硬X射线光电子能谱对体积的敏感度如何：在研究氧还原时考虑阴极-电解质界面。
How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode-Electrolyte Interface when Addressing Oxygen Redox.
作者信息
Lebens-Higgins Zachary W, Chung Hyeseung, Zuba Mateusz J, Rana Jatinkumar, Li Yixuan, Faenza Nicholas V, Pereira Nathalie, McCloskey Bryan D, Rodolakis Fanny, Yang Wanli, Whittingham M Stanley, Amatucci Glenn G, Meng Ying Shirley, Lee Tien-Lin, Piper Louis F J
机构信息
Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, United States.
Department of NanoEngineering, University of California San Diego, La Jolla, California 92093, United States.
出版信息
J Phys Chem Lett. 2020 Mar 19;11(6):2106-2112. doi: 10.1021/acs.jpclett.0c00229. Epub 2020 Mar 4.
Sensitivity to the "bulk" oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes-LiMnO, Li-rich NMC, and NMC 442-that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.
对“体相”氧核心轨道的敏感性使硬X射线光电子能谱（HAXPES）成为研究氧氧化还原候选物的一种有吸引力的技术。各种研究报告称，在高电压下会出现一个额外的O 1s峰（530 - 531 eV），这被认为是体相氧氧化还原过程的直接特征。在此，我们发现三种模型阴极——LiMnO、富锂NMC和NMC 442——出现了530.4 eV的O 1s HAXPES峰，该峰与氧氧化还原没有明显联系。相反，这三个体系的530.4 eV峰归因于近表面区域的过渡金属还原和电解质分解。基于光电子能谱的氧氧化还原论断必须明确考虑该技术的表面敏感性以及阴极降解层的程度。
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