区熔n型Bi1.96Sb0.04Te2.70Se0.30热电材料均匀性研究

doi:10.15541/jim20250045

摘要/Abstract

摘要： 区熔制备技术是商业化制备Bi₂Te₃基热电材料的重要方法,区熔纯化过程受材料分凝的影响,但迄今为止,区熔工艺对Bi₂Te₃基材料分凝机制影响的研究尚未形成统一的认识,特别是材料组元增加后会显著影响分凝过程和均匀性。本研究以n型Bi_1.96Sb_0.04Te_2.694Se_0.3Br_0.006材料为研究对象,采用熔融-区熔-退火工艺,系统探讨了区熔温度对材料组成和热电性能均匀性的影响规律,发现区熔温度对棒材均匀性有很大影响,轴向组成分凝是影响其均匀性的重要因素,在高区熔温度(≥ 988 K)下,棒材顶部出现了Bi₂Te₃富集相的分凝,这种组成分凝现象不利于材料热电性能的均匀性差。区熔温度为988 和1003 K样品的室温ZT在不同区域(顶部中心、顶部边缘、底部中心、底部边缘)最大差异达到了31.5%和28.6 %。降低区熔温度至958 K显著抑制了Bi₂Te₃富集相分凝,制备出了具有优异热电性能和均匀性的圆柱型锭体(内径16 mm,高55 mm),样品不同区域的室温ZT最大差异仅为14%,并且958 K-ET样品在350 K下获得最大ZT为1.05。本研究揭示了区熔温度对多组元n型(Bi, Sb)₂(Te, Se)₃基材料组成成分及热电性能均匀性的调控机制,为制备具有优异均匀性的高性能热电材料提供了重要指导。

关键词: n型碲化铋, 区熔工艺, 均匀性, 热电性能

Abstract: Zone melting technique is an important method for the commercial preparation of Bi₂Te₃-based thermoelectric materials. The zone melting purification process is affected by the segregation of materials. However, so far, the effect of zone melting process on the segregation mechanism of Bi₂Te₃-based materials has not yet formed unified understanding. In particular, the increase of material components significantly affect the segregation process and uniformity. In this study, n-type Bi_1.96Sb_0.04Te_2.694Se_0.3Br_0.006 material was used as the research object, and the melting-zone melting-annealing process was used to systematically explore the influence of zone melting temperature on the composition and uniformity of thermoelectric performance for the material. It was found that the zone melting temperature had a great influence on the uniformity of the ingot, and the axial composition segregation was an important factor affecting its uniformity. At high zone melting temperature (≥ 988 K), the segregation of Bi₂Te₃-rich phase appeared at the top of the ingot, which made the poor uniformity of thermoelectric properties of the material. The maximum difference of ZT at room temperature in different regions (top center, top edge, bottom center, bottom edge) of samples with zone melting temperature of 988 and 1003 K reached 31.5% and 28.6%, respectively. Reducing the zone melting temperature to 958 K significantly inhibited the segregation of Bi₂Te₃-enriched phase, and a cylindrical ingot (inner diameter of 16 mm, height of 55 mm) with excellent thermoelectric properties and uniformity was prepared. The maximum difference of ZT at room temperature in different regions was only 14%, and the maximum ZT of 958 K-ET sample was 1.05 at 350 K. This study reveals the regulation mechanism of zone melting temperature on the composition and thermoelectric performance uniformity of multi-component n-type (Bi, Sb)₂(Te, Se)₃-based materials, which provides important guidance for the preparation of high-performance thermoelectric materials with excellent uniformity.

Key words: n-type bismuth telluride, zone melting process, homogeneity, thermoelectric properties

中图分类号:

TQ174

吴明轩, 李珺杰, 陈硕, 鄢永高, 苏贤礼, 张清杰, 唐新峰. 区熔n型Bi_1.96Sb_0.04Te_2.70Se_0.30热电材料均匀性研究[J]. 无机材料学报, DOI: 10.15541/jim20250045.

WU Mingxuan, LI Junjie, CHEN Shuo, YAN Yonggao, SU Xianli, ZHANG Qingjie, TANG Xinfeng. Homogeneity of Zone-melted n-type Bi_1.96Sb_0.04Te_2.70Se_0.30Thermoelectric Material[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250045.

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