RESUMEN
The long-term cycling stability of LiCoO2 under high-voltage operation in lithium-ion batteries is still not satisfactory and the mechanism of capacity decay is not well understood. Here we mainly apply 17O MAS NMR spectroscopy to probe the phase transformation of cycled LiCoO2 cathodes in both liquid cells and solid cells. It turns out that deterioration into the spinel phase is the main cause.
Asunto(s)
Suministros de Energía Eléctrica , Litio , ElectrodosRESUMEN
Solid-state NMR has been a vital tool for the study of structural evolution of cathodes in lithium-ion and sodium-ion batteries. However, the differentiation of relaxation parameters for certain sites is difficult owing to limited spectral resolution associated with strong anisotropic hyperfine interaction. Here we propose a novel IR-pjMATPASS method that can measure T1 relaxation with site-specific resolution for paramagnetic solids. We apply this method to the characterization of ball-milling induced order-disorder phase transition in Li6CoO4 as a case study. The quasi-quantitate 7Li NMR enables the synthetic optimization of high energy ball-milling conditions to harvest a disordered cubic phase through site-specific 7Li T1 measurements. The example study shown here provides a quantitative strategy for NMR studies of paramagnetic solids.