The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits. Three-dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity; however, uncontrollable and nonuniform deposition of Li remains a challenge. In this study, we synthesize metal–organic framework-derived carbon microcapsules with heteroatom clusters (Zn and Ag) on the capsule walls and it is demonstrated that Ag-assisted nucleation of Li metal alters the outward-to-inward growth in the microcapsule host. Zn-incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework-8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag⁺ and metallic Zn. Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating. Through combined electrochemical, microstructural, and computational studies, we verify the beneficial role of Ag-assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and, in turn, enhancing electrochemical performance. This study provides new insights into the design of reversible host materials for practical Li metal batteries.

中文翻译：

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通过杂原子控制成核驱动空心微胶囊主体中锂金属的向内生长

由于严重的体积变化和枝晶锂沉积物的形成而产生的安全问题阻碍了锂金属负极在可充电电池中的应用。三维空心碳作为能够在其空腔内容纳锂金属的主体材料而受到越来越多的关注；然而，锂的不可控和不均匀沉积仍然是一个挑战。在这项研究中，我们合成了胶囊壁上具有杂原子簇（锌和银）的金属有机骨架衍生的碳微胶囊，并证明银辅助锂金属的成核改变了微胶囊主体中由外向内的生长。掺锌微胶囊是通过化学蚀刻沸石咪唑骨架 8 多面体制备的，随后通过 Ag ⁺和金属 Zn 之间的电置换反应用 Ag 装饰。电镀引入的银显着降低了能量势垒，并提高了镀锂时微胶囊主体中锂成核的反应速率。通过结合电化学、微观结构和计算研究，我们验证了银辅助锂成核在促进微胶囊主体空腔内向内生长并进而增强电化学性能方面的有益作用。这项研究为实用锂金属电池的可逆主体材料的设计提供了新的见解。