Alloy-based anodes are considered to be a promising choice for next-generation high-energy density devices; nevertheless, lithiation-induced anisotropic swelling and ongoing solid electrolyte interphase growth and cracking severely limit practical applicability. Herein, an anionic and cationic co-driving strategy is proposed for the alloy-based (Si) anode that aims to improve structural stability with controlled ion migration pathways and enhanced reaction kinetics, eventually leading to better capacity, high-rate performance, and cycle performance for lithium storage. Ex-situ tests and density functional theory simulations show that Co-HHTP has both anionic and cationic co-storage capabilities. Furthermore, the strong interactions between Co-HHTP and anionic species may impede anion transport towards the silicon surface, hence mitigating the recurrent degradation of the solid electrolyte interphase. As a proof of concept, the Si-based anode, fitted with Co-HHTP, delivers a high initial Coulombic efficiency of 80.4 %, a large reversible capacity (1648.0 mAh g⁻¹ at 0.2 A g⁻¹), and an ultralow attenuation rate of 0.034 % per cycle over 1000 cycles. The proposed approach provides a new strategy for a high-performance anode through functional coating structural construction coupled with anionic and cationic co-storage that confine anion diffusion and facilitate lithium storage and migration.

合金基阳极被认为是下一代高能量密度器件的有前途的选择；然而，锂化引起的各向异性膨胀和持续的固体电解质界面生长和开裂严重限制了实际应用。在此，提出了一种用于合金基（Si）阳极的阴离子和阳离子共同驱动策略，旨在通过受控的离子迁移路径和增强的反应动力学来提高结构稳定性，最终导致更好的容量、高倍率性能和循环锂存储性能。异位测试和密度泛函理论模拟表明Co-HHTP同时具有阴离子和阳离子共储存能力。此外，Co-HHTP和阴离子物质之间的强相互作用可能会阻碍阴离子向硅表面的传输，从而减轻固体电解质界面的反复降解。作为概念验证，配备 Co-HHTP 的硅基阳极具有 80.4% 的高初始库仑效率、大可逆容量（0.2 A g ^{-1时为 1648.0 mAh g -1}）和超低衰减超过 1000 个周期时，每个周期的损耗率为 0.034%。该方法通过功能涂层结构构造与阴离子和阳离子共存储相结合，限制阴离子扩散并促进锂存储和迁移，为高性能阳极提供了一种新策略。