双金属ZnSe/CoSe2@C核壳结构复合材料作为阳极用于高性能钠离子电池

ZnSe/CoSe2 Hetero-Nanocrystals Confined into Carbonaceous Core-Shell Structure for High-Performance Sodium-Ion Batteries

  • 摘要: 金属硒化物凭借高比容量和优异的氧化还原特性,成为钠离子电池负极材料的研究热点。然而,较大的 \textNa^+ 半径使其在可逆嵌/脱钠过程中,面临着反应动力学迟缓、体积效应显著等,成为制约此类材料实际应用的关键痛点。为此,本文提出了一种结合空间设计与界面工程的协同策略,通过单宁酸(TA)诱导的配位-刻蚀与原位硒化/碳化重构过程,构筑出以氮掺杂碳为导电骨架、双金属异质结为活性组分的ZnSe/CoSe2@C核壳结构复合材料,并系统探究其金属成分占比对储钠行为的关键影响。其中,碳基骨架形成的核壳结构与内部空腔构建出连续的电子传输网络为体积变化预留缓冲空间,活性组分ZnSe/CoSe2间的异质界面形成内建电场能调控电荷分布、降低 \textNa^+ 扩散能垒来加速反应动力学。得益于复合材料结构和成分之间的协同作用,最优配比ZnSe/CoSe2@C(1∶2)电极展现出优异的储钠性能,在0.1 A·g−1电流密度下循环100圈后,可逆比容量高达737.3 mAh·g−1;即便在1 A·g−1的高电流密度下经过400次循环,仍能保持319.6 mAh·g−1的可逆比容量。本研究通过异质界面场效应与结构空间效应协同储钠机制的设计与探究,为面向应用的金属硒化物负极材料提供一种可行的解决路径。

     

    Abstract: Metal selenides have become a research hotspot as anode materials for sodium-ion batteries (SIBs) owing to their high specific capacity and favorable redox properties. However, the large ionic radius of Na+ results in sluggish reaction kinetics and severe volume expansion during reversible intercalation/deintercalation, posing major obstacles to their practical application. Herein, we propose a synergistic strategy integrating spatial construction and interface engineering. Through a tannic acid (TA)-induced etching-coordination process followed by in situ selenization/carbonization evolution, a core-shell ZnSe/CoSe2@C composite featuring a nitrogen-doped carbon skeleton and bimetallic heterojunction components is successfully constructed. Moreover, the key influence of the metal composition ratio on the sodium storage behavior is systematically investigated. In this composite, the carbon-based skeleton forms a core-shell architecture with internal cavities, establishing continuous electron transport pathways and providing buffering space for volume expansion. Meanwhile, the heterointerface between ZnSe and CoSe2 generates a built-in electric field, which modulates charge distribution and reduces the Na+ diffusion barrier, thereby accelerating reaction kinetics. Benefiting from the synergistic effects of structure and composition, the optimized ZnSe/CoSe2@C(1∶2) electrode exhibits superior sodium storage performance, achieving a reversible specific capacity of 737.3 mAh·g−1 after 100 cycles at 0.1 A·g−1. Moreover, it retains a reversible specific capacity of 319.6 mAh·g−1 even after 400 cycles at a high current density of 1 A·g−1. This work elucidates the synergistic sodium storage mechanism combining heterointerface field effects and structural confinement, providing valuable design insights for the development of application-oriented metal selenide anodes.

     

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