Collaborative Innovation Center of Steel Technology, University of Science and Technology Beijing, Beijing, 100083, P. R. China.
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing, 100083, P. R. China.
Adv Sci (Weinh). 2023 Feb;10(5):e2205556. doi: 10.1002/advs.202205556. Epub 2023 Jan 1.
Iron group metals chalcogenides, especially NiS, are promising candidates for K-ion battery anodes due to their high theoretical specific capacity and abundant reserves. However, the practical application of NiS-based anodes is hindered by slow electrochemical kinetics and unstable structure. Herein, a novel structure of Ni S -Ni hybrid nanosphere with intra-core voids encapsulated by N-doped carbon shells (Ni S -Ni@NC-AE) is constructed, based on the first electrodeposited NiS nanosphere particles, dopamine coating outer layer, oxygen-free annealing treatment to form Ni S -Ni core and N-doped carbon shell, and selective etching of the Ni phase to form intra-core void. The electron/K transport and K storage reaction kinetics are enhanced due to shortened diffusion pathways, increased active sites, generation of built-in electric field, high K adsorption energies, and large electronic density of states at Fermi energy level, resulting from the multi-structures synergistic effect of Ni S -Ni@NC-AE. Simultaneously, the volume expansion is alleviated due to the sufficient buffer space and strong chemical bonding provided by intra-core void and yolk-shell structure. Consequently, the Ni S -Ni@NC-AE exhibits excellent specific capacity (438 mAh g at 0.1 A g up to 150 cycles), outstanding rate performances, and ultra-stable long-cycle performance (176.4 mAh g at 1 A g up to 5000 cycles) for K-ion storage.
铁族金属硫属化物,特别是 NiS,由于其高的理论比容量和丰富的储量,是钾离子电池负极的有前途的候选材料。然而,基于 NiS 的负极的实际应用受到缓慢的电化学动力学和不稳定结构的阻碍。在此,基于首次电沉积的 NiS 纳米球颗粒,构建了一种具有核内空隙的新型 NiS-Ni 混合纳米球结构,该纳米球由掺杂氮的碳壳(NiS-Ni@NC-AE)封装,其外层包裹有聚多巴胺,经过无氧退火处理形成 NiS-Ni 核和掺杂氮的碳壳,然后选择性刻蚀 Ni 相以形成核内空隙。由于 NiS-Ni@NC-AE 的多结构协同效应,缩短了扩散路径,增加了活性位点,产生了内置电场,提高了 K 的吸附能,增加了费米能级附近的电子态密度,从而增强了电子/K 传输和 K 存储反应动力学。同时,由于核内空隙和蛋黄壳结构提供了充足的缓冲空间和强化学键,缓解了体积膨胀。因此,NiS-Ni@NC-AE 表现出优异的比容量(在 0.1 A g 下循环 150 次可达 438 mAh g)、卓越的倍率性能和超稳定的长循环性能(在 1 A g 下循环 5000 次可达 176.4 mAh g)。