In situ Study of Phase Transitions in La$_2$NiO$_{4+\delta}$ using Raman Spectroscopy

TL;DR

This study uses Raman spectroscopy to investigate how oxygen doping affects the phase transitions and structure of La$_2$NiO$_{4+eta}$, providing insights crucial for its applications in fuel cells, electrolysers, and memristive devices.

Contribution

It offers new experimental data on the phase diagram and structural changes of La$_2$NiO$_{4+eta}$ with oxygen doping using Raman spectroscopy, including in thin film form.

Findings

Identification of phase transitions with varying oxygen content.

Observation of chemical expansion related to doping levels.

Insights into the effects of grain size on phase stability.

Abstract

La$_2$NiO$_{4+\delta}$ has attracted increasing interest in recent years, both as oxygen electrode in solid oxide fuel cells and electrolysers due to its high electrochemical activity at intermediate to high temperatures, and as key component of memristive devices for neuromorphic computing, owing to its variable oxygen stoichiometry. The integration of La$_2$NiO$_{4+\delta}$ into devices operating at different temperatures and oxygen partial pressures requires knowledge of the effects of hyper-stoichiometry ($\delta$) on its crystalline structure. La$_2$NiO$_{4+\delta}$ is known to accommodate oxygen at interstitial sites allowing for large delta values, up to ~ 0.16. In addition, the O-doping - temperature phase diagram is known to be complex, exhibiting several phase transitions with increasing delta. Herein, we use Raman spectroscopy to monitor the effects of O-doping in the phase diagram and the various structures it contains. Throughout this work, we studied this material in its usual ceramic form, as well as in the form of thin films. Results are discussed in terms of phase transitions, chemical expansion, and some of the possible consequences of the low mean grain size inherent to such thin films.