Understanding the Nature of Capacity Decay and Interface Properties in Li//LiNi_0.5Mn_1.5O₄Cells by Cycling Aging and Titration Techniques

The spinel structure LiNi0.5Mn1.5O4 (LNMO) is a propitious cathode material for next-generation lithium-ion batteries for fast charge-discharge applications, but its capacity decay mechanism and rate-limiting process are not yet well understood. In this study, electrochemical impedance spectroscopy (EIS) with galvanostatic intermittent titration (GITT) and cycling aging techniques were employed to investigate the nature of capacity decay in disordered-phase LNMO. Different resistive components were separated after every 10 cycles. Cell overvoltages (ΔVs) due to ohmic conduction, charge transfer (CT), and concentration polarization (CP) were individually determined. Results revealed that the cell exhibited a higher ΔV at a higher discharged state. However, the ΔV value for CP was higher at a higher state of charge (SOC), and the overall LNMO/electrolyte interface played a major role in the rate-determining step. Battery life was estimated based on the results. Battery calendar life was found to be more vulnerable than cycle life. Results also indicated that the working SOC range could be optimized based on the resistance analysis by avoiding those SOCs that have the most detrimental impact (e.g., heat generation and fire hazard).