invention relates to the technical field of thermoelectric materials, in particular to a processing method for improving the performance of N-type bismuth telluride-based powder sintered block thermoelectric materials.
背景技术Background technique
热电材料是一种可以直接实现热能与电能相互转换的新能源材料，其机理建立于塞贝克效应、帕帖尔效应及汤姆逊效应这三个热电转换效应之上。过去几十年，由于能源问题日益受到人们的关注，热电材料的研究因此进入了一个新的阶段。利用P型和N型两种半导体热电材料串联可以制作热电制冷和发电器件。热电器件具有无污染、无噪声、无运动部件、无振动等诸多优点。热电器件的转换效率主要取决于材料的无量纲热电优值：ZT＝(α2σ/κ)T。其中α为塞贝克系数，σ为电导率，κ为热导率，T为热力学温度。Thermoelectric materials are new energy materials that can directly convert heat energy and electric energy. Its mechanism is based on the three thermoelectric conversion effects of Seebeck effect, Patel effect and Thomson effect. In the past few decades, due to the increasing attention to energy issues, the research on thermoelectric materials has entered a new stage. Using P-type and N-type semiconductor thermoelectric materials in series can make thermoelectric refrigeration and power generation devices. Thermoelectric devices have many advantages such as no pollution, no noise, no moving parts, and no vibration. The conversion efficiency of a thermoelectric device mainly depends on the dimensionless thermoelectric figure of merit of the material: ZT=(α 2 σ/κ)T. Where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the thermodynamic temperature.
碲化铋是目前室温附近性能最优，商业化应用最广的热电材料。目前报道的P型碲化铋合金的ZT值达到1.4，而N型碲化铋合金的ZT值相对较低。如Teo Sung Oh等(T.S.Oh,D.B.Hyun,and N.V Kolomoets,Thermoelectric Properties of The Hot-Pressed(Bi,Sb)2(Te,Se)3Alloys.Scripta Materialia,2000.42(9):849-854)利用粉末冶金的方法制备的N型材料最大ZT值为0.58。又如，Jiang等(J.Jiang,L.D.Chen,Q.Yao,S.Q.Bai,andQ.Wang,Effect of TeI4Content On The Thermoelectric Properties of n-type-Bi-Te-Se Crystals Prepared by Zone Melting.Materials Chemistry and Physics,2005.92(1):39-42.)利用区熔法制备了掺杂Tel4的N型碲化铋材料，掺杂后样品的ZT值达到0.9。Bismuth telluride is currently the thermoelectric material with the best performance near room temperature and the most widely used commercially. The reported ZT value of P-type bismuth telluride alloy reaches 1.4, while the ZT value of N-type bismuth telluride alloy is relatively low. Such as Teo Sung Oh et al. (TSOh, DBHyun, and NV Kolomoets, Thermoelectric Properties of The Hot-Pressed (Bi, Sb) 2 (Te, Se) 3 Alloys. Scripta Materialia, 2000.42 (9): 849-854) using powder metallurgy The maximum ZT value of the N-type material prepared by the method is 0.58. As another example, Jiang et al. (J. Jiang, LDChen, Q. Yao, SQ Bai, and Q. Wang, Effect of TeI4Content On The Thermoelectric Properties of n-type-Bi-Te-Se Crystals Prepared by Zone Melting. 2005.92(1):39-42.) Prepared Tel4-doped N-type bismuth telluride material by zone melting method, and the ZT value of the sample after doping reached 0.9.
近年来，提出了一种通过新型的热挤压工艺来优化碲化铋材料的热电和机械性能的方法，如Hong和Lee等(S.J.Hong,Y.S.Lee,J.W.Byeon,andB.S.Chun,Optimum DopantContent of n-tyPe95％Bi2Te3+5％Bi2Se3Compounds Fabricated by Gas Atomizationand Extrusion Process.Journal of Alloys and ComPounds,2006.414(1-2):146-151)通过将N型Bi-Te-Se合金按照一定比例进行热挤压，研究得到的N型材料的最高Z值为0.92。但采用该方法制备得到的Z值大多在1附近，再次提升较为困难。In recent years, a method to optimize the thermoelectric and mechanical properties of bismuth telluride materials through a novel hot extrusion process has been proposed, such as Hong and Lee et al. -tyPe95%Bi 2 Te 3 +5%Bi 2 Se 3 Compounds Fabricated by Gas Atomization and Extrusion Process.Journal of Alloys and ComPounds, 2006.414(1-2):146-151) by making the N-type Bi-Te-Se alloy according to A certain proportion of hot extrusion, the highest Z value of the obtained N-type material is 0.92. However, most of the Z values prepared by this method are around 1, and it is difficult to increase it again.
