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水系锌双离子电池中硒锚定的氯氧化还原化学

Selenium-Anchored Chlorine Redox Chemistry in Aqueous Zinc Dual-Ion Batteries.

作者信息

Chen Ze, Hou Yue, Wang Yiqiao, Wei Zhiquan, Chen Ao, Li Pei, Huang Zhaodong, Li Nan, Zhi Chunyi

机构信息

Department of Materials Science and Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, 999077, China.

Hong Kong Center for Cerebro-Cardiovascular Health Engineering (COCHE), NT, HKSAR, Shatin, 999077, China.

出版信息

Adv Mater. 2024 Feb;36(6):e2309330. doi: 10.1002/adma.202309330. Epub 2023 Dec 6.

DOI:10.1002/adma.202309330
PMID:38009647
Abstract

Chlorine-based batteries with Cl to Cl redox reaction (ClRR) are promising for high-performance energystorage due to their high redox potential and large theoretical capacity. However, the inherent gas-liquid conversion feature of ClRR together with poor Cl fixation can cause Cl leakage, reducing battery reversibility. Herein, we utilize a Se-based organic molecule, diphenyl diselenide (di-Ph-Se), as the Cl anchoring agent and realize an atomic level-Cl fixation through chalcogen-halogencoordinating chemistry. The promoted Cl fixation, with two oxidized Cl anchoring on a single Ph-Se, and the multivalence conversion of Se contributeto a six-electron conversion process with up to 507 mAh g and an average voltage of 1.51 V, as well as a high energy density of 665 Wh Kg . Based on the superior reversibility of thedeveloped di-Ph-Se electrode with ClRR, a remarkable rate performance (205 mAh g at 5 A g ) and cycling performance (capacity retention of 77.3 % after 500cycles) are achieved. Significantly, the pouch cell delivers a record arealcapacity of up to 6.87 mAh cm and extraordinary self-discharge performance. This chalcogen-halogen coordination chemistry between the Se electrode and Cl provides a new insight for developing reversible and efficientbatteries with halogen redox reactions.

摘要

具有氯到氯氧化还原反应(ClRR)的氯基电池因其高氧化还原电位和大理论容量而有望用于高性能储能。然而,ClRR固有的气液转化特性以及较差的氯固定性会导致氯泄漏,降低电池的可逆性。在此,我们利用一种基于硒的有机分子二苯基二硒化物(di-Ph-Se)作为氯锚定剂,并通过硫族元素-卤素配位化学实现了原子级的氯固定。促进的氯固定,即两个氧化态的氯锚定在单个Ph-Se上,以及硒的多价态转化促成了一个六电子转化过程,其容量高达507 mAh g ,平均电压为1.51 V,以及665 Wh Kg 的高能量密度。基于所开发的具有ClRR的di-Ph-Se电极的优异可逆性,实现了出色的倍率性能(在5 A g 时为205 mAh g )和循环性能(500次循环后容量保持率为77.3%)。值得注意的是,软包电池实现了高达6.87 mAh cm 的创纪录面积容量和非凡的自放电性能。硒电极和氯之间的这种硫族元素-卤素配位化学为开发具有卤素氧化还原反应的可逆且高效的电池提供了新的见解。

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