Studies on spinel cobaltites,MCo2O4 (M = Mn,Zn, Fe,Ni and Co) and their functional properties

Optimization of electrodes for charge storage with appropriate processing conditions places significant challenges in the developments for high performance charge storage devices. In this article, metal cobaltite spinels of formula MCo₂O₄ (where M = Mn, Zn, Fe, Ni and Co) are synthesized by oxalate decomposition method followed by calcination at three typical temperatures, viz. 350, 550, and 750 °C and examined their performance variation when used as anodes in lithium ion batteries. Phase and structure of the materials are studied by powder x-ray diffraction (XRD) technique. Single phase MnCo2O4,ZnCo2O4 and Co3O4 are obtained for all different temperatures 350 °C, 550 °C and 750 °C; whereas FeCo₂O₄ and NiCo₂O₄ contained their constituent binary phases even after repeated calcination. Morphologies of the materials are studied via scanning electron microscopy (SEM): needle-shaped particles of MnCo₂O₄ and ZnCo₂O₄, submicron sized particles of FeCo₂O₄ and agglomerated submicron particle of NiCo₂O₄ are observed. Galvanostatic cycling has been conducted in the voltage range 0.005–3.0 V vs. Li at a current density of 60 mA g^?1 up to 50 cycles to study their Li storage capabilities. Highest observed charge capacities are: MnCo₂O₄ – 365 mA h g^?1 (750 °C); ZnCo₂O₄ – 516 mA h g^?1 (550 °C); FeCo₂O₄ – 480 mA h g^?1 (550 °C); NiCo₂O₄ – 384 mA h g^?1 (750 °C); and Co₃O₄ – 675 mA h g^?1 (350 °C). The Co₃O₄ showed the highest reversible capacity of 675 mA h g^?1; the NiO present in NiCo₂O₄ acts as a buffer layer that results in improved cycling stability; the ZnCo₂O₄ with long needle-like shows good cycling stability.