高优值系数In4Se3多晶的制备及其热电输运特性

doi:10.15541/jim20140396

摘要/Abstract

摘要：

分别采用不同的熔炼、退火工艺, 结合放电等离子烧结方法制备了块状多晶In₄Se₃热电材料。研究了熔炼时间和退火时间对材料物相、成分、显微结构及热电性能的影响。熔炼后铸锭中存在In及InSe杂相, Se缺失量随熔炼时间的延长而增加, 使得样品载流子浓度增大, 电导率有所提高, 熔炼48 h样品ZT值相对较高。在确定熔炼工艺的基础上, 进行不同时间的退火处理后, InSe相消失, 显微结构中分布有较大尺寸的台阶状结构, 这种台阶状结构有利于降低热导率, 而对电导率无明显影响。实验结果表明: 一定程度延长熔炼时间、退火时间对提高样品的热电性能有积极作用, 其中熔炼48 h再退火96 h后的样品ZT值最高, 在702 K达到0.83, 比文献值提高约32%。

关键词: In4Se3, 热电性能, 真空熔炼, 退火

Abstract:

Polycrystalline In₄Se₃ thermoelectric materials were synthesized in the processing sequence of vacuum melting, annealing and spark plasma sintering. The effect(s) of melting and annealing duration periods on the phase, composition, microstructure, and thermoelectric properties of polycrystalline In₄Se₃ were investigated. After the melting process, both In and InSe phase were detected in the ingots. With increasing melting duration time, an increase in Se deficiency was observed, leading to an increase of carrier concentration, which contributed to the observed improvement of electrical conductivity. The specimen melted for 48 h showed relatively higher ZT. Thus on the basis of 48 h melting process, the ingots were then annealed for different periods of time, which eliminated the presence of InSe phase. After annealing, scattered large step-like structures were observed in the matrix, which favored the reduction of thermal conductivity but had no significant influence on the electrical conductivity. The ZT was significantly enhanced to 0.83 at 702 K by extending melting and annealing duration time to 48 h and 96 h, respectively, which is 32% higher than that reported in literature. It was concluded that both the extension of melting and annealing duration periods could improve the thermoelectric performance of polycrystalline In₄Se₃.

Key words: In4Se3, thermoelectric properties, vacuum melting, annealing

中图分类号:

TB34

赵然, 马立民, 郭福, 胡扬端瑞, 舒雨田. 高优值系数In₄Se₃多晶的制备及其热电输运特性[J]. 无机材料学报, 2015, 30(3): 249-255.

ZHAO Ran, MA Li-Min, GUO Fu, HU Yang-Duan-Rui, SHU Yu-Tian. Preparation and Thermoelectric Transport of Polycrystalline In₄Se₃
with High Figures of Merit[J]. Journal of Inorganic Materials, 2015, 30(3): 249-255.

图/表 8

图1 不同熔炼时间得到样品的XRD图谱

Fig. 1 XRD patterns for the specimens melted for different periods

表1 不同熔炼时间获得样品的XRF测试结果

Table 1 XRF results for the specimens melted for different periods

Melting time/h	In/at%	Se/at%	In:Se
12	59.37	40.63	4:2.74
24	59.70	40.30	4:2.70
48	61.16	38.84	4:2.54

图2 不同熔炼时间获得样品热电性能随温度变化关系曲线

Fig. 2 Temperature dependence of thermoelectric property for the specimens melted for different periods

表2 不同熔炼时间获得样品的室温电输运性能

Table 2 Electrical properties at room temperature for the specimens melted for different periods

Melting time/h	Carrier concentration/cm^-3	Carrier mobility /(cm²·V^-1·s^-1)
12	-2.22×10¹⁷	184.95
24	-4.65×10¹⁷	138.59
48	-5.42×10¹⁷	116.03

图3 不同退火时间后样品XRD衍射花样

Fig. 3 XRD patterns for specimens annealed for different periods

表3 不同退火时间获得样品的XRF测试结果

Table 3 XRF results for the specimens annealed for different periods

Annealing time/h	In/at%	Se/at%	In: Se
0	61.16	38.84	4: 2.54
48	61.04	38.96	4: 2.53
96	61.27	38.73	4: 2.53
144	61.19	38.81	4: 2.54

图4 不同退火时间样品SPS烧结断口形貌

Fig. 4 Fractographies of the specimens annealed for different periods (a) 0 h; (b) 48 h; (c) 96 h; (d) 144 h; (e) Enlarged image of (c)

图5 不同退火时间样品热电性能随温度变化关系曲线

Fig. 5 Temperature dependence of thermoelectric property for specimens annealed for different periods (a) Electrical conductivity; (b) Seebeck coefficient; (c) Thermal conductivity; (d) ZT value[11, 16]

参考文献 33

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高优值系数In₄Se₃多晶的制备及其热电输运特性

Preparation and Thermoelectric Transport of Polycrystalline In₄Se₃
with High Figures of Merit

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