High-capacity Class Research Articles

Hydrothermal synthesis of Co-free NMA cathodes for high performance Li-ion batteries

Scalable and sustainable production of high voltage cathodes is required to meet the increasing demands for Li-ion batteries. Additionally, the anticipated scarcity of critical materials like cobalt necessitates demonstration of Co-free alternatives that can match the performance metrics of conventional cathodes. Herein, a hydrothermal synthesis route for production of a new class of high-capacity, cobalt-free cathode material, LiNi0.9Mn0.05Al0.05O2 (NMA9055) for next-generation Li-ion batteries is reported. The synthesized cathode material shows high crystallinity and purity with monodispersed spherical morphology. Extensive electrochemical, structural, and post-mortem characterization of this novel NMA material is carried out. NMA-Li half cells show an initial discharge capacity of 200 mAh/g with a 96% capacity retention over 100 cycles when cycled between 3.0 and 4.4 V. On the other hand, NMA full cells with Li4Ti5O12 (LTO) electrodes as the anode, show an initial discharge capacity of 186 mAh/g with 81% capacity retention over 200 cycles. Post-mortem structural and morphological characterization show that the NMA morphology and crystal structure do not degrade significantly over 200 charge/discharge cycles. This new class of cobalt free cathode material containing nickel, manganese and aluminum synthesized by an ammonia-free synthesis route is expected to provide a facile solution towards sustainable cathode production.

Effect of electrolyte anions on the cycle life of a polymer electrode in aqueous batteries

Redox polymers are a class of high-capacity, low-cost electrode materials for electrochemical energy storage, but the mechanisms governing their cycling stability are not well understood. Here we investigate the effect of anions on the longevity of a p-dopable polymer through comparing two aqueous zinc-based electrolytes. Galvanostatic cycling studies reveal the polymer has better capacity retention in the presence of triflate anions than that with sulfate anions. Based on electrode microstructural analysis and evolution profiles of the cell stacking pressure, the origin of capacity decay is ascribed to mechanical fractures induced by volume change of the polymer active materials during repeated cycling. The volume change of the polymer with the triflate anion is 61% less than that with the sulfate anion, resulting in fewer cracks in the electrodes. The difference is related to the different anion solvation structures—the triflate anion has fewer solvated water molecules compared with the sulfate anion, leading to smaller volume expansion. This work highlights that anions with low solvation degree are preferable for long-term cycling.