Influence of Ga2O3, CuGa2O4 and Cu4O3 phases on the sodium-ion storage behaviour of CuO and its gallium composites

Abstract

CuO and its gallium composites with various compositions are successfully fabricated by using a hydrothermal technique followed by calcination at 900 °C. The added Ga precursors formed oxides in the composites, such as Ga₂O₃, CuGa₂O₄ and Cu₄O₃, as confirmed through the X-ray diffraction patterns as well as the HRTEM and SAED patterns. Further HRTEM analysis also confirmed that Cu₄O₃ and CuGa₂O₄ phases reside on the surface of CuO in the composites with a CuO : Ga ratio of 90 : 10. The contents of various oxide phases varied when we increased the amount of Ga in the CuO composites. Changing the ratios of CuO and Ga precursors in the composites is quite effective in tailoring the sodium-ion storage behaviour of CuO. The resultant CuO/Ga composites exhibit remarkable electrochemical performance for sodium-ion batteries in terms of capacity, rate capability and cycling performance. The composite containing 90% CuO and 10% Cu/Ga oxides delivers the highest charge capacity of 661 mA h g⁻¹ at a current density of 0.07 A g⁻¹ with a capacity retention of 73.1% even after 500 cycles. The structure and morphology of the composite (90% CuO and 10% Cu/Ga oxides) was successfully retained after 500 cycles, which was confirmed through ex situ XRD, SEM and HRTEM analyses. The composite also exhibited remarkable rate capability in which it delivered 96 mA h g⁻¹ even at a high current density of 6.6 A g⁻¹. The enhanced electrochemical performances of CuO and its gallium composites are attributed to the presence of Cu₄O₃ and CuGa₂O₄ phases. The Cu₄O₃ phase is actively involved in the redox reaction and the CuGa₂O₄ phase stabilizes the CuO phase and buffers the volume expansion of CuO during cycling. The present approach eplores great opportunities for improving the electrochemical performance of oxide based anode materials for sodium-ion batteries.