A mechanistic perspective of anion intercalation in graphite cathodes for dual-ion batteries

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics Pub Date : 2025-09-02 DOI:10.1016/j.ssi.2025.117010

Zexin Su , Yuanyuan Yang , Yuchen Zhang , Zheng Chen , Pengxian Han , Jingwen Zhao , Guanglei Cui

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引用次数: 0

Abstract

Graphite cathodes enable high-voltage dual-ion batteries (DIBs) through reversible anion intercalation. However, the molecular identity and dynamic evolution of intercalated anionic species, which critically govern the thermodynamic stability and electrochemical reversibility of this process, remain insufficiently understood. This Perspective synthesizes emerging evidence challenging the prevalent but oversimplified “naked anion” intercalation model, emphasizing how solvent co-intercalation potentially influences thermodynamic equilibria, interlayer anion transport kinetics, and charge storage mechanisms. The structural evolution of graphite during anion intercalation is also critically analyzed, with a focus on how interlayer spacing adjustments evolve during electrochemical cycling under solvent co-intercalation conditions. Furthermore, we present a systematic analysis of anion packing configurations within solvent-containing interlayers and their intrinsic link to theoretical capacity limits, offering new insights for optimizing intercalation efficiency. To advance the field, targeted research directions encompassing operando characterization of speciation dynamics, multiscale modeling of solvent co-intercalation pathways and mechanistic investigation into the origins of voltage hysteresis, are proposed to inform the rational design of next-generation high-performance DIB systems.

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双离子电池负离子插入石墨负极的机理研究

石墨阴极通过可逆的阴离子插入实现高压双离子电池（DIBs）。然而，对这一过程的热力学稳定性和电化学可逆性起关键作用的插层阴离子物种的分子特性和动态演化仍然知之甚少。本观点综合了挑战流行但过于简化的“裸阴离子”插层模型的新证据，强调了溶剂共插层如何潜在地影响热力学平衡、层间阴离子传输动力学和电荷存储机制。本文还分析了负离子插入过程中石墨的结构演变，重点研究了溶剂共插入条件下电化学循环过程中层间间距调整的变化。此外，我们还系统分析了含溶剂中间层中阴离子填充结构及其与理论容量限制的内在联系，为优化插层效率提供了新的见解。为了推动该领域的发展，提出了有针对性的研究方向，包括物种形成动力学的operando表征，溶剂共插层途径的多尺度建模以及电压滞后起源的机理研究，为下一代高性能DIB系统的合理设计提供信息。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Solid State Ionics 物理-物理：凝聚态物理

CiteScore

6.10

自引率

3.10%

发文量

152

审稿时长

58 days

期刊介绍： This interdisciplinary journal is devoted to the physics, chemistry and materials science of diffusion, mass transport, and reactivity of solids. The major part of each issue is devoted to articles on: (i) physics and chemistry of defects in solids; (ii) reactions in and on solids, e.g. intercalation, corrosion, oxidation, sintering; (iii) ion transport measurements, mechanisms and theory; (iv) solid state electrochemistry; (v) ionically-electronically mixed conducting solids. Related technological applications are also included, provided their characteristics are interpreted in terms of the basic solid state properties. Review papers and relevant symposium proceedings are welcome.