How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode-Electrolyte Interface when Addressing Oxygen Redox

被引：41

作者：

Lebens-Higgins, Zachary W. ^{[2
]}

Chung, Hyeseung ^{[3
]}

Zuba, Mateusz J. ^{[4
]}

Rana, Jatinkumar ^{[4
]}

Li, Yixuan ^{[3
]}

Faenza, Nicholas, V ^{[5
]}

Pereira, Nathalie ^{[5
]}

McCloskey, Bryan D. ^{[6
,7
]}

Rodolakis, Fanny ^{[8
]}

Yang, Wanli ^{[9
]}

Whittingham, M. Stanley ^{[4
]}

Amatucci, Glenn G. ^{[5
]}

Meng, Ying Shirley ^{[3
]}

Lee, Tien-Lin ^{[10
]}

Piper, Louis F. J. ^{[1
,4
]}

机构：

[1] SUNY Binghamton, Dept Phys Appl Phys & Astron & Mat Sci & Engn, Binghamton, NY 13902 USA

[2] SUNY Binghamton, Dept Phys Appl Phys & Astron, Binghamton, NY 13902 USA

[3] Univ Calif San Diego, Dept NanoEngn, La Jolla, CA 92093 USA

[4] SUNY Binghamton, Mat Sci & Engn, Binghamton, NY 13902 USA

[5] Rutgers State Univ, Dept Mat Sci & Engn, Energy Storage Res Grp, North Brunswick, NJ 08902 USA

[6] Lawrence Berkeley Natl Lab, Energy Storage & Distributed Resources Div, Berkeley, CA 94720 USA

[7] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA

[8] Argonne Natl Lab, Argonne, IL 60439 USA

[9] Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA

[10] Diamond Light Source Ltd, Didcot OX11 0DE, Oxon, England

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2020年 / 11卷 / 06期

基金：

美国国家科学基金会;

关键词：

ANIONIC REDOX; 1ST CYCLE; LI; LITHIUM; EVOLUTION; BATTERIES; OXIDES; STATES; XPS; QUANTIFICATION;

D O I：

10.1021/acs.jpclett.0c00229

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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-Li2MnO3, 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.

引用

页码：2106 / 2112

页数：7

共 25 条

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Malmgren, S.
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SCIENTIFIC REPORTS, 2012, 2
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