n型填充方钴矿热电材料的快速制备研究

doi:10.15541/jim20160136

摘要/Abstract

摘要：

如何有效控制方钴矿基热电材料的制备成本成为其商业化应用的瓶颈。本课题组采用一种简单并且可放量的方法来制备n型填充方钴矿热电材料。该法由感应熔融淬、火和放电等离子烧结(SPS)组成, 制备周期(少于30 min)远小于传统制备方法: 电阻炉熔融(超过24 h),退火(1 w)和SPS。该法同传统制备工艺相当, 制备的方钴矿块体材料具有相对均匀的物相成份和组织结构, 以及良好的热电性能, 这得益于将经历感应熔融、淬火冷凝工艺形成的Sb/CoSb/CoSb₂包晶偏析结构破坏, 能同时实现快速反应和致密化。良好的热电性能和较少的生产周期及能耗, 使该法有望发展成为具有潜在应用前景的填充方钴矿热电材料工业化制备工艺。

关键词: 填充方钴矿材料, 熔融-淬火/放电等离子烧结, 微观组织结构, 热电性能

Abstract:

The cost-effective fabrication of CoSb₃-based filled skutterudites (SKD) thermoelectric materials is a bottleneck issue preventing their successful commercial application. In this study, we employed a simple and scalable process to simultaneously produce a rapid formation and consolidation of n-type filled skutterudites. This method, consisting of RF-induction melting, quenching and spark plasma sintering (SPS), required less than a half-hour, significantly shorter than conventional process of furnace melting (over 24 h), annealing (about one week) and SPS. The fabricated bulk SKD materials possessed homogeneous composition and structures with a good thermoelectric performance which are analogous to those materials fabricated according to a conventional process. The homogeneous microstructures and phase composition distribution which was a result of the simultaneously proceeded rapid reaction and densification of the grinding-destructed dendrite networks of the Sb/CoSb/CoSb₂ peritectic structure formed in the RF-induction melting and quenching. The good thermoelectric TE performance and the very low consumption of process time and energy would make this simple process a potential and practical method for industrial-level mass production of filled skutterudite thermoelectric materials.

Key words: filled skutterudites, melting-quenching/SPS, microstructure, thermoelectric performance

中图分类号:

TQ174

姚铮, 仇鹏飞, 李小亚, 陈立东. n型填充方钴矿热电材料的快速制备研究[J]. 无机材料学报, 2016, 31(12): 1375-1382.

YAO Zheng, QIU Peng-Fei, LI Xiao-Ya, CHEN Li-Dong. Investigation on Quick Fabrication of n-type Filled Skutterudites[J]. Journal of Inorganic Materials, 2016, 31(12): 1375-1382.

图/表 8

Fig. 1(a) represents the Co-Sb binary phase diagram from Ref.[26]. Due to the presence of a Co-Sb peritectic reaction at a temperature of about 876℃, the CoSb3 skutterudite phase could not be directly formed after quenching. This was confirmed by investigating the XRD pattern of the quenched ingot which experienced a 300 s induction-melting at 1353 K (see Fig. 1(b)). The ingot consisted of a mixture of CoSb, CoSb2, Sb and YbSb2. No X-ray diffraction peaks belonging to the Skutterudite phase were detected. SEM and EDS analyses shown in Fig. 1(c) further proved the coexistence of CoSb, CoSb2, and Sb in the quenched ingot. Presence of these phases formed typical dendrite networks, in which CoSb primary phases encircled with CoSb2 peritectic phases were unevenly distributed in the Sb matrix. Under higher magnification (see Fig. 1(d)), some bar-shape areas with brighter contrast were also observed in the Sb matrix, which were identified as YbSb2 by EDS. Such microstructure features are identical to that observed in the ingots prepared using a traditional long-term (48 h) melting process reported in Ref.[27]. However, the melting duration in this study is greatly reduced to as short as 300 s, which is meaningful for future industrial-level mass production.

Fig. 1 (a) Co-Sb binary phase diagram from Ref. [26], (b) XRD patterns of the quenched sample, and (c, d) back scattering electron images of the quenched sample under different magnification

Fig. 2 XRD patterns for the melting-quenching/SPSed samples

Fig. 3 Back scattering electron images of the melting-quenching/ SPSed samples

Fig. 4 Yb filling fractions in the melting-quenching/SPSed samples

Fig. 5 Cross-section morphologies for the samples (a) 863 K-5 min, (b) 943 K-5 min and (c) TM, respectively, and (d) magnified image of (a), and (e, f) the EDS analyses on the two points (spectrum 115 and 116) shown in (d)

Fig. 6 Sketch of the reaction mechanism in the annealing process for the traditional melting-quenching/annealing method

Fig. 7 Temperature dependences of TE properties of the samples prepared by the melting-quenching/SPS method The data for the TM sample are also included for comparison

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