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有机-无机杂化 TMCM-CdCl₂ 中的大低场驱动电热效应

Large low-field-driven electrocaloric effect in organic-inorganic hybrid TMCM-CdCl.

作者信息

Lin Yuan, Chai Congcong, Liu Zhijie, Wang Jing, Jin Shifeng, Yang Yurong, Gao Yihong, Hao Munan, Li Xinyue, Hou Yuxuan, Ma Xingyue, Wang Bingjie, Wang Zheng, Kan Yue, Zheng Jie, Bai Yang, Chen Yunzhong, Sun Jirong, Zhao Tongyun, Law Jia Yan, Franco Victorino, Hu Fengxia, Shen Baogen

机构信息

Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, PR China.

School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, PR China.

出版信息

Nat Commun. 2025 Apr 29;16(1):4009. doi: 10.1038/s41467-025-58914-z.

Abstract

Due to environmental-friendliness and high-efficiency, electrocaloric effect (ECE) is widely regarded as a refrigeration technology for tomorrow. Herein, utilizing organic-inorganic hybridization strategy, we achieve the largest low-field-driven ECE and highest directly-measured electrocaloric strength (ECS) via packing sphere-like organic cation (CH)NCHCl (TMCM) into inorganic one-dimension (1-D) CdCl chain framework. Single-crystal X-ray (SC-XRD) diffraction combined with Raman Spectra reveals that the simultaneous order-disorder transition of organic cations and dramatic structure change of inorganic framework are responsible for the large ECE. Moreover, the measured P-E loops and density function theory (DFT) calculations convey that the distinctive electric-field-induced metastable phase and consequential two-step meta-electric transition could lower the transition energy barrier and account for the low driving field. This work shows that the low-symmetry interaction between inorganic framework and organic cations plays a key role in achieving large ECE under low-field, which provides a method for designing high-performance electrocaloric materials via organic-inorganic hybridization.

摘要

由于具有环境友好性和高效性,电热效应(ECE)被广泛视为未来的一种制冷技术。在此,利用有机-无机杂化策略,通过将球状有机阳离子(CH)NCHCl(TMCM)填充到无机一维(1-D)CdCl链状框架中,我们实现了最大的低场驱动电热效应和最高的直接测量电热强度(ECS)。单晶X射线(SC-XRD)衍射结合拉曼光谱表明,有机阳离子的同时有序-无序转变和无机框架的显著结构变化是产生大电热效应的原因。此外,测量的P-E回线和密度泛函理论(DFT)计算表明,独特的电场诱导亚稳相和随之而来的两步亚电转变可以降低转变能垒,并解释低驱动场的原因。这项工作表明,无机框架与有机阳离子之间的低对称性相互作用在低场下实现大电热效应中起关键作用,这为通过有机-无机杂化设计高性能电热材料提供了一种方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0e18/12041295/28796a35ce2d/41467_2025_58914_Fig1_HTML.jpg

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