高性能的热电器件需要P型和N型材料的热电性能相匹配，所以寻求一种能有效提高N型碲化铋合金热电性能的加工工艺非常有意义。High-performance thermoelectric devices need to match the thermoelectric properties of P-type and N-type materials, so it is very meaningful to seek a processing technology that can effectively improve the thermoelectric properties of N-type bismuth telluride alloys.
发明内容Contents of the invention
本发明提供一种提高N型碲化铋基烧结块体热电材料性能的加工方法，利用重复低速热变形诱导工艺，大幅提升N型碲化铋基材料的热电性能。The invention provides a processing method for improving the performance of an N-type bismuth telluride-based sintered block thermoelectric material, which greatly improves the thermoelectric performance of the N-type bismuth telluride-based material by using repeated low-speed thermal deformation induction processes.
一种提高N型碲化铋基粉末烧结块体热电材料性能的加工方法，将热压成型的N型碲化铋基块体置于模具中，500～550℃、压力条件下进行低速热变形，控制块体沿高度方向的变化率为0.2～3mm/min，保持1～10min后，撤去压力，保温2～60min，重复上述过程至少一次。A processing method for improving the performance of N-type bismuth telluride-based powder sintered block thermoelectric materials. The hot-pressed N-type bismuth telluride-based block is placed in a mold, and subjected to low-speed thermal deformation under pressure conditions of 500-550°C , control the rate of change of the block along the height direction to 0.2-3 mm/min, keep it for 1-10 minutes, remove the pressure, keep it warm for 2-60 minutes, and repeat the above process at least once.
经本发明的研究发现，热变形诱导的多尺度微观效应，包括微米级的形变织构，再结晶诱导的原位纳米晶，原子级的晶体缺陷，可以有效改善材料的热电性能。这些效应一方面可以调节碲化铋材料内部的载流子浓度和输运过程，提高材料的电学性能；另一方面可以散射声子，降低材料的晶格热导率。两方面的共同作用导致材料热电性能的极大提升。本发明中，进一步通过对试样进行多次、低速热变形-保温处理，将有效地增强以上效应，进而大幅度提升材料的热电性能。尤其在N型碲化铋材料中，重复低速热变形对热电性能的提升作用颇为显著。According to the research of the present invention, it is found that thermal deformation-induced multi-scale microscopic effects, including micron-scale deformation texture, recrystallization-induced in-situ nanocrystals, and atomic-level crystal defects, can effectively improve the thermoelectric properties of materials. On the one hand, these effects can adjust the carrier concentration and transport process inside the bismuth telluride material to improve the electrical properties of the material; on the other hand, they can scatter phonons and reduce the lattice thermal conductivity of the material. The combined effect of the two aspects leads to a great improvement in the thermoelectric performance of the material. In the present invention, the above effects will be effectively enhanced by further performing multiple, low-speed thermal deformation-insulation treatments on the sample, thereby greatly improving the thermoelectric performance of the material. Especially in N-type bismuth telluride materials, repeated low-speed thermal deformation can significantly improve the thermoelectric performance.
将热压成型的N型碲化铋基块状材料放入常规模具中，重复低速热变形—保温可以得到多次形变的合金试样。通过控制试样的变形速度及程度，每道次将试样压缩至一定变形程度后进行保温。如此反复，直至试样完全充满模具，即可得到热电性能优异的试样。The hot-pressed N-type bismuth telluride-based bulk material is put into a conventional mold, and repeated low-speed thermal deformation-insulation can obtain alloy samples with multiple deformations. By controlling the deformation speed and degree of the sample, the sample is compressed to a certain degree of deformation in each pass and then kept warm. This is repeated until the sample is completely filled with the mold, and then a sample with excellent thermoelectric properties can be obtained.
