School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan, 453007, China.
School of Physics, Henan Normal University, Xinxiang, Henan, 453007, China.
Small. 2020 Mar;16(11):e1906946. doi: 10.1002/smll.201906946. Epub 2020 Feb 18.
Prussian blue (PB) and its analogues are recognized as promising cathodes for rechargeable batteries intended for application in low-cost and large-scale electric energy storage. With respect to PB cathodes, however, their intrinsic crystal regularity, vacancies, and coordinated water will lead to low specific capacity and poor rate performance, impeding their application. Herein, nanocubic porous Na FeFe(CN) coated with polydopamine (PDA) as a coupling layer to improve its electrochemical performance is reported, inspired by the excellent adhesive property of PDA. As a cathode for sodium-ion batteries, the Na FeFe(CN) electrode coupled with PDA delivers a reversible capacity of 93.8 mA h g after 500 cycles at 0.2 A g , and a discharge capacity of 72.6 mA h g at 5.0 A g . The sodium storage mechanism of this Na FeFe(CN) coupled with PDA is revealed via in situ Raman spectroscopy. The first-principles computational results indicate that Fe sites in PB prefer to couple with the robust PDA layer to stabilize the PB structure. Moreover, the sodium-ion migration in the PB structure is enhanced after coating with PDA, thus improving the sodium storage properties. Both experiments and computational simulations present guidelines for the rational design of nanomaterials as electrodes for energy storage devices.
普鲁士蓝(PB)及其类似物被认为是有前途的可充电电池阴极,适用于低成本和大规模的电能存储。然而,对于 PB 阴极来说,其内在的晶体规则性、空位和配位水会导致比容量低和倍率性能差,从而阻碍了它们的应用。在此,受聚多巴胺(PDA)优异的粘附性能的启发,报道了一种纳米立方多孔 NaFeFe(CN),其表面涂有聚多巴胺(PDA)作为偶联层,以提高其电化学性能。作为钠离子电池的阴极,在 0.2 A g 的电流密度下循环 500 次后,与 PDA 偶联的 NaFeFe(CN)电极可逆容量为 93.8 mA h g-1,在 5.0 A g-1的电流密度下的放电容量为 72.6 mA h g-1。通过原位拉曼光谱揭示了这种与 PDA 偶联的 NaFeFe(CN)的储钠机制。第一性原理计算结果表明,PB 中的 Fe 位倾向于与稳定 PB 结构的强 PDA 层偶联。此外,PDA 涂层后 PB 结构中的钠离子迁移增强,从而提高了钠离子的存储性能。实验和计算模拟都为合理设计作为储能器件电极的纳米材料提供了指导。