(17)O NMR Spectroscopy in Lithium-Ion Battery Cathode Materials: Challenges and Interpretation

[Image: see text] Modern studies of lithium-ion battery (LIB) cathode materials employ a large range of experimental and theoretical techniques to understand the changes in bulk and local chemical and electronic structures during electrochemical cycling (charge and discharge). Despite its being rich in useful chemical information, few studies to date have used (17)O NMR spectroscopy. Many LIB cathode materials contain paramagnetic ions, and their NMR spectra are dominated by hyperfine and quadrupolar interactions, giving rise to broad resonances with extensive spinning sideband manifolds. In principle, careful analysis of these spectra can reveal information about local structural distortions, magnetic exchange interactions, structural inhomogeneities (Li(+) concentration gradients), and even the presence of redox-active O anions. In this Perspective, we examine the primary interactions governing (17)O NMR spectroscopy of LIB cathodes and outline how (17)O NMR may be used to elucidate the structure of pristine cathodes and their structural evolution on cycling, providing insight into the challenges in obtaining and interpreting the spectra. We also discuss the use of (17)O NMR in the context of anionic redox and the role this technique may play in understanding the charge compensation mechanisms in high-capacity cathodes, and we provide suggestions for employing (17)O NMR in future avenues of research.