Role of Ligand-to-Metal Charge Transfer in Anionic Redox Activity of the Layered Oxide Cathode for Na-Ion Batteries

IF 7.1 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI:10.1021/acs.chemmater.6c00365

Abhinanda Sengupta, Amreen Bano, Kritika Thapliyal, Aakash Ahuja, Sri Harsha Akella, Malachi Noked, Dan T. Major, Sagar Mitra

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Abstract

Developing high-performance cathode materials is crucial for advancing grid-scale sodium-ion batteries (SIBs). Here, we introduce a P2-type layered oxide cathode material, Na_0·67Ni_0·33Mn_0·51Ru_0·16O₂, which demonstrates exceptional electrochemical performance through a robust dual cationic–anionic redox mechanism. This material delivers a high discharge capacity of 175.6 mAh g⁻¹ at an average voltage of 3.6 V and maintains remarkable cycling stability with ∼93% capacity retention after 1000 cycles. A key to this performance is the strategic Ru doping, which plays a pivotal role in electronically stabilizing the oxidized oxygen states. By mediating the reversible formation of oxygen holes and preventing oxygen undercoordination, the Ru dopant stabilizes the anionic redox process. Unlike Na-rich layered oxides, this ligand-to-metal charge-transfer mechanism effectively suppresses detrimental oxygen evolution and preserves the structural integrity of the layered Na-deficient P2-type framework. This design strategy enables a synergistic redox landscape, confirmed by ex situ and operando advanced characterizations and theoretical calculations such as Fukui functions, offering critical insights into the rational design of high-capacity cathode for next-generation SIBs.

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配体-金属电荷转移在钠离子电池层状氧化物阴极阴离子氧化还原活性中的作用

开发高性能正极材料是推进电网级钠离子电池发展的关键。在这里，我们介绍了一种p2型层状氧化物正极材料Na0·67Ni0·33Mn0·51Ru0·16O2，该材料通过强大的正阴离子氧化还原机制表现出优异的电化学性能。该材料在3.6 V的平均电压下提供175.6 mAh g−1的高放电容量，并在1000次循环后保持显着的循环稳定性，容量保持率为93%。这种性能的关键是Ru的战略性掺杂，它在电子稳定氧化氧态方面起着关键作用。钌掺杂剂通过介导氧空穴的可逆形成和防止氧欠配位，稳定了阴离子氧化还原过程。与富钠层状氧化物不同，这种配体到金属的电荷转移机制有效地抑制了有害的氧释放，并保持了层状缺钠p2型框架的结构完整性。这种设计策略实现了协同氧化还原景观，通过非原位和操作的高级特性和理论计算（如福井函数）得到了证实，为下一代sib的高容量阴极的合理设计提供了关键见解。

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

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.