We report novel electrode architectures for high capacity multivalent conversion compounds such as iron (ii and iii) fluoride. The material and electrode design approach addresses the intrinsically poor transport and diffusion kinetics associated with ionic solids such as iron fluorides and significantly improves their electrochemical and cycle life performance. A comparison is made between the performances of 3D electrode architecture versus the slurry coated fluoride electrodes. Detailed microstructural analysis and mechanistic scenarios are discussed that would enable development of practical high energy density conversion based electrodes for energy storage application. © 2014 The Royal Society of Chemistry.