Clarifying the origin of molecular O2 in cathode oxides

IF 37.2 1区 材料科学 Q1 CHEMISTRY, PHYSICAL
Xu Gao, Biao Li, Kurt Kummer, Andrey Geondzhian, Dmitry A. Aksyonov, Rémi Dedryvère, Dominique Foix, Gwenaëlle Rousse, Mouna Ben Yahia, Marie-Liesse Doublet, Artem M. Abakumov, Jean-Marie Tarascon
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Abstract

Anionic redox has reshaped the conventional way of exploring advanced cathode materials for Li-ion batteries. However, how anions participate in the redox process has been the subject of intensive debate, evolving from electron holes to O–O dimerization and currently to a focus on trapped molecular O2 based on high-resolution resonant X-ray inelastic scattering research. Here we show that the resonant X-ray inelastic scattering signal of molecular O2 is not exclusive to Li-rich oxide cathodes, but appears consistently in O-redox-inactive oxide materials even with a short beam exposure time as low as 1 min, indicating that molecular O2 species are not directly related to voltage hysteresis and voltage decay. We further demonstrated that molecular O2 is not a direct product of electrochemistry but more likely a consequence of the core excitation process in resonant X-ray inelastic scattering, for which the possible scenarios of the dissociation of ‘M-(O–O)’-like species on beam excitation must be considered. Collectively, our results reconcile the conflicting reported results on the (non-)observation of molecular O2 signal collected from different beamlines and suggest that molecular O2 is not the energetic engine of new battery oxide cathodes.

Abstract Image

澄清了阴极氧化物中O2分子的来源
阴离子氧化还原重塑了探索锂离子电池先进正极材料的传统方式。然而,阴离子如何参与氧化还原过程一直是激烈争论的主题,从电子空穴到O-O二聚化,以及目前基于高分辨率共振x射线非弹性散射的捕获分子O2研究的重点。我们发现O2分子的谐振x射线非弹性散射信号并非只存在于富锂氧化物阴极中,即使在短束曝光时间低至1 min的o -氧化还原活性氧化物材料中也一致出现,这表明O2分子种类与电压滞后和电压衰减没有直接关系。我们进一步证明了分子O2不是电化学的直接产物,而更可能是共振x射线非弹性散射中核心激发过程的结果,因此必须考虑光束激发下‘ M-(O-O) ’类物质解离的可能情况。总的来说,我们的结果调和了从不同光束线收集的分子O2信号的(非)观察结果的冲突,并表明分子O2不是新电池氧化物阴极的能量引擎。
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来源期刊
Nature Materials
Nature Materials 工程技术-材料科学:综合
CiteScore
62.20
自引率
0.70%
发文量
221
审稿时长
3.2 months
期刊介绍: Nature Materials is a monthly multi-disciplinary journal aimed at bringing together cutting-edge research across the entire spectrum of materials science and engineering. It covers all applied and fundamental aspects of the synthesis/processing, structure/composition, properties, and performance of materials. The journal recognizes that materials research has an increasing impact on classical disciplines such as physics, chemistry, and biology. Additionally, Nature Materials provides a forum for the development of a common identity among materials scientists and encourages interdisciplinary collaboration. It takes an integrated and balanced approach to all areas of materials research, fostering the exchange of ideas between scientists involved in different disciplines. Nature Materials is an invaluable resource for scientists in academia and industry who are active in discovering and developing materials and materials-related concepts. It offers engaging and informative papers of exceptional significance and quality, with the aim of influencing the development of society in the future.
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