The major challenges of vanadium-based layered materials are their dissolution tendency and the instability of their bulk-phase structure, resulting in unsatisfactory cyclability, particularly at lower current densities. Herein, we propose a co-modification strategy of dual-ion doping and forming an in situ cathode-electrolyte interphase (CEI). The dual ions, consisting of an alkali-metal ion (Na⁺ or K⁺) and an alkaline-earth-metal ion (Ca²⁺ or Ba²⁺), stabilize the bulk phase. The latter forms a precipitate with SO₄²⁻ in the electrolyte as an in situ CEI with a balance of stability and pH adaptiveness. Based on the stabilized cathode from bulk phase to surface, Ca_0.56Na_1.19V₆O₁₆·4.09H₂O exhibits excellent cyclability, especially at lower current densities. The full cell retains 99.4% of capacity after 120 cycles at 0.2 A g⁻¹ and 25 °C while using Zn(OTF)₂ electrolyte. Moreover, it exhibits 84.5% capacity retention at 0.1 A g⁻¹ and −30 °C after 1000 cycles. The Zn²⁺/H⁺ intercalation mechanism was investigated by analytical characterizations and density functional theory (DFT) calculations, which implied that proton (de)intercalation is restrained at −30 °C, leading to the median discharge voltage increasing from 0.705 to 0.795 V. The co-modified cathode exhibits a significant performance in Zn(ClO₄)₂ electrolyte at 0.1 A g⁻¹ and −30 °C (90.8% capacity retention after 2000 cycles). The co-modification strategy provides a viable option for cathode design.

中文翻译：

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用于水性锌离子电池的层状水合钒酸盐正极的体表面共修饰


钒基层状材料的主要挑战是其溶解倾向和体相结构的不稳定性，导致循环性能不令人满意，特别是在较低电流密度下。在此，我们提出了双离子掺杂和原位形成阴极电解质界面（CEI）的共修饰策略。双离子，由碱金属离子（Na ⁺ 或 K ⁺ ）和碱土金属离子（Ca ²⁺ 或 Ba < b3>），稳定体相。后者与电解液中的 SO ₄ ²⁻ 形成沉淀物作为原位 CEI，具有稳定性和 pH 适应性的平衡。基于从体相到表面的稳定阴极，Ca _0.56 Na _1.19 V ₆ O ₁₆ ·4.09H ₂ 电解质时，全电池在 0.2 A g ⁻¹ 和 25 °C 下循环 120 次后仍保留 99.4% 的容量。此外，在0.1 A g ⁻¹ 和-30 °C下循环1000次后，其容量保持率为84.5%。通过分析表征和密度泛函理论（DFT）计算研究了 Zn ²⁺ /H ⁺ 插层机制，这表明质子（脱）插层在 -30 °C 时受到限制，导致中值放电电压从 0.705 增加到 0.795 V。共修饰阴极在 0.1 A g ⁻¹ ) ₂ 电解质中表现出显着的性能。 /b18> 和 −30 °C（2000 次循环后容量保持率为 90.8%）。共修饰策略为阴极设计提供了可行的选择。