Wu Sicheng, Taylor Mackenzie, Guo Haocheng, Wang Shuhao, Han Chen, Vongsvivut Jitraporn, Meyer Quentin, Sun Qian, Ho Junming, Zhao Chuan
School of Chemistry, the, University of New South Wales, Sydney, NSW, 2052, Australia.
School of Chemical Engineering, the, University of New South Wales, Sydney, 2052, NSW, Australia.
Angew Chem Int Ed Engl. 2024 Dec 20;63(52):e202412455. doi: 10.1002/anie.202412455. Epub 2024 Nov 9.
Quinone compounds, with the ability to uptake protons, are promising electrodes for aqueous batteries. However, their applications are limited by the mediocre working potential range and inferior rate performance. Herein, we examined quinones bearing different substituents, and for the first time introduce tetraamino-1,4-benzoquinone (TABQ) as anode material for proton batteries. The strong electron-donating amino groups can effectively narrow the band gap and lower the redox potentials of quinone materials. The protonation of amino groups and the amorphization of structure result in the formation of an intermolecular hydrogen-bond network, supporting Grotthuss-type proton conduction in the electrode with a low activation energy of 192.7 meV. The energy storage mechanism revealed by operando FT-IR and ex situ XPS features a reversible quinone-hydroquinone conversion during cycling. TABQ demonstrates a remarkable specific capacity of 307 mAh g at 1 A g, which is one of the highest among organic proton electrodes. An all-organic proton battery of TABQ//TCBQ has also been developed, achieving exceptional stability of 3500 cycles at room temperature and excellent performance at sub-zero temperature.
醌类化合物具有吸收质子的能力，是用于水系电池的有前景的电极材料。然而，它们的应用受到中等工作电位范围和较差倍率性能的限制。在此，我们研究了带有不同取代基的醌类化合物，并首次引入四氨基-1,4-苯醌（TABQ）作为质子电池的负极材料。强供电子氨基可有效缩小醌类材料的带隙并降低其氧化还原电位。氨基的质子化和结构的非晶化导致形成分子间氢键网络，支持电极中具有192.7 meV低活化能的Grotthuss型质子传导。通过原位傅里叶变换红外光谱（FT-IR）和非原位X射线光电子能谱（XPS）揭示的储能机制具有循环过程中醌-氢醌的可逆转化。TABQ在1 A g时表现出307 mAh g的显著比容量，这是有机质子电极中最高的之一。还开发了一种TABQ//TCBQ全有机质子电池，在室温下实现了3500次循环的出色稳定性以及在零下温度下的优异性能。
