Revealing Defects in Crystalline Lithium-Ion Battery Electrodes by Solid-State NMR: Applications to LiVPO₄F

Identifying and characterizing defects in crystalline solids is a challenging problem, particularly for lithium-ion intercalation materials, which often exhibit multiple stable oxidation and spin states as well as local ordering of lithium and charges. Here, we reveal the existence of characteristic lithium defect environments in the crystalline lithium-ion battery electrode LiVPO 4 F and establish the relative subnanometer-scale proximities between them. Well-crystallized LiVPO 4 F samples were synthesized with the expected tavorite-like structure, as established by X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) measurements. Solid-state 7 Li nuclear magnetic resonance (NMR) spectra reveal unexpected paramagnetic 7 Li environments that can account for up to 20% of the total lithium content. Multidimensional and site-selective solid-state 7 Li NMR experiments using finite-pulse radio frequency-driven recoupling (fp-RFDR) establish unambiguously that the unexpected lithium environments are associated with defects within the LiVPO 4 F crystal structure, revealing the existence of dipole–dipole-coupled defect pairs. The lithium defects exhibit local electronic environments that are distinct from lithium ions in the crystallographic LiVPO 4 F site, which result from altered oxidation and/or spin states of nearby paramagnetic vanadium atoms. The results provide a general strategy for identifying and characterizing lithium defect environments in crystalline solids, including paramagnetic materials with short 7 Li NMR relaxation times on the order of milliseconds.