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A new piezoelectric hybrid metal thiocyanide for energy harvesting and human motion sensing

新型杂化金属硫氰化物压电体用于能量收集和动作传感

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Abstract

Hybrid organic-inorganic piezoelectrics have received considerable attention in recent years owing to their fascinating performance, facile synthesis, and mechanical flexibility. However, the reported systems usually contain toxic heavy metals or are unstable due to sensitive metal halide bonds in air. In this context, eco-friendly and stable hybrid materials with excellent piezoelectric properties are highly sought after. Here, a new stable zero-dimensional hybrid piezoelectric, [Me-V]3Mn(SCN)5 (Me-V, 1-methyl-[4,4′]-bi-pyridinium), based on a pseudo-halogen environmentally friendly anion of SCN− was synthesized. More importantly, the mechanical energy harvesting properties of its flexible composite films, [Me-V]3Mn(SCN)5/PBAT (PBAT, polybutylene adipate terephthalate), with a series of weight ratios (1, 5, 10, 15, and 20 wt%) of [Me-V]3Mn(SCN)5 are reported. Experimental results demonstrate that the 15 wt% [Me-V]3Mn-(SCN)5/PBAT devices present an exceptional performance in energy harvesting, which can produce a maximum output voltage of 18.49 V and a power density of 7.88 µW cm−2 under an applied force of only 0.03 MPa, catching up with those of the state-of-the-art piezoelectric energy harvesting devices. Meanwhile, a typical device was demonstrated to exhibit excellent mechanical durability under 5500 cycles and environmentally stable over 60 days. Furthermore, the devices also show good sensitivity in monitoring human body motions, including finger tapping, wrist and elbow bending, and foot stepping. This work proves that lead- and halide-free hybrid piezoelectrics can serve as eco-friendly materials for flexible sensing and energy harvesting.

摘要

杂化有机-无机压电材料因其电光性能优异、合成简单以及机械柔性等优点而受到广泛关注, 在能源和传感领域显示出巨大的应用潜力. 本文合成了一例新的零维杂化压电材料[Me−V]3Mn(SCN)5, 并与聚己二酸丁二酯对苯二甲酸丁二酯复合成膜制备了用于机械能收集的压电器件. 实验结果表明, 15 wt%组分的压电器件具有优异的能量收集性能, 在仅0.03 MPa作用力下, 可产生18.49 V的最大输出电压和7.88 µW cm−2的功率密度. 同时, 该器件在循环5500圈及60天内仍保持优异的压电性能. 此外, 该器件在包括手指敲击、手腕/肘部弯曲和踩踏等动作传感方面表现出良好的敏感性. 这项工作证明了无铅无卤的杂化压电材料在柔性传感和能量收集方面具有巨大的应用潜力.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21975132 and 21991143), the Fundamental Research Funds for the Central Universities (63196006), and the PhD Candidate Research Innovation Fund of the School of Materials Science and Engineering, Nankai University.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Smart Sensing Interdisciplinary Science Center, Nankai University & TKL of Metal and Molecule Based Material Chemistry, Tianjin, 300350, China

    Ying Zhao  (赵盈), Lian-Cai An  (安连财), Tian-Meng Guo  (郭甜梦), Fei-Fei Gao  (高飞飞), Quanwen Li  (李泉文), Wei Li  (李伟) & Xian-He Bu  (卜显和)

  2. Department of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong, 030619, China

    Kai Li  (李凯)

  3. College of Materials and Metallurgy, Guizhou University, Guiyang, 550025, China

    Yong-Ji Gong  (龚勇吉) & Yang Lei  (雷阳)

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  1. Ying Zhao  (赵盈)
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  2. Lian-Cai An  (安连财)
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  3. Kai Li  (李凯)
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Contributions

Bu XH and Li W conceived the idea and supervised this work. Zhao Y synthesized the crystal, performed the characterization and wrote the manuscript. An LC and Li K revised the manuscript. Gong YJ, Guo TM, and Gao FF analyzed the piezoelectric properties. Lei Y performed the strain-stress curves and moduli test. Li Q performed the single crystal test. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Kai Li  (李凯) or Wei Li  (李伟).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Wei Li is a full professor of the School of Materials Science and Engineering, Nankai University. His research focuses on the materials physics and chemistry of coordination polymers and hybrid organic-inorganic perovskites.

Kai Li obtained his PhD degree in 2021 from the School of Materials Science and Engineering, Nankai University. He joined Jinzhong University in 2022. His research focuses on hybrid organic-inorganic perovskite ferroelectrics.

Ying Zhao received her MSc degree (2020) from Guizhou University with Prof. Min He. She is now a postgraduate student at Nankai University under the supervision of Prof. Wei Li. Her research interest focuses on piezoelectric hybrid organic-inorganic materials.

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Zhao, Y., An, LC., Li, K. et al. A new piezoelectric hybrid metal thiocyanide for energy harvesting and human motion sensing. Sci. China Mater. 66, 1854–1860 (2023). https://doi.org/10.1007/s40843-022-2360-x

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