Co-Free Heteroatom-Doped P2-Type Layered Oxide Cathodes: Advancing High Power Sodium-Ion Battery Technology

Abstract

Sodium-ion battery technology has been blooming as an indigenous solution to stationary storage applications, triggering the cultivation of a cutting-edge alternative to the archaic lithium-ion (Li-ion) batteries due to high abundance, inexpensiveness, sustainability, safety and similar redox chemistry as of Li-ion technology 1. Although Na-ion batteries are propitious however, challenges such as long-term stability, high energy density, high specific capacity have impeded the practical application 2. The stepping stone for a successful Na-ion battery lies in the cathode, thus researchers have focused on development of layered oxide cathode. These are classified into P2, P3, O3 phases, depending on the environment of Na (prismatic or octahedral) and the stacking sequence of the anionic layers 3. P2-type Na0.67Ni0.33Mn0.65O2 (NMNO) cathodes offer high theoretical capacity, environmental friendliness, air-moisture stability, facile synthesis, and direct sodium-ion diffusion. However, there are still some setbacks, such as limited reversible capacity, rapid capacity decay, sluggish Na-ion kinetics, cracking and exfoliation in the crystallites 4. In order to overcome the challenges faced by sodium-ion batteries, researchers have employed several strategies such as inert or active cation substitution, limiting the cut-off voltage, surface modification, preparation of mixed-phase materials, sodium compensation additives, selection of binder, and choice of electrolyte 5. One of the most effective strategies is the doping of electrochemically inactive transition metals in layered transition metal oxide cathodes. However, a better understanding of the parameters that govern the stability of these cathodes are still necessary.By exploring the various factors that impact the stability of layered transition metal oxide cathodes, we propose a novel approach to synthesize a durable P2-type Na0.67Ni0.33Mn0.65Nb0.02O2 (NMNNbO) electrode with robust hexagonal crystallites through a quick, energy-efficient and cost-effective microwave-irradiated synthesis technique. Previous studies have utilized modified Pechini or conventional solid-state routes for inactive transition metal doping, which can be expensive, time-consuming and energy-intensive 6. This leads to an efficient cathode material with higher capacity and improved rate capability, which could be produced on a commercial scale at a lower cost due to the reduced synthesis time. A comprehensive investigation of the cathode material through X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron microscopy (XPS), reveals its superior electrochemical performance, stability, and durability. Through the use of advanced in-situ and ex-situ characterization techniques, the mechanism of Na-ion insertion and extraction, phase transition, and crack formation have been elucidated. Additionally, first-principle calculations using density functional theory (DFT) have been employed to gain a deeper understanding on the role of Nb in the cathode material. Electrochemical characterization was done against Na-metal in a half-cell format utilizing the electrolyte, 1 M NaPF6 in ethylene carbonate and propylene carbonate (1:1). The practicality of the material has also been validated through the evaluation of a full-cell performance against pre-sodiated hard carbon anode. A deeper understanding of the parameters affecting the electrochemical performance, can accelerate the development of high power and durable sodium-ion batteries, making them a more viable option for energy storage applications.