In this manuscript, we report a detailed physico-chemical comparison between the α- and β-polymorphs of the NaMnO₂ compound, a promising material for application in positive electrodes for secondary aprotic sodium batteries. In particular, the structure and vibrational properties, as well as electrochemical performance in sodium batteries, are compared to highlight differences and similarities. We exploit both laboratory techniques (Raman spectroscopy, electrochemical methods) and synchrotron radiation experiments (Fast-Fourier Transform Infrared spectroscopy, and X-ray diffraction). Notably the vibrational spectra of these phases are here reported for the first time in the literature as well as the detailed structural analysis from diffraction data. DFT+U calculations predict both phases to have similar electronic features, with structural parameters consistent with the experimental counterparts. The experimental evidence of antisite defects in the beta-phase between sodium and manganese ions is noticeable. Both polymorphs have been also tested in aprotic batteries by comparing the impact of different liquid electrolytes on the ability to de-intercalated/intercalate sodium ions. Overall, the monoclinic α-NaMnO₂ shows larger reversible capacity exceeding 175 mAhg⁻¹ at 10 mAg⁻¹.

Transition metal substitution is a key strategy to optimize the functional properties of advanced crystalline materials used as positive electrodes in secondary lithium batteries (LIBs). Here we investigate the structural alterations in the olivine lattice of Mn and Ni substituted LiCoPO₄ phase and the impact on performance in LIBs. X-ray diffraction (XRD) and extended X-ray absorption experiments have been carried out in order to highlight the structural alterations induced by partial substitution of cobalt by manganese and nickel. XRD analysis suggests that substitution induces an expansion of the lattices and an increase of the antisite disorder between lithium and transition metal ions in the structure. XAS data highlight negligible electronic disorder but a relevant modulation in the local coordination around the different metal ions. Moreover, galvanostatic tests showed poor reversibility of the redox reaction compared to the pure LCP sample, and this failure is discussed in detail in view of the observed remarkable structural changes.