Electrochemical investigation of LiNi0.5Mn1.5O4 thin film intercalation electrodes

This work provides kinetic and transport parameters of Li-ion during its extraction/insertion into thin film LiNi_0.5Mn_1.5O₄ free of binder and conductive additive. Thin films of LiNi_0.5Mn_1.5O₄ (0.2 μm thick) were prepared on electronically conductive gold substrate utilizing the electrostatic spray deposition technique. High purity LiNi_0.5Mn_1.5O₄ thin film electrodes were observed with cyclic voltammetry, to exhibit very sharp peaks, high reversibility, and absence of the 4 V signal related to the Mn³⁺/Mn⁴⁺ redox couple. The electrode subjected to 100 CV cycles of charge/discharge delivered a capacity of 155 mAh g⁻¹ on the first cycle and sustained a good cycling behavior while retaining 91% of the initial capacity after 50 cycles. Kinetics and mass-transport of Li-ion extraction at LiNi_0.5Mn_1.5O₄ thin film electrode were investigated by means of electrochemical impedance spectroscopy. The apparent chemical diffusion coefficient (D_app) value determined from EIS measurements changed depending on the electrode potential in the range of 10⁻¹⁰-10⁻¹² cm² s⁻¹. The D_app profile shows two minimums at the potential values close to the peak potentials of the corresponding cyclic voltammogram.