Size and Composition Effects in Sb-Carbon Nanocomposites for Sodium-Ion Batteries.

Sodium-ion batteries are in the spotlight as viable alternatives to lithium-ion batteries in stationary storage and power grid applications. Among possible anode materials, Sb is one of the interesting candidates due to a combination of battery-type potential plateaus in the charge-discharge profiles, high capacity (theoretical capacity of 660 mAh g-1), and demonstrated good cyclic stability. The influence of Sb particle size (particularly at the nanoscale range) and the composition of Sb-carbon composites on the electrode performance, stability, and charge storage mechanism is systematically evaluated here for the first time. A range of Sb-carbon nanocomposites with varied Sb particle size (between 50 and ∼1 nm) are studied. The control of the particle size is achieved via varying the carbon and Sb weight ratio in the precursors. The shape of charge-discharge profiles, hysteresis, and the difference in cyclic stabilities and rate performance are analyzed. The nanocomposite with the smallest particle size (∼1 nm) and the largest carbon content provides the most stable cyclic behavior and a better rate capability but suffers from an increased hysteresis between charge and discharge curves. In situ synchrotron X-ray diffraction experiments indicate that the storage mechanism in the Sb-carbon nanocomposites containing Sb nanoparticles is different from the electrodes with bulkier, micron-sized Sb particles, and the electrochemical reaction proceeds through a number of crystalline intermediates.