Promoting Reversible Anionic Redox in Sodium-Ion Cathodes by Doping and Phase Control

IF 9.6 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2025-03-13 DOI:10.1021/acsmaterialslett.4c0259710.1021/acsmaterialslett.4c02597

Shipeng Jia, Marzieh Abdolhosseini, Yixuan Li, Sang-Jun Lee, Hirohito Ogasawara, Ning Chen, Alexander Hebert, J. Michael Sieffert, Maddison Margaret Eisnor and Eric McCalla*,

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Abstract

Important efforts are underway to harness anionic redox to obtain high-energy Na-ion cathodes. Previously, we identified disruptive dopants in Na–Mn–O that induced reversible oxygen redox. Here, we perform detailed mechanistic studies to understand why these dopants are effective. First, we confirm that no transition metals (TMs) are being oxidized─it is indeed oxygen redox. We also identify that reversible TM migration occurs in the P2 phase where reversible anionic redox occurs, while the migration is irreversible in the distorted P′2 phase. Structural control over the anionic redox is highly significant, but we further elucidate the role of the disruptive dopants. Localized oxygen holes are identified as the source of the reversible anionic redox, and these are deemed to remain stable due to the dopants minimizing the interactions between oxygens to prevent their dimerization. These important contributions to understanding anionic redox will help realize viable high-energy Na-ion batteries.

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掺杂与相控促进钠离子阴极阴离子可逆氧化还原

利用阴离子氧化还原来获得高能态 Na 离子阴极的重要工作正在进行中。此前，我们在 Na-Mn-O 中发现了可诱导可逆氧氧化还原的破坏性掺杂剂。在此，我们进行了详细的机理研究，以了解这些掺杂剂为何有效。首先，我们确认没有过渡金属（TMs）被氧化--确实是氧氧化还原。我们还发现，在发生可逆阴离子氧化还原的 P2 相中发生了可逆的 TM 迁移，而在扭曲的 P′2 相中迁移是不可逆的。阴离子氧化还原的结构控制非常重要，但我们进一步阐明了破坏性掺杂剂的作用。局部氧洞被确定为可逆阴离子氧化还原的来源，由于掺杂剂最大限度地减少了氧原子之间的相互作用以防止其二聚化，这些氧洞被认为保持了稳定。这些对理解阴离子氧化还原的重要贡献将有助于实现可行的高能纳离子电池。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.