A Fundamental Correlative Spectroscopic Study on Li1-x NiO2 and NaNiO2
Journal article, 2024
The intricate relationship between local atomic arrangements and electronic states significantly influences the electrochemical properties of Li-ion battery cathode materials. Despite decades of investigation, a consensus regarding the local atomic and electronic structure of LiNiO2 remains elusive. This ambiguity stems from the potential distortion of Ni sites, either via Jahn-Teller (JT) distortion or bond disproportionation (BD), complicating the understanding of the charge compensation mechanism involving Ni and O. This study compares the structures of LiNiO2 and NaNiO2, a JT system, using an innovative approach that integrates bulk spectroscopy techniques on standardized interoperable samples for enhanced reliability. While X-r and theoretical calculations fail to differentiate between the proposed scenarios, Raman spectroscopy highlights local structural distinctions between monoclinic NaNiO2 and rhombohedral LiNiO2. HAXPES confirms various formal oxidation states for Ni, supported by RIXS data indicating 3d8 states, emphasizing negative charge transfer from Ni and some bond disproportionation in LiNiO2. Regarding charge compensation, XRS and RIXS suggest oxygen hole involvement in redox activity, whereas Raman spectroscopy does not detect molecular oxygen. This comprehensive spectroscopic analysis highlights the importance of correlative characterization workflows in elucidating complex structural-electrochemical relationships.
batteries
correlative spectroscopy
electronic structure
local atomic structure
operando characterization
Author
Quentin Jacquet
Grenoble Alpes University
Nataliia Mozhzhukhina
Chalmers, Physics, Materials Physics
Peter N.O. Gillespie
Consiglo Nazionale Delle Richerche
Gilles Wittmann
SOLEIL Synchrotron
Lucia Perez Ramirez
SOLEIL Synchrotron
Federico G. Capone
Centre national de la recherche scientifique (CNRS)
Physicochimie des Electrolytes et Nanosystèmes Interfaciaux
Jean Pascal Rueff
SOLEIL Synchrotron
Pierre and Marie Curie University (UPMC)
Stephanie Belin
SOLEIL Synchrotron
R. Dedryvere
Centre national de la recherche scientifique (CNRS)
Universite de Pau et des Pays de L'Adour
L. Stievano
Institut Charles Gerhardt Montpellier
Centre national de la recherche scientifique (CNRS)
Aleksandar Matic
Chalmers, Physics, Materials Physics
E. Suard
Institut Laue-Langevin
Nicholas B. Brookes
European Synchrotron Radiation Facility (ESRF)
Alessandro Longo
Istituto per lo Studio dei Materiali Nanostrutturati del C.N.R.
European Synchrotron Radiation Facility (ESRF)
Deborah Prezzi
Consiglo Nazionale Delle Richerche
Sandrine Lyonnard
Grenoble Alpes University
A. Iadecola
Centre national de la recherche scientifique (CNRS)
Physicochimie des Electrolytes et Nanosystèmes Interfaciaux
Advanced Energy Materials
1614-6832 (ISSN) 1614-6840 (eISSN)
Vol. 14 41 2401413Subject Categories
Materials Chemistry
Areas of Advance
Materials Science
DOI
10.1002/aenm.202401413