Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, School of Materials Science and Engineering, Peking University, Beijing, 100871, China.
Advanced Technology Institute, Department of Electrical and Electronic Engineering, University of Surrey, Guildford, GU2 7XH, UK.
Nat Commun. 2023 Jul 3;14(1):3909. doi: 10.1038/s41467-023-39258-y.
Conventional solid-to-solid conversion-type cathodes in batteries suffer from poor diffusion/reaction kinetics, large volume changes and aggressive structural degradation, particularly for rechargeable aluminium batteries (RABs). Here we report a class of high-capacity redox couples featuring a solution-to-solid conversion chemistry with well-manipulated solubility as cathodes-uniquely allowed by using molten salt electrolytes-that enable fast-charging and long-lived RABs. As a proof-of-concept, we demonstrate a highly reversible redox couple-the highly soluble InCl and the sparingly soluble InCl-that exhibits a high capacity of about 327 mAh g with negligible cell overpotential of only 35 mV at 1 C rate and 150 °C. The cells show almost no capacity fade over 500 cycles at a 20 C charging rate and can sustain 100 mAh g at 50 C. The fast oxidation kinetics of the solution phase upon initiating the charge enables the cell with ultrafast charging capability, whereas the structure self-healing via re-forming the solution phase at the end of discharge endows the long-term cycling stability. This solution-to-solid mechanism will unlock more multivalent battery cathodes that are attractive in cost but plagued by poor reaction kinetics and short cycle life.
在电池中,传统的固-固转化型阴极存在扩散/反应动力学性能差、体积变化大和结构稳定性差等问题,尤其是对于可再充电铝电池 (RAB) 更是如此。在此,我们报告了一类具有溶液-固转化化学特性的高容量氧化还原对,其特点是采用熔融盐电解质,具有良好的可调控溶解度,这使得快速充电和长寿命的 RAB 成为可能。作为一个概念验证,我们展示了一种高度可逆的氧化还原对-高溶解度的 InCl 和低溶解度的 InCl-在 150°C 下以 1C 的速率充电时,具有约 327 mAh g 的高容量,且电池过电位仅为 35 mV。在 20°C 的充电速率下,经过 500 次循环后,电池几乎没有容量衰减,在 50°C 时可以保持 100 mAh g 的容量。在充电开始时,溶液相的快速氧化动力学使得电池具有超快的充电能力,而在放电结束时通过重新形成溶液相来实现结构自修复,从而赋予了长期循环稳定性。这种溶液-固机制将解锁更多具有成本效益但反应动力学性能差和循环寿命短的多价电池阴极。