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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.

A range of high-capacity Li-ion anode materials (conversion reactions with lithium) suffer from poor cycling stability and limited high-rate performance. These issues can be addressed through hybridization of multiple nanostructured components in an electrode. Using a Co3O4-Fe2O3/C system as an example, we demonstrate that the cycling stability and rate performance are improved in a hybrid electrode. The hybrid Co3O4-Fe2O3/C electrode exhibits long-term cycling stability (300 cycles) at a moderate current rate with a retained capacity of approximately 700 mAh g(-1). The reversible capacity of the Co3O4-Fe2O3/C electrode is still about 400 mAh g(-1) (above the theoretical capacity of graphite) at a high current rate of ca. 3 A g(-1), whereas Co3O4-Fe2O3, Fe2O3/C, and Co3O4/C electrodes (used as controls) are unable to operate as effectively under identical testing conditions. To understand the structure-function relationship in the hybrid electrode and the reasons for the enhanced cycling stability, we employed a combination of ex situ and in situ techniques. Our results indicate that the improvements in the hybrid electrode originate from the combination of sequential electrochemical activity of the transition metal oxides with an enhanced electronic conductivity provided by percolating carbon chains.