Layered NaNi0.5Mn0.5O2, employed as cathode materials in sodium ion batteries, is attracting interest due to its high working potential and high-capacity values, thanks to the big sodium amount hosted in the lattice. Many issues are, however, related to their use, particularly, the complex phase transitions occurring during sodium intercalation/deintercalation, detrimental for the structure stability, and the possible Mn dissolution into the electrolyte. In this paper, the doping with Ti, V, and Cu ions (10% atoms with respect to Ni/Mn amount) was used to stabilize different polymorphs or mixtures of them with the aim to improve the capacity values and cells cyclability. The phases were identified and quantified by means of X-ray powder diffraction with Rietveld structural refinements. Complex voltammograms with broad peaks, due to multiple structural transitions, were disclosed for most of the samples. Ti-doped sample has, in general, the best performances with the highest capacity values (120 mAh/g at C/10), however, at higher currents (1C), Cu-substituted sample also has stable and comparable capacity values.

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Na0.67MnO2 (NMO) stands out among the layered cathode materials used for sodium batteries due to its high-capacity values, low cost, and environmental friendliness. Unfortunately, many drawbacks arise during cycling, but nanostructure tailoring and doping can help to mitigate them. Our aim was to synthesize undoped and Cu- or Fe-doped NMO samples via the sol-gel route, with a different cooling step to room temperature, i.e., in a natural way or via quenching. The formation of a mixture of polymorphs was observed, as well as differences in the external morphology of the powders’ grains. The use of spectroscopic techniques, Mössbauer spectroscopy for the Fe-doped samples and Electron paramagnetic resonance, allowed us to gain insights into the oxidation states of transition metals and to make suggestions about the magnetic ordering, as well as on the possible presence of magnetic impurities. Cyclic voltammetry and galvanostatic cycling results were interpreted on the basis of the spectroscopic data: the introduction of substituents, in general, worsens the capacity values, due to the decrease in the P2 amount and the introduction of structural distortions. The structural stability of the samples in air as a function of time was also analyzed via X-ray diffraction, demonstrating the positive effect of Cu presence.

Ferrites, a broad class of ceramic oxides, possess intriguing physico-chemical properties, mainly due to their unique structural features, that, during these last 50–60 years, made them the materials of choice for many different applications. They are, indeed, applied as inductors, high-frequency materials, for electric field suppression, as catalysts and sensors, in nanomedicine for magneto-fluid hyperthermia and magnetic resonance imaging, and, more recently, in electrochemistry. In particular, ZnFe2O4 and its solid solutions are drawing scientists’ attention for the application as anode materials for lithium-ion batteries (LIBs). The main reasons are found in the low cost, abundance, and environmental friendliness of both Zn and Fe precursors, high surface-to-volume ratio, relatively short path for Li-ion diffusion, low working voltage of about 1.5 V for lithium extraction, and the high theoretical specific capacity (1072 mA h g−1). However, some drawbacks are represented by fast capacity fading and poor rate capability, resulting from a low electronic conductivity, severe agglomeration, and large volume change during lithiation/delithiation processes. In this review, the main synthesis methods of spinels will be briefly discussed before presenting the most recent and promising electrochemical results on ZnFe2O4 obtained with peculiar morphologies/architectures or as composites, which represent the focus of this review.

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