所述的热压成型的N型碲化铋基块体为由N型商业化碲化铋合金经热压烧结制成的块体；The hot-pressed N-type bismuth telluride-based block is a block made of N-type commercial bismuth telluride alloy through hot-press sintering;
或者为，由高纯元素铋、碲、硒熔炼得到的N型多晶碲化铋基材料经热压烧结制成的块体。Alternatively, it is a block made of N-type polycrystalline bismuth telluride-based material obtained by smelting high-purity elements bismuth, tellurium, and selenium through hot-pressing sintering.
作为优选，所述模具的直径为热压成型的N型碲化铋基块体直径的1.25～2倍。在相同的变形速率下，模具的尺寸影响试样的变形程度，实验证明模具尺寸过小，变形程度较小，织构发展不充分，模具尺寸过大，容易由于摩擦力的作用造成非均匀变形，不利于整体性能的优化。Preferably, the diameter of the mold is 1.25 to 2 times the diameter of the hot-pressed N-type bismuth telluride-based block. Under the same deformation rate, the size of the mold affects the degree of deformation of the sample. Experiments have shown that the size of the mold is too small, the degree of deformation is small, the texture is not fully developed, and the size of the mold is too large, which is easy to cause non-uniform deformation due to the effect of friction , which is not conducive to the optimization of the overall performance.
作为优选，保温的温度等于低速热变形的温度。Preferably, the temperature of heat preservation is equal to the temperature of low-speed thermal deformation.
作为优选，所述低速热变形时，控制块体沿高度方向的变化率为0.2～2.5mm/min，保持的时间为1～2min。进一步优选，所述的热压成型的N型碲化铋基块体为由高纯元素铋、碲、硒熔炼得到的N型多晶碲化铋基材料经热压烧结制成的块体，在550℃、压力下控制块体沿高度方向的变化率为2.5mm/min，保持的时间为1min，撤下压力后的保温时间为2～50min。再优选，撤下压力后的保温时间为50min。更优选，所述N型碲化铋基块状材料为由高纯元素铋、碲、硒根据化学式Bi2Te2.2Se0.8的配比经熔炼、热压烧结制备得到的。Preferably, during the low-speed thermal deformation, the rate of change of the block along the height direction is controlled to be 0.2-2.5 mm/min, and the holding time is 1-2 min. Further preferably, the hot-pressed N-type bismuth telluride-based block is a block made of N-type polycrystalline bismuth telluride-based material obtained by smelting high-purity elements bismuth, tellurium, and selenium through hot-press sintering, At 550°C and under pressure, the rate of change of the block along the height direction is controlled to be 2.5 mm/min, the holding time is 1 min, and the holding time after the pressure is removed is 2 to 50 min. More preferably, the heat preservation time after the pressure is removed is 50min. More preferably, the N-type bismuth telluride-based bulk material is prepared from high-purity elements bismuth, tellurium, and selenium according to the chemical formula Bi 2 Te 2.2 Se 0.8 through melting and hot-pressing sintering.
作为优选，所述低速热变形-保温处理的次数为2～4次。Preferably, the number of times of the low-speed thermal deformation-insulation treatment is 2 to 4 times.
本发明的有益效果是：The beneficial effects of the present invention are:
热变形诱导的多尺度微观效应可调控材料的载流子浓度和材料微结构。多次、低速热变形可有效的增强这一效应，从而显著改善N型碲化铋材料的热电性能，本发明成功地将N型材料的ZT值提高到1.2，是目前世界上报道的N型材料的最高值。Thermal deformation-induced multi-scale microscopic effects can regulate the carrier concentration and material microstructure of materials. Multiple, low-speed thermal deformation can effectively enhance this effect, thereby significantly improving the thermoelectric properties of N-type bismuth telluride materials. The invention successfully increases the ZT value of N-type materials to 1.2, which is the N-type bismuth telluride reported in the world. The highest value for the material.
与高性能P型材料组成器件后，热电转换效率可以得到大幅的提升。并且整个反复低速热变形—保温过程中可在同一模具中完成，生产效率极大提高。After the device is composed of high-performance P-type materials, the thermoelectric conversion efficiency can be greatly improved. Moreover, the entire repeated low-speed thermal deformation-heat preservation process can be completed in the same mold, and the production efficiency is greatly improved.
本发明的加工方法可重复性好，效果显著，调控简单，是一种有效地生产高性能N型碲化铋材料的方法，具有一定的工业实用价值和理论研究意义。The processing method of the invention has good repeatability, remarkable effect and simple control, is a method for effectively producing high-performance N-type bismuth telluride materials, and has certain industrial practical value and theoretical research significance.
