The development of low-cost and long-lasting all-climate cathode materials for the sodium ion battery has been one of the key issues for the success of large-scale energy storage. One option is the utilization of earth-abundant elements such as iron. Here, we synthesize a NASICON-type tuneable Na₄Fe₃(PO₄)₂(P₂O₇)/C nanocomposite which shows both excellent rate performance and outstanding cycling stability over more than 4400 cycles. Its air stability and all-climate properties are investigated, and its potential as the sodium host in full cells has been studied. A remarkably low volume change of 4.0% is observed. Its high sodium diffusion coefficient has been measured and analysed via first-principles calculations, and its three-dimensional sodium ion diffusion pathways are identified. Our results indicate that this low-cost and environmentally friendly Na₄Fe₃(PO₄)₂(P₂O₇)/C nanocomposite could be a competitive candidate material for sodium ion batteries.

The local structure phase diagram of (Li ₂ S) _x (P ₂ S ₅ ) _100−x thiophosphates derived from pair distribution function crystallization experiments.

One major challenge in the field of lithium-ion batteries is to understand the degradation mechanism of high-energy lithium- and manganese-rich layered cathode materials. Although they can deliver 30 % excess capacity compared with today’s commercially- used cathodes, the so-called voltage decay has been restricting their practical application. In order to unravel the nature of this phenomenon, we have investigated systematically the structural and compositional dependence of manganese-rich lithium insertion compounds on the lithium content provided during synthesis. Structural, electronic and electrochemical characterizations of Li_xNi_0.2Mn_0.6O_y with a wide range of lithium contents (0.00 ≤ x ≤ 1.52, 1.07 ≤ y < 2.4) and an analysis of the complexity in the synthesis pathways of monoclinic-layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ oxide provide insight into the underlying processes that cause voltage fading in these cathode materials, i.e. transformation of the lithium-rich layered phase to a lithium-poor spinel phase via an intermediate lithium-containing rock-salt phase with release of lithium/oxygen.