Investigating the effect of pH on the growth of coprecipitated Ni0.8Co0.1Mn0.1(OH)2 agglomerates as precursors of cathode materials for Li-ion batteries

Understanding how the morphology and microstructure of secondary particles are affected by pH is essential to design spherical and dense hydroxide aggregates as precursors of high-performance cathode materials for lithium-ion batteries. To investigate the interplay between thermodynamic reaction conditions and the physicochemical properties of precursors, a chemical equilibrium model is used to describe the evolution of metal ammonia complexes. Furthermore, the formation and growth of aggregates are studied by monitoring the changes in surface morphologies and crystal structures of precursors at different reaction times. As the pH value varied, two notable phenomena occurred during crystal growth: the fast growth of grains in the early stage as the pH decreased and the layered growth of grains in the later stage with increased pH values. Such findings could be explained from the following two perspectives. First, the decrease in pH causes a significant increase in the complex ion concentration, thereby facilitating the growth of crystals along the [010] direction. Second, an increase in pH generally accelerates deprotonation of the crystal surface, thus strengthening the adsorption of complex ions on the crystal surface and promoting layer-by-layer growth of primary grains along the [001] direction.