Cu2S在脉冲电场下的超快速制备及其热电性能

doi:10.15541/jim20190096

无机材料学报 ›› 2019, Vol. 34 ›› Issue (12): 1295-1300.DOI: 10.15541/jim20190096

所属专题：热电材料与器件

Cu₂S在脉冲电场下的超快速制备及其热电性能

龚皓,苏贤礼,鄢永高(),唐新峰()

武汉理工大学材料复合新技术国家重点实验室, 武汉 430070

收稿日期:2019-03-04 修回日期:2019-04-24 出版日期:2019-12-20 网络出版日期:2019-06-17
作者简介:龚皓(1991-), 男, 硕士研究生. E-mail:441512157@qq.com
基金资助:
国家重点研发计划(2018YFB0703600);国家自然科学基金(51772232)

Ultra-fast Synthesis of Cu₂S Thermoelectric Materials under Pulsed Electric Field

GONG Hao,SU Xian-Li,YAN Yong-Gao(),TANG Xin-Feng()

State Key Laboratory of Advanced Technology for Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

Received:2019-03-04 Revised:2019-04-24 Published:2019-12-20 Online:2019-06-17
Supported by:
National Key Research and Development Program of China(2018YFB0703600);National Natural Science Foundation of China(51772232)

摘要/Abstract

摘要：

Cu₂S是一种声子液体-电子晶体材料, 具有优良的热电性能, 但是传统的制备方法过程繁琐而且难以得到成分均匀、致密度高以及性能优良的块体材料。本研究引入了仅耗时30 s的强脉冲电场合成法来一步完成Cu₂S材料的合成与烧结。在强脉冲电场作用下Cu₂S的合成分为三步, 最初是形成了少量的CuS和Cu₂S, 接着生成了大部分Cu₂S与部分Cu_1.96S, 最终未完全反应的Cu_1.96S与Cu生成了完全单相的Cu₂S。本方法得到的Cu₂S块体是致密且均匀的单相, 并且包含丰富的多尺度微观结构。通过Cu缺失比可以使Cu_2-_xS的性能得到优化, 其中Cu_1.97S能在873 K时获得最高的ZT(0.72), 相比于本征样品提升了49%。

关键词: Cu₂S热电材料, 脉冲电场, 超快速制备, Cu缺失

Abstract:

Cu₂S shows excellent thermoelectric properties as a material with phonon liquid-electron crystal characteristics. However, traditional preparation methods are cumbersome and difficult to afford bulk Cu₂S with uniform composition, high density and excellent thermoelectric properties. In this study, a novel method named Pulsed Electric Current Sintering was introduced to synthesize and sinter Cu₂S materials in one step consuming only 30 s. The synthesis of Cu₂S under intense pulsed electric field includes three steps. A small amount of CuS and Cu₂S forms in the first step; most of Cu₂S and part of Cu_1.96S are produced in the second step; finally, the remained Cu_1.96S and Cu react to form completely pure Cu₂S. The Cu₂S bulk obtained by this method is a dense bulk with homogeneous composition, and contained abundant multi-scale microstructures. The thermoelectric performance is optimized by regulation of Cu-deficient Cu_2-_xS. The maximum ZT of Cu_1.97S bulk at 873 K is 0.72, which is 49% higher than that of the pristine sample.

Key words: Cu₂S thermoelectric material, pulsed electric current, ultra-fast synthesis, Cu deficiency

中图分类号:

TN377

龚皓, 苏贤礼, 鄢永高, 唐新峰. Cu₂S在脉冲电场下的超快速制备及其热电性能[J]. 无机材料学报, 2019, 34(12): 1295-1300.

GONG Hao, SU Xian-Li, YAN Yong-Gao, TANG Xin-Feng. Ultra-fast Synthesis of Cu₂S Thermoelectric Materials under Pulsed Electric Field[J]. Journal of Inorganic Materials, 2019, 34(12): 1295-1300.

图/表 11

图1 样品烧结过程示意图

Fig. 1 Schematic diagram of sample sintering process

图2 DCS样品与PECS样品在合成过程中电流与温度随时间的变化图

Fig. 2 Variations of current and temperature of DCS sample and PECS sample during the synthetic process

图3 DCS典型样品在电流方向上的两侧表面

Fig. 3 Surfaces of both sides of a typical DCS sample in the current direction

图4 PECS典型样品在电流方向上的两侧表面

Fig. 4 Surfaces of both sides of a typical PECS sample in the current direction

图5 PECS样品与DCS样品两侧表面的XRD图谱

Fig. 5 XRD patterns of both sides of PECS sample and DCS sample

图6 在不同反应时间下PECS样品的XRD图谱

Fig. 6 XRD patterns of PECS samples prepared at different reaction time

图7 脉冲电流和模具位移与时间的关系图

Fig. 7 Profiles of the pulse current and sintering displacement varied with time

图8 PECS样品的抛光面的Cu元素(a)与S元素(b)的面分布图, 对应区域的背散射电子图(c)与微区成分(d)分析结果

Fig. 8 Distribution mapping of element Cu (a) and S (b) on polished surface of PECS sample, with back scattering image (c) and chemical compositions (d) of the same area as above figures

图9 PECS样品的断面在不同尺度下的二次电子成像照片

Fig. 9 Secondary electron images of a fracture surface of PECS sample on different magnification scales

图10 PECS-Cu2-xS(0<x≤0.2)的XRD图谱

Fig. 10 XRD patterns of PECS-Cu2-xS(0<x≤0.2)

图11 PECS-Cu2S的比热容(a)、热扩散系数(b)以及PECS-Cu2-xS样品的电导率(c)、Seebeck系数(d)、热导率(e)和ZT(f)与温度的曲线

Fig. 11 Temperature dependence of heat capacity(a), thermal diffusivity(b) of PECS-Cu2S, and electrical conductivity (c), Seebeck coefficient (d), thermal conductivity (e), ZT (f) of PECS-Cu2-xS

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Cu₂S在脉冲电场下的超快速制备及其热电性能

Ultra-fast Synthesis of Cu₂S Thermoelectric Materials under Pulsed Electric Field

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