First-principles computation is recognized as an invaluable tool in designing new electrode materials for lithium ion batteries (LIBs). Numerous achievements in predicting relevant properties (including voltage, structure stability, electronic property and ionic mobility) of electrode materials for LIBs using Density Functional Theory has been reported in the last two decades (see, for instance, reference 1). Beyond the LIB technology, computational tools are critically important to enable the development of alternative energy storage technologies. In the last years, concerns on Li availability have prompted the search for suitable alternatives to rechargeable LIBs.  Batteries based on multivalent charge carriers (Mⁿ⁺) can exhibit advantages in terms of energy density since for a certain amount of M carriers the capacity is doubled (n=2) or tripled (n=3) when compared to single valent carriers like Li⁺ or Na⁺. Calcium is an attractive candidate due to its low cost, natural abundance and low reduction potential. The feasibility and reversibility of calcium plating in conventional alkyl carbonate electrolytes at moderate temperatures has been recently reported [2]. Such finding opens the way to the development of a new rechargeable battery technology using calcium anodes.  The identification of potential cathode and anode materials is a must to open the research avenues for the new calcium based battery technology (CIBs). In this contribution, we will show recent progress in first principles computation in predicting, understanding and improving the electrochemical properties of selected electrode materials for Li, Na, Mg and Ca ion batteries. 

Acknowledgments: The author thanks P. Tartaj (LIBs), F. Bardé (CIBs) and M.R. Palacin for the experimental work. Financial support from Ministerio de Ciencia e Innovación (grant MAT-2011-24757) and Toyota Battery Research division at Higashi Fuji (M6) is acknowledged.

[1] Y.S. Meng and M.E. Arroyo-de Dompablo, Energy and Environ. Science 2, 589, 2009

[2] A. Ponrouch, C. Frontera, F. Barde, M. R. Palacin. Nature Materials, DOI:10.1038/NMAT4461