Surface chemistry dependence on aluminum doping in Ni-rich LiNi0.8Co0.2−yAlyO2 cathodes

DOI: 10.1038/s41598-019-53932-6

Authors: Zachary W. Lebens-higgins (Binghamton University) , David M. Halat (University of Cambridge) , Nicholas V. Faenza (Rutgers University) , Matthew J. Wahila (Binghamton University) , Manfred Mascheck (Scienta Omicron AB) , Tomas Wiell (Scienta Omicron AB) , Susanna K. Eriksson (Scienta Omicron AB) , Paul Palmgren (Scienta Omicron AB) , Jose Rodriguez (Binghamton University) , Fadwa Badway (Rutgers University) , Nathalie Pereira (Rutgers University) , Glenn G. Amatucci (Rutgers University) , Tien-lin Lee (Diamond Light Source) , Clare P. Grey (University of Cambridge) , Louis F. J. Piper (Binghamton University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Scientific Reports , VOL 9

State: Published (Approved)
Published: December 2019
Diamond Proposal Number(s): 22250 , 22148

Abstract: Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2−yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes.

Journal Keywords: Batteries; Characterization and analytical techniques

Subject Areas: Chemistry, Energy


Instruments: I09-Surface and Interface Structural Analysis

Documents:
s41598-019-53932-6.pdf