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

被引：42

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

[21] Quantitative study of valence and configuration interaction parameters of the Kondo semiconductors CeM2Al10 (M = Ru, Os and Fe) by means of bulk-sensitive hard X-ray photoelectron spectroscopy
Strigari, F.
Sundermann, M.
Muro, Y.
Yutani, K.
Takabatake, T.
Tsuei, K. -D.
Liao, Y. F.
Tanaka, A.
Thalmeier, P.
Haverkort, M. W.
Tjeng, L. H.
Severing, A.
[J]. JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 2015, 199 : 56 - 63
[22] Ether Based Electrolyte, LiB(CN)4 Salt and Binder Degradation in the Li-O2 Battery Studied by Hard X-ray Photoelectron Spectroscopy (HAXPES)
Younesi, Reza
Hahlin, Maria
Treskow, Marcel
Scheers, Johan
Johansson, Patrik
Edstrom, Kristina
[J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2012, 116 (35) : 18597 - 18604
[23] A synchrotron x-ray diffraction and hard x-ray photoelectron spectroscopy study of Zn negative electrodes at different charge and discharge states of Zn/MnO2 batteries using an ionic liquid-based gel polymer electrolyte
Abad, Jose
Santos, Florencio
Tafur, Juan P.
Urbina, Antonio
Roman, Elisa
Gonzalez-Martinez, J. F.
Rubio-Zuazo, J.
Castro, G. R.
Fernandez Romero, Antonio J.
[J]. JOURNAL OF POWER SOURCES, 2017, 363 : 199 - 208
[24] Spontaneous solid electrolyte interface formation in uncycled sodium half-cell batteries: using X-ray photoelectron spectroscopy to explore the pre-passivation of sodium metal by fluoroethylene carbonate before potentials are applied
Gimble, Nathan J.
Prieto, Amy L.
[J]. SUSTAINABLE ENERGY & FUELS, 2022, 6 (20) : 4736 - 4740
[25] Operando Observation of Lithiation and Delithiation Reactions of a LiCoO2-Li3BO3 Composite Electrode Formed on a Li6.6La3Zr1.6Ta0.4O12 Solid Electrolyte Sheet by Laboratory-based Hard X-ray Photoelectron Spectroscopy
Iwama, Tsukasa
Ohnishi, Tsuyoshi
Masuda, Takuya
[J]. ELECTROCHEMISTRY, 2023, 91 (11)

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