Understanding LiNiO2 Electronic Structure and Redox Mechanism by Raman and X-Ray Techniques

Abstract

LiNiO2 (LNO) is considered a very promising and high energy density alternative to Co-containing Li-ion battery cathodes. It is also the benchmarked cathode material of the European BIGMAP project, which aim is to combine advance operando characterization, computational modelling and artificial intelligence in order to accelerate the research and development of new generation batteries.However, the material suffers from several degradation issues resulting in fading cell performance. In particular, the presence of highly reactive Ni4+ species at the electrode/electrolyte interface1, Ni dissolution from the cathode leading to the loss of active material 2, and O2 release at high voltage are the major drawbacks precluding commercial applications. A recent in situ study1 has shown that O2 release compromises the structural stability and triggers reactions with ethylene carbonate (EC), prompting CO2evolution3,4.In parallel, solid state physics community is also largely interested into LiNiO2 in the framework of a larger investigation around the electronic and atomic structure of nickelates, in particular rare-earth nickelates. This interest rises from the fact that there is still no consensus on the atomic/electronic structure of LiNiO2, while different descriptions exist in literature. Local probe techniques demonstrate the distortion of NiO6 octahedra, and there are two on-going theories for explaining the presence of this distortion: (i) Ni3+ (t2g6 eg1) Jahn-Teller (JT) distortion, (ii) 2 Ni3+ → Ni2+ + Ni4+ bond disproportionation (BD)5. Surprisingly, the local order distortion does not result in the long-range distortion, the mechanism behind this phenomenon is not completely understood.In this contribution we present a detailed study of LNO cathode material by operando Raman and X-ray absorption spectroscopy (XAS) at the Ni K-edge, ex situ X-ray emission spectroscopy (XES) and resonant Inelastic X-ray scattering (RIXS). Distinguishing between JT and BD models is challenging, and therefore NaNiO2 reference is used, which is isoelectronic material to LiNiO2, and is known to feature long-range JT distortion.While XAS is widely established technique to probe local structure and transition metal oxidation state, RIXS is useful for assessing d-d transitions and bond disproportionation. Operando Raman spectroscopy is an excellent tool for studying phase transitions in Li-ion battery cathodes and is therefore complementary to the employed X-ray techniques6. It provides information on two characteristic for layered oxides crystalline phonon modes A1g and Eg, and sheds light on both short-range order and cationic/anionic redox. The penetration depth is estimated as top few hundred nanometers of around five micrometres sized secondary particle, therefore near-surface area is probed. The results show a complex behaviour of band positions and intensities during cycling (figure 1), corresponding to four phases transformations. Notably the peaks intensities increase considerably, while the widths are decreased, which is evidence of increased order upon material delithiation, and is in agreement with the Extended X-ray Absorption Fine Structure (EXAFS). Raman is also used to evaluate the contribution of anionic redox, since all the reduced oxygen species (superoxide, peroxide and molecular oxygen) have well-known Raman-active modes.To conclude, we demonstrate how a combination of multiple vibrational and X-rays based spectroscopies provides a better understanding of both LNO ground state electronic structure and redox mechanism. This increased fundamental understanding will stimulate the design of better strategies for prevention of the material degradation and improved cycle retention.