(Invited) Delineating the Intricacies Involved in the Synthesis of Cobalt-Free High-Nickel Layered Oxide Cathodes for Lithium-Ion Batteries

Abstract

Improving the energy density and cost of lithium-ion batteries (LIBs) requires a rational compositional design of layered oxide LiNi1-x-yMnxCoyO2 (NMC) cathodes. The prevailing trend is to increase the nickel content in the cathode to maximize energy density, but high-nickel NMC generally suffers from surface and bulk instabilities that shorten battery life. Dopants, such as cobalt, can help mitigate these issues, but its supply shortage issue prohibits its usage especially in the massive electric vehicle market. Our recent finding suggests that a combination of manganese and aluminum in LiNi0.9Mn0.05Al0.05O2 (NMA-90) promotes attractive energy density, cycle life, rate capability and thermal stability, proving that cobalt can be eliminated in high-nickel cathodes. Post-mortem analysis further reveals that the Mn-Al combination provides synergistic improvements in structural and surface stabilities compared to LiNi0.9Mn0.05Co0.05O2 (NMC-90) and LiNi0.9Co0.05Al0.05O2 (NCA-90). A thorough understanding of the relationship between the synthesis condition and optimal materials properties of NMA-90 is necessary to enable its large-scale deployment. We will present findings from the calcination and coprecipitation study of several cobalt-free cathodes to elucidate this relationship. It is revealed that the cycle stability of LiNi0.9Mn0.1O2 (NM-90) is not dependent on Li/Ni mixing or primary particle size, but is dependent on the calcination temperature. Incorporating Al into NM-90 during coprecipitation reactions cause high internal porosity in the hydroxide precursor, which impacts the final morphology of the calcined cathodes and thus their electrochemical stability. The ongoing work in our lab provides insight on the synthesis sensitivity of NMA and strategizes methods to control its electrochemical properties.