Tailoring Primary Particle Growth via Controlled Ammonia Feeding for Enhanced Electrochemical Stability of Hierarchical NCM622 Cathodes

Abstract

Ni-rich layered LiNi0.6Co0.2Mn0.2O2 (NCM622) cathodes are the most promising candidates for high-energy lithium-ion batteries, but their performance is often limited by structural instability and capacity fading due to large primary particle sizes and surface degradation. Precise control of the primary particle size significantly impacts the performance of NCM622 cathodes and can mitigate fatigue mechanisms, but the underlying processes remain unclear. In this study, NCM622 cathodes with various primary particle sizes were synthesized by applying a controlled co-precipitation strategy by systematically controlling the ammonia feed rate and solution pH during precursor formation. Interestingly, higher ammonia feed rates promoted the formation of smaller, more ordered primary particles, whereas lower feed rates and reduced pH produced larger primary particles in spherical secondary structures. Electrochemical evaluation revealed that cathodes composed of smaller primary particles exhibited enhanced Li+ diffusion kinetics and superior electrochemical performance compared to those synthesized under lower ammonia feeding or reduced pH conditions. Moreover, the optimized NCM622 electrode demonstrated excellent rate capability and maintained a stable layered microstructure during cycling, retaining ~86% of its initial capacity. These results demonstrate that fine-tuning the ammonia feeding conditions during co-precipitation provides a simple and effective approach to control primary particle growth, thereby improving the structural integrity and electrochemical durability of NCM622 cathode materials.