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中国物理学会期刊

Cu1.8–x Sbx S热电材料的相结构与电热输运性能

CSTR: 32037.14.aps.70.20201852

Phase structure and thermoelectric properties of Cu1.8–x Sbx S thermoelectric material

CSTR: 32037.14.aps.70.20201852
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  • Cu1.8S基热电材料因其丰富的原料储备、低毒性及优良的电学和热学性能而成为具有应用潜力的热电材料. 本文采用机械合金化(mechanical alloying, MA)结合放电等离子烧结(spark plasma sintering, SPS)工艺制备了一系列Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)块体材料, 研究了不同Sb掺杂量对Cu1.8–x Sbx S相结构、微观形貌及热电性能的影响. 结果表明, 随着Sb含量的增加, Cu1.8–x Sbx S材料相结构由单相Cu1.8S转变为多相共存, 其块体均呈p型导电特征. 样品Cu1.77Sb0.03S在723 K时取得最高ZT值约为0.37, 比未掺杂Cu1.8S(0.33)提高了12%.

     

    Cu1.8S-based materials have become potential thermoelectric materials due to their rich raw material reserves, low toxicity, and excellent electrical and thermal properties. In this study, a series of Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04) bulk materials is synthesized by using mechanical alloying combined with spark plasma sintering process. This preparation method can shorten the preparation cycle of materials, and effectively improve the research and development efficiency of thermoelectric (TE) materials due to its simple process. The effects of different Sb doping amounts on the structure, micromorphology, and thermoelectric transport properties of Cu1.8–x Sbx S phase are investigated. The results show that when 0 ≤ x < 0.02, the bulk samples are single-phase Cu1.8S. With the further increase of Sb doping to 0.02 ≤ x ≤ 0.04, the second phase CuSbS2 is formed when Sb content exceeds the solid solubility limit of x = 0.02 in Cu1.8S, all Cu1.8–x Sbx S bulk samples exhibit p-type conductivity characteristics. Benefitting from the synergistic phonon scattering effect by multiscale defects, such as point defects (\rmSb_\rmCu^ \bullet\bullet , \rmV_\rmS^ \bullet \bullet ), nanopores, secondary phases (CuSbS2), and dislocations, the thermal conductivity κ declines significantly from 1.76 W·m–1·K–1 (x = 0) to 0.99 W·m–1·K–1 at 723 K for the Cu1.76Sb0.04S sample. Finally, the peak dimensionless TE figure of merit (ZT ) value of 0.37 is achieved at 723 K for Cu1.77Sb0.03S resulting from a low thermal conductivity of 1.11 W·m–1·K–1 combining an appropriate power factor of 563 μW·m–1·K–2, which is 12% higher than that (0.33) of pristine Cu1.8S. Although the Sb doped Cu1.8S-based samples have lower thermal conductivity κ, the reduced power factor cannot be offset by reducing the thermal conductivity κ, so the TE figure of merit (ZT ) value is not significantly improved. Therefore, there is still much room for improving the performance of Sb doped Cu1.8S-based thermoelectric material, and its thermoelectric performance can be further optimized through nano-second phase recombination, energy band engineering, and introducing multi-scale defects, etc. Our results suggest that the introduction of Sb into thermoelectric materials is an effective and convenient strategy to improve ZT value by reducing thermal conductivity κ.

     

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