Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV₃O₈, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV₃O₈ can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg⁻¹ after 10 cycles in the potential window of 0.8–3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li⁺ and Na⁺ cations into LiV₃O₈, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li_0.7Na_0.7V₃O₈ in Na-rich electrolytes, or to Li₄V₃O₈ in Li-rich electrolytes. The chemical diffusion coefficients of Na⁺ and Li⁺ in crystalline LiV₃O₈ are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li_0.7Na_0.7V₃O₈-type structure favors intercalation of Na⁺, whereas the LiV₃O₈-type prefers to accommodate Li⁺ cations.

含钒（V）的氧化物对碱性离子表现出优异的嵌入性能，尽管该材料的性能很大程度上取决于其表面形态。在这项工作中，通过传统的固态合成方法制备的LiV ₃ O _8的嵌入活性首次在以Na为负极，Na / Li比例不同的非水Li，Na离子混合电池中得到了证明。电解质。在纯Na离子电池中，每个分子单位的LiV ₃ O ₈可以通过两步过程在室温下可逆地插入一个Na ，而进一步的插入会导致材料逐渐非晶化，比容量为190 mAhg ^-1在0.8-3.4 V的电势窗口中经过10个循环后。锂，钠离子混合电池的特征是同时将Li ⁺和Na ⁺阳离子嵌入LiV ₃ O _8中，导致形成第二相。根据电解质的组成，该第二相在富钠电解质中与Li _0.7 Na _0.7 V ₃ O _8或在富锂电解质中与Li ₄ V ₃ O ₈具有结构相似性。Na ⁺和Li ⁺在晶体LiV ₃ O _8中的化学扩散系数它们非常接近，因此可以解释这些阳离子的共嵌入。如DFT计算所示，一旦形成Li _0.7 Na _0.7 V ₃ O ₈型结构，则有利于Na ^+的嵌入，而LiV ₃ O ₈型则倾向于容纳Li ⁺阳离子。