Anode-free sodium metal batteries hold significant promise for high-energy-density storage but face critical challenges related to sodium deposition dynamics and interfacial instability. Traditional approaches, such as alloy-based current collectors or fluorinated interfaces, often suffer from irreversible volume expansion or corrosive fabrication processes. This study introduces a solvent co-intercalation-mediated in situ sodiophilic interface engineering strategy to overcome these limitations. A graphitized carbon-modified aluminum current collector dynamically regulates interfacial evolution through solvated sodium-ion co-intercalation during initial cycling, prompting the formation of a C-NaF interface with ultralow Na⁺ adsorption energy. This sodiophilic interface not only facilitates uniform sodium nucleation by providing abundant sodium-philic sites but also encourages the preferential decomposition of anions in the electrolyte, leading to the creation of a robust and NaF-rich solid electrolyte interphase. Consequently, the asymmetric half-cell delivers an ultralow nucleation overpotential (9.7 mV at 0.5 mA cm⁻²) and maintains an average coulombic efficiency of 99.8% over 400 cycles at 1 mA cm⁻². When combined with a Na₃V₂(PO₄)₂O₂F (NVPOF) cathode, the full cell achieves an energy density of 363 Wh kg⁻¹ with 80% capacity retention after 250 cycles at 0.5 C. This work integrates molecular-level dynamic interfacial engineering with macroscopic electrochemical stability, providing a scalable industrial solution for next-generation battery systems.

Aqueous zinc (Zn)-ion batteries (AZIBs) present safe and environmentally friendly features thereby emerging as an attractive energy storage device. The V₂O₅-based cathodes are promising because of their high theoretical capacity and energy density. However, insufficient interlayer distance, easy dissolution and structural collapse due to irreversible crystalline phase transition limit the development of V₂O₅ cathodes in AZIBs. Herein, doubly modified V₂O₅-based cathode which was in-situ intercalated by polyaniline (PANI) and composited with MXene (Ti₃C₂T_x) (denoted PVM) were synthesized by one-step method for the first time. The in situ intercalation of PANI provides a channel for the rapid diffusion of Zn²⁺ and the heterogeneous structures effectively promote charge transfer and enable structural integrity of cathode during cycling. Meanwhile, the conductivity of PVM electrode is greatly improved. Specifically, the PVM electrode shows a superior rate performance of 82 mAh·g⁻¹ after 2000 cycles at 10 A·g⁻¹. And it shows high pseudocapacitance behavior (80.23% capacitor contribution ratio at 0.1 mV·s⁻¹). A novel method of intercalation composite modification for the cathode is proposed, which provides fundamental guidance for the development of high-performance cathodes for AZIBs.