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Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems

DOI: 10.1039/C9MH00765B DOI Help

Authors: Zachary W. Lebens-higgins (Binghamton University) , Nicholas V. Faenza (Rutgers University) , Maxwell D. Radin (University of California Santa Barbara) , Hao Liu (Binghamton University) , Shawn Sallis (Binghamton University; Advanced Light Source) , Jatinkumar Rana (Binghamton University) , Julija Vinckeviciute (University of California Santa Barbara) , Philip J. Reeves (University of Cambridge) , Mateusz Zuba (Binghamton University) , Fadwa Badway (Rutgers University) , Nathalie Pereira (Rutgers University) , Karena W. Chapman (Stony Brook University) , Tien-lin Lee (Diamond Light Source) , Tianpin Wu (Argonne National Laboratory) , Clare P. Grey (University of Cambridge) , Brent Melot (University of Southern California) , Anton Van Der Ven (University of California Santa Barbara) , Glenn G. Amatucci (Rutgers University) , Wanli Yang (Advanced Light Source) , Louis F. J. Piper (Binghamton University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Materials Horizons , VOL 5

State: Published (Approved)
Published: July 2019
Diamond Proposal Number(s): 19162

Open Access Open Access

Abstract: Oxygen participation, arising from increased transition metal–oxygen covalency during delithiation, is considered essential for the description of charge compensation in conventional layered oxides. The advent of high-resolution mapping of the O K-edge resonant inelastic X-ray scattering (RIXS) provides an opportunity to revisit the onset and extent of oxygen participation. Combining RIXS with an array of structural and electronic probes for the family of Ni-rich LiNi0.8Co0.2−yAlyO2 cathodes, we identify common charge compensation regimes that are assigned to formal transition metal redox (<4.25 V) and oxygen participation through covalency (>4.25 V). From O K-edge RIXS maps, we find the emergence of a sharp RIXS feature in these systems when approaching full delithiation, which has previously been associated with lattice oxidized oxygen in alkali-rich systems. The lack of transition metal redox signatures and strong covalency at these high degrees of delithiation suggest this RIXS feature is similarly attributed to lattice oxygen charge compensation as in the alkali-rich systems. The RIXS feature's evolution with state of charge in conventional layered oxides is evidence that this feature reflects the depopulation of occupied O 2p states associated with oxygen participation.

Subject Areas: Chemistry

Instruments: I09-Surface and Interface Structural Analysis

Other Facilities: Advanced Light Source