Authors: Jianping Yan, Bo Wang, Yongchao Tang, Jiaming Xiong, Guigui Liu, Zhenfeng Feng, Jintu Qi, Hongqing Li, Zhipeng Wen, Minghui Ye, Yufei Zhang, Wencheng Du, Xiaoqing Liu, Cheng Chao Li
Published: 2024-10-28
Source: Full article
AbstractEarth‐rich Ca2+ ions for energy storage can endow batteries with low‐cost and high‐energy merits, yet remain hampered by difficult Ca2+ plating/stripping and (de)intercalation. Herein, by bridging Zn2+/Ca2+‐storage chemistries, a high‐voltage and stable Ca2+‐based hybrid battery (CHB) in a hetero‐solvation electrolyte (HSE) is initially achieved. With a [Ca2+(H2O)(acetonitrile)(CF3SO3)−] hetero‐solvation unit, the HSE not only allows a reversible in situ Zn stripping/plating to circumvent the low‐capacity/high‐potential limitation of non‐stripping/plating‐type anodes for Ca2+ storage but also effectively overcomes kinetics‐sluggish Ca2+ (de)intercalation usually occurring in conventional organic electrolytes. The acetonitrile‐rich water‐lean anode interface synergized by the electrostatic shielding effect of Ca2⁺ ions plays a conducive role in facilitating highly reversible Zn stripping/plating. Moreover, the lubricating/shielding properties of water molecules in the hetero‐solvation unit effectively boost the Ca2+/Zn2+ co‐insertion/extraction into/from the KNiMnPB/G cathode. Consequently, the HSE affords an endurable Zn stripping/plating over 1600 h, endows KNiMnPB/G//Zn battery with a high operating voltage of up to 1.85 V at 0.1 A g−1, and demonstrates decent stability over 400 cycles at 1 A g−1, outperforming most aqueous Ca2+‐based batteries with non‐stripping/plating‐type anodes. This work sheds new light on the development of high‐voltage aqueous CHBs by bridging Zn2+/Ca2+‐storage chemistries, which would boost to pursue other high‐energy multivalent‐ion batteries.