Liu Bo, Wei Cong, Zhu Zixuan, Fang Yanyan, Bian Zenan, Lei Xin, Zhou Ya, Tang Chongyang, Qian Yitai, Wang Gongming
Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Angew Chem Int Ed Engl. 2022 Nov 2;61(44):e202212780. doi: 10.1002/anie.202212780. Epub 2022 Sep 29.
Designing water-deficient solvation sheath of Zn by ligand substitution is a widely used strategy to protect Zn metal anode, yet the intrinsic tradeoff between Zn nucleation/dissolution kinetics and the side hydrogen evolution reaction (HER) remains a huge challenge. Herein, we find boric acid (BA) with moderate ligand field interaction can partially replace H O molecules in the solvation sheath of Zn , forming a stable water-deficient solvation sheath. It enables fast Zn nucleation/dissolution kinetics and substantially suppressed HER. Crucially, by systematically comparing the ligand field strength and solvation energies between BA and the ever-reported electrolyte additives, we also find that the solvation energy has a strong correlation with Zn nucleation/dissolution kinetics and HER inhibition ability, displaying a classic volcano behavior. The modulation map could provide valuable insights for solvation sheath design of zinc batteries and beyond.
通过配体取代设计锌的缺水溶剂化鞘层是保护锌金属负极的一种广泛使用的策略，然而锌成核/溶解动力学与副反应析氢反应（HER）之间固有的权衡仍然是一个巨大的挑战。在此，我们发现具有适度配体场相互作用的硼酸（BA）可以部分取代锌溶剂化鞘层中的水分子，形成稳定的缺水溶剂化鞘层。这使得锌具有快速的成核/溶解动力学，并显著抑制析氢反应。至关重要的是，通过系统地比较BA与以往报道的电解质添加剂之间的配体场强度和溶剂化能，我们还发现溶剂化能与锌的成核/溶解动力学和析氢反应抑制能力有很强的相关性，呈现出典型的火山行为。该调控图谱可为锌电池及其他电池的溶剂化鞘层设计提供有价值的见解。
