X-ray photoelectron spectroscopy and electrochemical behaviour of 4 V cathode, Li(Ni1/2Mn1/2)O2

Layered Li(Ni_1/2Mn_1/2)O₂ was prepared by the solution and mixed hydroxide methods, characterised by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and studied by cyclic voltammetry (CV) and charge discharge cycling in CC and CCCV modes at room temperature (r.t.) and at 50 °C. The XPS studies show about 8% of Ni³⁺ and Mn³⁺ ions are present in Li(Ni²⁺_1/2Mn_1/2⁴⁺)O₂ due to valency-degeneracy. The compound prepared at 950 °C, 12 h, solution method gives a second cycle discharge capacity of 150 mA h g⁻¹ (2.5-4.4 V) at a specific current of 30 mA g⁻¹ and retains 137 mA h g⁻¹ at the end of 40 cycles. CV shows that the redox process at 3.7-4.0 V corresponds to Ni²⁺↔Ni⁴⁺ and clear indication of Mn^3+/4+ couple was noted at 4.2-4.5 V. The observed capacity-fading (2.5-4.4 V) is shown to be contributed by the polarisation at the end of charging. The cathodic capacity is stable up to 40 cycles in the voltage window, 2.5-4.2 V both at room temperature and 50 °C.