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Dejwikom Theprattanakorn, Thanayut Kaewmaraya, and Supree Pinitsoontorn, Boosting thermoelectric efficiency of Ag2Se through cold sintering process with Ag nano-precipitate formation, Int. J. Miner. Metall. Mater., 31(2024), No. 12, pp.2760-2769. https://dx.doi.org/10.1007/s12613-024-2973-x
Dejwikom Theprattanakorn, Thanayut Kaewmaraya, and Supree Pinitsoontorn, Boosting thermoelectric efficiency of Ag2Se through cold sintering process with Ag nano-precipitate formation, Int. J. Miner. Metall. Mater., 31(2024), No. 12, pp.2760-2769. https://dx.doi.org/10.1007/s12613-024-2973-x
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银纳米颗粒沉淀冷烧结工艺提高Ag2Se热电效率

摘要: 硒化银(Ag2Se)是一种极具潜力的近室温热电(TE)材料。本研究提出了一种在较低温度(170°C)下,以AgNO3溶液为瞬态液体,通过冷烧结工艺(CSP)制备块状Ag2Se新方法并考察AgNO3对其微观结构和TE性能的影响。物相成分和微观结构分析结果表明:AgNO3的加入诱导Ag2Se基体中Ag纳米颗粒沉淀形成,该沉淀颗粒不影响正交相β-Ag2Se晶体结构,抑制了晶体的生长,导致晶体尺寸减小。含有银纳米沉淀颗粒样品具有高孔隙率和低堆积密度,电导率显著提高,塞贝克系数略有下降,平均功率因数较纯Ag2Se的1540 μW⋅m−1⋅K−2增加至1670 μW⋅m−1⋅K−2,但过量添加AgNO3对功率因数不利。此外,利用AgNO3通过CSP制备的Ag2Se由于晶体界面、孔隙和Ag纳米颗粒沉淀处的声子散射增强,其热导率被有效抑制。在CSP制造过程中,添加Ag质量分数0.5%的Ag2Se在300 K时达到了最高zT值(0.92),相较于不添加Ag的Ag2Se提高20%以上。本研究为定制块状Ag2Se的微观结构和提高室温TE性能提供了一种有效策略。

 

Boosting thermoelectric efficiency of Ag2Se through cold sintering process with Ag nano-precipitate formation

Abstract: Silver selenide (Ag2Se) stands out as a promising thermoelectric (TE) material, particularly for applications near room temperatures. This research presents a novel approach for the fabrication of bulk Ag2Se samples at a relatively low temperature (170°C) using the cold sintering process (CSP) with AgNO3 solution as a transient liquid agent. The effect of AgNO3 addition during CSP on the microstructure and TE properties was investigated. The results from phase, composition and microstructure analyses showed that the introduction of AgNO3 solution induced the formation of Ag nano-precipitates within the Ag2Se matrix. Although the nano-precipitates do not affect the phase and crystal structure of orthorhombic β-Ag2Se, they suppressed crystal growth, leading to reduced crystallite sizes. The samples containing Ag nano-precipitates also exhibited high porosity and low bulk density. Consequently, these effects contributed to significantly enhanced electrical conductivity and a slight decrease in the Seebeck coefficient when small Ag concentrations were incorporated. This resulted in an improved average power factor from ~1540 µW·m−1·K−2 for pure Ag2Se to ~1670 µW·m−1·K−2 for Ag2Se with additional Ag precipitates. However, excessive Ag addition had a detrimental effect on the power factor. Furthermore, thermal conductivity was effectively suppressed in Ag2Se fabricated using AgNO3-assisted CSP, attributed to enhanced phonon scattering at crystal interfaces, pores, and Ag nano-precipitates. The highest figure-of-merit (zT) of 0.92 at 300 K was achieved for the Ag2Se with 0.5wt% Ag during CSP fabrication, equivalent to >20% improvement compared to the controlled Ag2Se without extra Ag solution. Thus, the process outlined in this study presents an effective strategy to tailor the microstructure of bulk Ag2Se and enhance its TE performance at room temperature.

 

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