Kagomé lattices as cathode: Effect of particle size and fluoride substitution on electrochemical lithium insertion in sodium- and ammonium Jarosites

•Synthesis of natro- and ammonium Jarosites.•Jarosites as cathodes for lithium ion batteries.•Li-ion electrochemistry of Jarosites.•Mössbauer spectroscopy of Jarosites.

Highly crystalline sodium and ammonium Jarosites, NaFe3(SO4)2(OH)6 and NH4Fe3(SO4)2(OH)6, have been synthesized employing hydrothermal synthesis routes. The structures consist of anionic layers of vertex-sharing FeO6 octahedra and SO4 tetrahedral units with interlayer space occupied by Na and ammonium ions, respectively. The corner-sharing FeO6 octahedral units form six and three rings similar to hexagonal tungsten bronze sheets also known as kagomé lattice. These sodium and ammonium Jarosites are thermally stable up to 400 °C and undergo facile electrochemical lithium insertion through the reduction of Fe3+ to Fe2+. Galvanostatic charge–discharge indicates that up to 2.25 and 2 lithium ions per formula unit can be inserted at an average voltage of 2.49 and 2.26 V to the sodium and the ammonium Jarosites, respectively, under slow discharge rate of C/50. The cycle-life and experimental achievable capacity show strong dependence on particle sizes and synthesis conditions. A small amount of fluoride substitution improves both achievable capacity and average voltage.

Graphical abstractDischarge capacity of jarosite phases as a function of particle size and fluoride substitution.Figure optionsDownload full-size imageDownload as PowerPoint slide