具体实施方式detailed description
以下结合实例对本发明进行下一步详细阐述：The present invention is described in detail in the next step in conjunction with examples:
参比例1Reference example 1
选用区熔法制备的N型商业化碲化铋合金，球磨粉碎过筛后放入Ф12.6mm的模具热压烧结后制成块体。烧结试样的ZT值在500K达到最大值0.57。The N-type commercial bismuth telluride alloy prepared by the zone melting method was selected, ball milled and sieved, put into a Ф12.6mm mold for hot pressing and sintering, and then made into a block. The ZT value of the sintered sample reaches a maximum value of 0.57 at 500K.
参比例2Reference example 2
利用高纯元素铋、碲、硒按照化学式Bi2Te2.2Se0.8配比，真空熔炼得到铸锭，球磨过筛后放入Ф12.6mm的模具热压烧结后制成块体。烧结试样的ZT值在450K达到最大值0.52。Using high-purity elements bismuth, tellurium, and selenium according to the chemical formula Bi 2 Te 2.2 Se 0.8 , the ingot is vacuum smelted, ball milled and sieved, put into a Ф12.6mm mold for hot pressing and sintering to make a block. The ZT value of the sintered sample reaches a maximum value of 0.52 at 450K.
实施例1Example 1
取参比例1中制备的块体，放入Ф20mm的模具中，500℃、压力条件下进行低速热变形，控制块体沿高度方向的变化率为0.3mm/min，保持2min后，停止施加压力，500℃下保温5min。然后再次施加压力进行低速热变形，控制块体沿高度方向的变化率为0.3mm/min，变形至试样完全充模，得到二次热变形试样。该试样在500K时ZT值为0.87，较参比例1中烧结试样提升53％。Take the block prepared in Reference Example 1, put it into a Ф20mm mold, and perform low-speed thermal deformation at 500°C under pressure, control the rate of change of the block along the height direction to 0.3mm/min, keep it for 2min, and stop applying pressure , kept at 500°C for 5 minutes. Then apply pressure again for low-speed thermal deformation, control the change rate of the block along the height direction to 0.3mm/min, and deform until the sample is completely filled in the mold to obtain a secondary thermal deformation sample. The ZT value of this sample at 500K is 0.87, which is 53% higher than that of the sintered sample in Reference Example 1.
实施例2Example 2
取参比例1中制备的块体，放入Ф20mm的模具中，500℃、压力条件下进行低速热变形，控制块体沿高度方向的变化率为0.3mm/min，保持2min后，停止施加压力，500℃下保温5min。重复相同的操作，控制块体沿高度方向的变化率为0.3mm/min，再次保持2min，卸压，500℃下保温5min。最后控制块体沿高度方向的变化率为0.3mm/min，变形至试样完全充模，得到三次热变形试样。测得该试样在500K时ZT值为0.92，较参比例1中烧结试样提升了61％。Take the block prepared in Reference Example 1, put it into a Ф20mm mold, and perform low-speed thermal deformation at 500°C under pressure, control the rate of change of the block along the height direction to 0.3mm/min, keep it for 2min, and stop applying pressure , kept at 500°C for 5 minutes. Repeat the same operation, control the rate of change of the block along the height direction to 0.3mm/min, keep it for 2 minutes again, release the pressure, and keep warm at 500°C for 5 minutes. Finally, the rate of change of the block along the height direction is controlled to 0.3 mm/min, and the deformation is performed until the sample is completely filled in the mold, and three thermal deformation samples are obtained. It is measured that the ZT value of the sample is 0.92 at 500K, which is 61% higher than that of the sintered sample in Reference Example 1.
