One of the challenges in enhancing the performance of Lithium ion batteries for stable energy storage is looking beyond extraction of single electron per formula unit of cathode material during the delithiation without phase change of the material. We have investigated lithium ferrous silicate by partial substitution of lithium by sodium atoms using density functional theory to achieve this. Our calculations have suggested that the substitution of lithium with sodium in controlled amounts is just sufficient to provide structural and phase stability during delithiation process. The larger size of sodium atom assists in easier extraction of lithium ions by providing wider pathways. These studies suggest the possibility of extracting more than one Li-ion per formula unit making this a promising cathode material for use in Li-ion battery applications. (C) 2015 Elsevier B.V. All rights reserved.