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

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [1];  [1];  [2];  [3];  [3];  [4];  [5];  [6];  [1];  [3];  [2];  [7];  [1]
  1. Binghamton Univ., NY (United States)
  2. Univ. of California, San Diego, CA (United States)
  3. Rutgers Univ., New Brunswick, NJ (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  7. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
+ Show Author Affiliations
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.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1608575
Alternate ID(s):
OSTI ID: 1633266
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 6 Vol. 11; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electrodes
Oxides
Oxygen
Redox reactions
Transition metals