Alloying‐type anodes show capacity and density advantages for sodium/potassium‐ion batteries (SIBs/PIBs), but they encounter serious structural degradation upon cycling, which cannot be resolved through conventional nanostructuring techniques. Herein, we present an in‐depth study to reveal the intrinsic reason for the pulverization of bismuth (Bi) materials upon (de)alloying and report a novel particle‐in‐bulk architecture with Bi nanospheres inlaid in the bulk carbon (BiNC) to achieve durable Na/K storage. We simulate the volume‐expansion‐resistant mechanism of Bi during the (de)alloying reaction and unveil that the irreversible phase transition upon (de)alloying underlies the fundamental origin for the structural degradation of Bi anode, while a proper compressive stress (~10%) raised by the bulk carbon can trigger a “domino‐like” Bi crystal recovering. Consequently, the as obtained BiNC exhibits a record high volumetric capacity (823.1 mAh cm−3 for SIBs, 848.1 mAh cm−3 for PIBs) and initial coulombic efficiency (95.3% for SIBs, 96.4% for PIBs), and unprecedented cycling stability (15000 cycles for SIBs with only 0.0015% degradation per cycle), outperforming the state‐of‐the‐art literature. This work provides new insights on the undesirable structural evolution and proposes basic guidelines for design of the anti‐degradation structure for alloy‐type electrode materials.

中文翻译：

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实现铋阳极的多米诺骨牌结构恢复，实现快速、持久的 Na/K 存储

合金型负极在钠/钾离子电池（SIB/PIB）中表现出容量和密度优势，但它们在循环时遇到严重的结构退化，这是传统纳米结构技术无法解决的。在此，我们提出了一项深入的研究，以揭示铋（Bi）材料在合金化（脱）合金化时粉化的内在原因，并报告了一种新颖的块状颗粒结构，其中Bi纳米球镶嵌在块状碳（BiNC）中实现持久的Na/K存储。我们模拟了 Bi 在（去）合金反应过程中的体积膨胀抵抗机制，并揭示了（去）合金时的不可逆相变是 Bi 阳极结构退化的根本原因，而适当的压应力（〜10 %）由大块碳引发可以触发“多米诺骨牌式”Bi晶体的恢复。因此，所获得的BiNC表现出创纪录的高体积容量（SIB为823.1 mAh cm−3，PIB为848.1 mAh cm−3）和初始库仑效率（SIB为95.3％，PIB为96.4％），以及前所未有的循环稳定性（ SIB 进行 15000 次循环，每次循环仅降解 0.0015%），优于最先进的文献。这项工作提供了关于不良结构演变的新见解，并为合金型电极材料的抗降解结构的设计提出了基本准则。