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阴离子掺杂和双碳限制策略协同提升钴基硫化物的钠存储性能

Anion Doping and Dual-Carbon Confinement Strategies to Synergistically Boost the Sodium Storage Performance of Cobalt-Based Sulfides.

作者信息

Wang Peng, Xie Min, Liao Xiangyue, Zheng Qiaoji, Chen Yuxiang, Xie Haijiao, Zhang Heng, Lin Dunmin

机构信息

College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610066, China.

Hangzhou Yanqu Information Technology Co., Ltd., Hangzhou 310003, China.

出版信息

ACS Appl Mater Interfaces. 2024 Oct 2;16(39):52210-52219. doi: 10.1021/acsami.4c09171. Epub 2024 Sep 17.

Abstract

Cobalt-based sulfides (CSs) are generally regarded as potentially valuable anode materials for sodium-ion batteries (SIBs) due to their excellent theoretical capacity and natural abundance. Nevertheless, their slow reaction kinetics and poor structural stability restrict the practical application of the materials. In this study, the dual-carbon-confined Se-CoS@NC@C hollow nanocubes with anion doping are synthesized using ZIF-67 as the substrate by resorcin-formaldehyde (RF) encapsulation and subsequent carbonization and sulfurization/selenization. RF- and ZIF-67-derived dual-carbon skeleton hollow structures with a robust carbon skeleton and abundant internal space minimize cyclic stress, mitigate volume changes and maintain the structural integrity of the material. More importantly, Se doping increases the lattice spacing of CoS, weakens the strength of Co-S bonds, and modulates the electronic structure around Co atoms, thereby optimizing the adsorption energy of the material. As a result, the hollow nanocubes of Se-CoS@NC@C demonstrates excellent electrochemical performance as the anode for SIBs, delivering a high reversible capacity of 549.4 mAh g at 0.5 A g after 100 cycles and a superb rate performance (541.1 mAh g at 0.2  A  g, and 393.3 mAh g at 5 A g). This study proposes a neoteric strategy for synthesizing advanced anodes for SIBs through the synergy of anion doping engineering and dual-carbon confinement strategy.

摘要

钴基硫化物(CSs)因其出色的理论容量和天然丰度,通常被视为钠离子电池(SIBs)潜在的有价值负极材料。然而,其缓慢的反应动力学和较差的结构稳定性限制了该材料的实际应用。在本研究中,以ZIF-67为基底,通过间苯二酚-甲醛(RF)封装以及随后的碳化和硫化/硒化,合成了具有阴离子掺杂的双碳限制Se-CoS@NC@C空心纳米立方体。由RF和ZIF-67衍生的具有坚固碳骨架和丰富内部空间的双碳骨架空心结构可将循环应力降至最低,减轻体积变化并保持材料的结构完整性。更重要的是,硒掺杂增加了CoS的晶格间距,削弱了Co-S键的强度,并调节了Co原子周围的电子结构,从而优化了材料的吸附能。结果,Se-CoS@NC@C空心纳米立方体作为SIBs的负极表现出优异的电化学性能,在100次循环后,在0.5 A g电流密度下可逆容量高达549.4 mAh g,并且倍率性能出色(在0.2 A g电流密度下为541.1 mAh g,在5 A g电流密度下为393.3 mAh g)。本研究通过阴离子掺杂工程和双碳限制策略的协同作用,提出了一种合成SIBs先进负极的新策略。

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