Wang Yichao, Liu Jiahe, Jiang Ning, Yang Jianhua, Yang Cheng, Liu Yu
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Small. 2024 Nov;20(44):e2403211. doi: 10.1002/smll.202403211. Epub 2024 Jul 3.
Prussian blue analogs (PBAs) have been widely recognized as superior cathode materials for sodium-ion batteries (SIBs) owing to numerous merits. However, originating from the rapid crystal growth, PBAs still suffer from considerable vacancy defects and interstitial water, making the preparation of long-cycle-life PBAs the greatest challenge for its practical application. Herein, a novel equilibrium chelation strategy is first proposed to synthesize a high crystallinity (94.7%) PBAs, which is realized by modulating the chelating potency of strong chelating agents via "acid effect" to achieve a moderate chelating effect, forcefully breaking through the bottleneck of poor cyclic stability for PBAs cathodes. Impressively, the as-prepared highly crystalline PBAs represent an unprecedented level of electrochemical performance including ultra-long lifespan (10000 cycles with 86.32% capacity maintenance at 6 A g), excellent rate capability (82.0 mAh g at 6 A g). Meanwhile, by pairing with commercial hard carbon, the as-prepared PBAs-based SIBs exhibit high energy density (350 Wh kg) and excellent capacity retention (82.4% after 1500 cycles), highlighting its promising potential for large-scale energy storage applications.
普鲁士蓝类似物(PBAs)因其众多优点而被广泛认为是钠离子电池(SIBs)的优质阴极材料。然而,由于晶体快速生长,PBAs仍然存在大量空位缺陷和间隙水,这使得制备长循环寿命的PBAs成为其实际应用面临的最大挑战。在此,首次提出了一种新颖的平衡螯合策略来合成高结晶度(94.7%)的PBAs,这是通过“酸效应”调节强螯合剂的螯合能力以实现适度的螯合效果来实现的,有力地突破了PBAs阴极循环稳定性差的瓶颈。令人印象深刻的是,所制备的高结晶度PBAs展现出前所未有的电化学性能水平,包括超长寿命(在6 A g下循环10000次,容量保持率为86.32%)、优异的倍率性能(在6 A g下为82.0 mAh g)。同时,与商业硬碳配对时,所制备的基于PBAs的SIBs表现出高能量密度(350 Wh kg)和出色的容量保持率(1500次循环后为82.4%),突出了其在大规模储能应用中的广阔前景。