实施例3Example 3
取参比例1中制备的块体，放入Ф20mm的模具中，500℃、压力条件下进行低速热变形，控制块体沿高度方向的变化率为0.3mm/min，保持2min后，停止施加压力，500℃下保温5min。再重复相同的操作两次，控制块体沿高度方向的变化率为0.3mm/min，再次保持2min，卸压，500℃下保温5min。最后控制块体沿高度方向的变化率为0.3mm/min，变形至试样完全充模，得到四次热变形试样。测得该试样在500K时的ZT值为1.00，较参比例1中烧结试样提升了75.4％。Take the block prepared in Reference Example 1, put it into a Ф20mm mold, and perform low-speed thermal deformation at 500°C under pressure, control the rate of change of the block along the height direction to 0.3mm/min, keep it for 2min, and stop applying pressure , kept at 500°C for 5 minutes. Repeat the same operation two more times, control the rate of change of the block along the height direction to 0.3mm/min, keep it for 2 minutes again, release the pressure, and keep warm at 500°C for 5 minutes. Finally, the rate of change of the block along the height direction is controlled to 0.3 mm/min, and the deformation is performed until the sample is completely filled in the mold to obtain four thermally deformed samples. It is measured that the ZT value of the sample at 500K is 1.00, which is 75.4% higher than that of the sintered sample in Reference Example 1.
实施例4Example 4
取参比例2中制备的块体，放入Ф20mm的模具中，550℃、压力条件下进行低速热变形，控制块体沿高度方向的变化率为2.5mm/min，保持1min后，停止施加压力，550℃下保温50min。然后再控制块体沿高度方向的变化率为2.5mm/min，变形至试样完全充模，得到二次热变形试样。该试样在450K时ZT值为1.1，较参比例2中烧结试样提升了104％。Take the block prepared in Reference Example 2, put it into a Ф20mm mold, and perform low-speed thermal deformation under pressure at 550°C, control the rate of change of the block along the height direction to 2.5mm/min, keep it for 1min, and stop applying pressure , kept at 550°C for 50min. Then control the rate of change of the block along the height direction to 2.5 mm/min, deform until the sample is completely filled in the mold, and obtain a secondary thermally deformed sample. The sample has a ZT value of 1.1 at 450K, which is 104% higher than that of the sintered sample in reference example 2.
实施例5Example 5
取参比例2中制备的块体，放入Ф20mm的模具中，550℃、压力条件下进行低速热变形，控制块体沿高度方向的变化率为2.5mm/min，保持1min后，停止施加压力，550℃下保温50min。重复该过程一次，最后控制块体沿高度方向的变化率为2.5mm/min，变形至试样完全充模，得到三次热变形试样。该试样在450K时ZT值达到1.2，较参比例2中烧结试样提升了125％。Take the block prepared in Reference Example 2, put it into a Ф20mm mold, and perform low-speed thermal deformation under pressure at 550°C, control the rate of change of the block along the height direction to 2.5mm/min, keep it for 1min, and stop applying pressure , kept at 550°C for 50min. Repeat this process once, and finally control the rate of change of the block along the height direction to 2.5 mm/min, deform until the sample is completely filled, and obtain three thermally deformed samples. The ZT value of this sample reaches 1.2 at 450K, which is 125% higher than that of the sintered sample in Reference Example 2.
对比例1Comparative example 1
取参比例1中制备的块体，放入Ф20mm的模具中，550℃下采用热锻的工艺，80Mpa保压30min得到最终产品的ZT值为0.82。Take the block prepared in Reference Example 1, put it into a Ф20mm mold, adopt a hot forging process at 550°C, and hold the pressure at 80Mpa for 30min to obtain a ZT value of the final product of 0.82.
对比例2Comparative example 2
取参比例2中制备的块体，放入Ф20mm的模具中，550℃下采用热锻的工艺，80MPa保压30min得到最终产品的ZT值为0.97。Take the block prepared in Reference Example 2, put it into a Ф20mm mold, adopt a hot forging process at 550°C, and hold the pressure at 80MPa for 30min to obtain a ZT value of the final product of 0.97.
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| CN111875381A (en) * | 2020-08-03 | 2020-11-03 | 深圳见炬科技有限公司 | Preparation method of N-type bismuth telluride thermoelectric block material |
| CN114408876B (en) * | 2022-01-07 | 2023-04-18 | 武汉理工大学 | High-strength high-plasticity silver telluride and preparation method thereof |
| CN114735658A (en) * | 2022-04-12 | 2022-07-12 | 广西自贸区见炬科技有限公司 | N-type bismuth telluride-based alloy and preparation method thereof |
| CN115287754B (en) * | 2022-07-15 | 2024-02-02 | 湖北赛格瑞新能源科技有限公司 | Preparation method of n-type polycrystalline bismuth telluride-based thermoelectric material based on mold-free upsetting |
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