Transition-Metal Pyrophosphates As Cathodes for Rechargeable Na-Ion Batteries: Effects on the Electrochemical Properties of Composition and Preparation Methods

The urgency of decreasing atmosphere pollution is driving industry toward more environmentally-friendly power sources, including solar, wind and hydro. As intermittent renewable energy technologies will become prevalent and integrated into the electrical grid, however, availability of large-scale storage systems will be crucial. At present, Li-ion batteries (LIBs) are one of the most encouraging technologies. On the other hand, grid-scale storage requires low cost, safety, and eco-friendly devices, and LIBs are approaching their technical limits combined with fast lithium sources pauperisation. Therefore, other chemistries must be considered, and Na-ion batteries (SIBs) are under rapidly development. In this context, materials for Na-ion batteries, in particular cathodic ones, are the subject of a growing research interest. [1,2] Among the cathode materials which are currently proposed for use in Na-ion batteries, an interesting family is that of sodium metal pyrophosphates having general formula Na 2 MP 2 O 7 (M = Co, Cu, Fe, Mn).[3] In fact, chiefly when Fe is employed as the transition metal, all the involved elements are non-toxic, abundant and environmentally-friendly. Pyrophosphate-based cathodes are normally prepared by means of a solid-state reaction process, possibly followed by reduction of the particle size and carbon coating. [4] In this study we focused our attention both on the Mn-Fe substitution and on the relationships among synthesis procedure and functional properties in determining the electrochemical properties of the cathode material. The solid solution Na 2 Fe 1− x Mn x P 2 O 7 ( x = 0, 0.25, 0.5, 0.75, 1) was prepared by conventional solid-state reaction. In addition, the Na 2 FeP 2 O 7 end-member was also prepared through different synthetic procedures: glucose-assisted, solid-state reaction and wet-chemistry (citrate) methods. The materials were characterized for what concerns their structural, morphological and electrochemical process through X-ray diffraction, scanning electron microscopy, cyclic voltammetry, charge/discharge curves. The results show that the system forms a complete solid solution over the entire composition range. The electrochemical performances are severely affected by the increase of Mn content, at least in the case of conventional high temperature solid-state reaction and standard slurry preparation. [5] The electrochemical results are compared and discussed in terms of morphological considerations. Interestingly, the electrochemical behavior of the Na 2 FeP 2 O 7 compound is strongly dependent upon the preparation method, especially for high C-rates. This is consistent with the fact that different preparation methods can modulate the morphological properties and the carbon coating of the material. References [1] N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba Chem. Rev. 2014 , 114 , 11636. [2] S.-W. Kim, D.-H. Seo, X. Ma, G. Ceder, K. Kang Adv. Energy Mater. 2012 , 2 , 710. [3] P. Barpanda, S.-I. Nishimura, A. Yamada Adv. Energy Mater. 2012 , 2 , 841. [4] P. Barpanda, T. Ye, S. Nishimura, S.-C. Chung, Y. Yamada, M. Okubo, H. Zhou, A. Yamada Electrochem. Commun. 2012 , 24 , 116. [5] C. Tealdi, M. Ricci, C. Ferrara, G. Bruni, E. Quartarone, P. Mustarelli Batteries 2016 , 2 , 1.