Facile and Scalable Development of High-Performance Carbon-Free Tin-Based Anodes for Sodium-Ion Batteries.

Tin (Sn)-based anodes for sodium (Na)-ion batteries possess higher Na-storage capacity and better safety aspects compared to hard carbon -based anodes but suffer from poor cyclic stability due to volume expansion/contraction and concomitant loss in mechanical integrity during sodiation/desodiation. To address this, the usage of nanoscaled electrode-active particles and nanoscaled-carbon-based buffers has been explored, but with compromises with the tap density, accrued irreversible surface reactions, overall capacity (for "inactive" carbon), and adoption of non-scalable/complex preparation routes. Against this backdrop, anode-active "layered" bismuth (Bi) has been incorporated with Sn via a facile-cum-scalable mechanical-milling approach, leading to individual electrode-active particles being composed of well-dispersed Sn and Bi phases. The optimized carbon-free Sn-Bi compositions, benefiting from the combined effects of "buffering" action and faster Na transport of Bi, to go with the greater Na-storage capacity and lower operating potential of Sn, exhibit excellent cyclic stability (viz., ∼83-92% capacity retention after 200 cycles at 1C) and rate capability (viz., no capacity drop from C/5 to 2C, with only ∼25% drop at 5C), despite having fairly coarse particles (∼5-10 µm). As proven by operando synchrotron X-ray diffraction and stress measurements, the sequential sodiation/desodiation of the components and, concomitantly, stress build-ups at different potentials provide "buffering" action even for such "active-active" Sn-Bi compositions. Furthermore, the overall stress development upon sodiation of Bi has been found to be significantly lower than that of Sn (by a factor of ∼3.8), which renders Bi promising as a "buffer" material, in general. Dissemination of such complex interplay between electrode-active components during electrochemical cycling also paves the way for the development of high-performance, safe, and scalable "alloying-reaction"-based anode materials for Na-ion batteries and beyond, sans the need for ultrafine/nanoscaled electrode particles or "inactive" nanoscaled-carbon-based "buffer" materials.

Faceted Antimony Particles with Interiors Reinforced with Reduced Graphene Oxide as High-Performance Anode Material for Sodium-Ion Batteries.

The attainment of "true reinforcement" in a composite and harnessing of the associated beneficial effects have been demonstrated here through the development of faceted crystalline Sb particles having the interiors reinforced with reduced graphene oxide (rGO). Such a unique and "near-ideal" micro/nanocomposite architecture has been achieved via a facile/cost-effective route by facilitating heterogeneous nucleation/growth of Sb-oxide particles on/around dispersed rGO sheets upon incorporation of the same directly into the precursor suspension, followed by the reduction of Sb-oxide to Sb, in intimate contact with the rGO, during the subsequent single heat-treatment step. As a potential anode material for Na-ion batteries, the as-developed Sb/rGO composite exhibits a reversible Na-storage capacity of ∼550 mAh/g (@ 0.2 A/g) and a fairly high first cycle Coulombic efficiency (CE) of ∼79%, with the good reversibility being attributed to the coarse particle size of Sb and encompassing of rGO sheets inside the Sb particles. Furthermore, despite the coarse particle size, the Sb/rGO-based electrode exhibits outstanding cyclic stability, with negligible capacity fade up to 150 cycles (viz., ∼97% capacity retention), and rate capability, with >86% capacity being obtained upon raising the current density from 0.1 to 2 A/g, resulting in a capacity of ∼490 mAh/g, even at 2 A/g.