Revisiting the charge compensation mechanisms in LiNi0.8Co0.2−yAlyO2 systems

Zachary W. Lebens-Higgins; Nicholas V. Faenza; Maxwell D. Radin; Hao Liu; Shawn Sallis; Jatinkumar Rana; Julija Vinckeviciute; Philip J. Reeves; Mateusz J. Zuba; Fadwa Badway; Nathalie Pereira; Karena W. Chapman; Tien-Lin Lee; Tianpin Wu; Clare P. Grey; Brent C. Melot; Anton Van Der Ven; Glenn G. Amatucci; Wanli Yang; Louis F. J. Piper

doi:10.1039/C9MH00765B

Revisiting the charge compensation mechanisms in LiNi_0.8Co_0.2−yAl_yO₂ systems†

Zachary W. Lebens-Higgins,

^a Nicholas V. Faenza,^b Maxwell D. Radin,^c Hao Liu,^d Shawn Sallis,^ef Jatinkumar Rana,

^a Julija Vinckeviciute,

^c Philip J. Reeves,

^g Mateusz J. Zuba,^e Fadwa Badway,^b Nathalie Pereira,^b Karena W. Chapman,^h Tien-Lin Lee,ⁱ Tianpin Wu,^j Clare P. Grey,

^g Brent C. Melot,

^k Anton Van Der Ven,^c Glenn G. Amatucci,^b Wanli Yang

^f and Louis F. J. Piper

*^ae

Author affiliations

* Corresponding authors

^a Department of Physics, Applied Physics, and Astronomy, Binghamton University, New York 13902, USA
E-mail: lpiper@binghamton.edu

^b Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers University, North Brunswick, New Jersey 08902, USA

^c Materials Department, University of California Santa Barbara, Santa Barbara, CA 93106, USA

^d Department of Chemistry, Binghamton University, New York 13902, USA

^e Materials Science & Engineering, Binghamton University, Binghamton, New York 13902, USA

^f Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

^g Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK

^h Department of Chemistry, Stony Brook University, 100 Nicolls Rd, Stony Brook, NY, USA

ⁱ Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, UK

^j X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

^k Department of Chemistry, University of Southern California, Los Angeles, USA

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 LiNi_0.8Co_0.2−yAl_yO₂ 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.

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Revisiting the charge compensation mechanisms in LiNi_0.8Co_0.2−yAl_yO₂ systems†

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Revisiting the charge compensation mechanisms in LiNi_0.8Co_0.2−yAl_yO₂ systems

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