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Controllable heat release of phase-change azobenzenes by optimizing molecular structures for low-temperature energy utilization

通过优化分子结构实现相变偶氮苯的可控热释放用于低温能量利用

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Abstract

Phase-change azobenzene derivatives can store and release heat upon isomerization. The amount and rate of heat output are affected by the azobenzene crystallization and isomerization, which are in turn governed by molecular structure and interactions. Thus, optimizing molecular structure is a promising method to control heat release at different temperatures. Herein, we prepared three asymmetric alkoxy-substituted azobenzene molecules (s-Azo) with similar molecular weights but different substituents to investigate the trade-off between crystallization and isomerization. Temperature-dependent crystallizability and photo-induced iso-merization kinetics of all s-Azo were studied. Results indicate that n-alkoxy substitution endows s-Azo with high crystallization enthalpy (ΔHCE) due to strong van der Waals forces, but steric hindrance lowers the degree of isomerization. Short branched alkyl substitution reduces intermolecular interactions and favors the isomerization, which leads to an increase in isomerization enthalpy (ΔHIE) but decreases ΔHCE. The n-alkoxy-substituted s-Azo exhibits photoinduced high-energy heat release with an enthalpy of up to 343.3 J g−1 and a power density of 413 W kg−1 at a wide temperature range from −60.49 to 34.76°C. The synchronous heat release in a distributed energy utilization annular device achieves a temperature rise of 6.3°C at a low temperature environment (−5°C). Results demonstrate that phase-change azobenzene derivatives can be designed and developed for ideal energy-storage systems by optimizing molecular structures and interactions.

摘要

相变偶氮苯衍生物可以基于异构化储存和释放热量. 热量输出量和速率受偶氮苯结晶和异构化的影响, 同时也受分子结构和相互作用的制约. 因此, 优化分子结构是控制不同温度下热量释放的一种有效方式. 在此, 我们制备了三个不对称的烷氧基取代的偶氮苯分子(s-Azo), 其分子量相似但取代基不同, 以研究结晶和异构化之间的权衡. 我们研究了s-Azo的温控结晶性和光诱导的异构化动力学. 结果表明, 由于较强的范德华力, 正烷氧基取代使s-Azo具有较高的结晶焓(ΔHCE), 但立体阻碍降低了异构化程度. 短烷基支化降低了分子相互作用, 有利 于异构化, 使异构化焓(ΔHIE)增加, 但降低了ΔHCE. 正烷氧基取代的s-Azo在−60.49至34.76°C的宽温度范围内表现出光诱导的高能热释放, 焓值高达343.3 J g−1, 功率密度为413 W kg−1. 同步放热使分布式能量利 用的环形装置在低温环境(−5°C)下实现了6.3°C的温升. 结果表明, 相变 偶氮苯衍生物可以通过优化分子结构和相互作用应用于理想的储能 系统.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (2022YFB3805702), the State Key Program of National Natural Science Foundation of China (51973152 and 52130303), and the Science Foundation for Distinguished Young Scholars in Tianjin (19JCJQJC61700). The authors would like to thank Dr. Joseph Elliot at the University of Kansas for her assistance with English language and grammatical editing of the manuscript.

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Authors and Affiliations

  1. School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Qingbin Yang  (杨庆宾), Jing Ge  (葛婧), Mengmeng Qin  (秦盟盟), Hui Wang  (王慧), Xiaoyu Yang  (杨晓玉), Xinlei Zhou  (周鑫磊), Bo Zhang  (张博), Yiyu Feng  (冯奕钰) & Wei Feng  (封伟)

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  1. Qingbin Yang  (杨庆宾)
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Contributions

Feng W and Feng Y conceived the project and supervised the research. Yang Q performed the synthesis and characterization of s-Azo. Ge J, Qin M, Wang H, Yang X, Zhou X and Zhang B helped in the analysis of the results. Yang Q wrote the manuscript. All authors discussed the results and revised the manuscript.

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Correspondence to Yiyu Feng  (冯奕钰) or Wei Feng  (封伟).

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

Qingbin Yang is now pursuing his MS degree under the supervision of Prof. Wei Feng at the School of Materials Science and Engineering, Tianjin University. His research interests include the synthesis, mechanism and applications of photo-responsive azobenzene-based phase change materials.

Yiyu Feng is a professor at the School of Materials Science and Engineering, Tianjin University. He obtained his PhD degree from Tianjin University in 2009 and held an academic position at Tianjin University in 2009. Currently, his research is focused on solar-thermal conversion and thermal interfacial materials and composites, as well as their applications in heat-control systems.

Wei Feng is a professor at the School of Materials Science and Engineering, Tianjin University. He obtained his PhD degree from Xi’an Jiaotong University (China) in 2000. Then, he worked at Osaka University and Tsinghua University as a JSPS fellow and postdoctoral researcher, respectively. In 2004, he became a full professor at Tianjin University. His research interests include photoresponsive organic molecules and their derivatives, thermal conductive and high-strength carbon-based composites, and new fuorinated carbon materials and functional polymers.

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40843_2023_2477_MOESM1_ESM.pdf

Controllable Heat Release of Phase-Change Azobenzenes by Optimizing Molecular Structures for Low-temperature Energy Utilization

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Yang, Q., Ge, J., Qin, M. et al. Controllable heat release of phase-change azobenzenes by optimizing molecular structures for low-temperature energy utilization. Sci. China Mater. 66, 3609–3620 (2023). https://doi.org/10.1007/s40843-023-2477-x

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