Ultrafast and Highly Reversible Sodium Storage in Zinc‐Antimony Intermetallic Nanomaterials

Abstract

The progress on sodium-ion battery technology faces many grand challenges, one of which is the considerably lower rate of sodium insertion/deinsertion in electrode materials due to the larger size of sodium (Na) ions and complicated redox reactions compared to the lithium-ion systems. Here, it is demonstrated that sodium ions can be reversibly stored in Zn-Sb intermetallic nanowires at speeds that can exceed 295 nm s −1 . Remarkably, these values are one to three orders of magnitude higher than the sodiation rate of other nanowires electrochemically tested with in situ transmission electron microscopy. It is found that the nanowires display about 161% volume expansion after the fi rst sodiation and then cycle with an 83% reversible volume expansion. Despite their massive expansion, the nanowires can be cycled without any cracking or facture during the ultrafast sodiation/desodiation process. In addition, most of the phases involved in the sodiation/desodiation process possess high electrical conductivity. More specifi cally, the NaZnSb exhibits a layered structure, which provides channels for fast Na + diffusion. This observation indicates that Zn-Sb intermetallic nanomaterials offer great promise as high rate and good cycling stability anodic materials for the next generation of sodium-ion batteries.

Unveiling the Unique Phase Transformation Behavior and Sodiation Kinetics of 1D van der Waals Sb2S3 Anodes for Sodium Ion Batteries

“…The barriers were relatively low in all these phases, as shown in Table 1. This value is lower than that of NaTiO 2 (≈220 meV), [60] SnO 2 (410 meV), [52] bulk MoS 2 (≈700 meV), [61] and tetragonal NaZnSb (470 meV), [46] consistent with the ultrafast initial Na + ion intercalation speed. This value is lower than that of NaTiO 2 (≈220 meV), [60] SnO 2 (410 meV), [52] bulk MoS 2 (≈700 meV), [61] and tetragonal NaZnSb (470 meV), [46] consistent with the ultrafast initial Na + ion intercalation speed.…”

“…The single crystal orthorhombic stibnite in the pristine state (Figure 2d-1) differed from the almost amorphous state of the fully expanded SSNR/C electrode (Figure 2d-2) with two bright diffraction rings which can be indexed to Na 2 O (Fm-3m). [46,51,56,57] No other crystalline phase was found in the fully expanded SSNR/C electrode, indicating an amorphous state of the products. [46,51,56,57] No other crystalline phase was found in the fully expanded SSNR/C electrode, indicating an amorphous state of the products.…”

“…Figure chalcogenide SIB electrodes, with the exception of β-Zn 4 Sb 3 nanowires. The linear L∝t relation is known to be controlled by the short-range interface reaction kinetics, [46,47] instead of being limited by the ion transport in the Sb 2 S 3 nanorods. The linear L∝t relation is known to be controlled by the short-range interface reaction kinetics, [46,47] instead of being limited by the ion transport in the Sb 2 S 3 nanorods.…”

Alloy‐Based Anode Materials toward Advanced Sodium‐Ion Batteries

“…In the latest years, some work reported that Sb-based intermetallic compounds including Fe-Sb, [140][141][142][143] Cu 2 Sb, [144,145] Mo 3 Sb 7 , [146] Zn-Sb, [131,[147][148][149] Bi-Sb alloys [132] are capable of sodium storage due to the metallic nanocrystals formed during Na + intercalation process, which effectively enhance electrical conductivity as well as buffer the expansion stress upon cycling. Specifically, Bi can be alloyed with Sb at any molar ratio because of the similar physiochemical properties with Sb, which will partly solve the problem of shortened plateau in the voltage profile when introducing a second element into the Sb system.…”

Na‐Ion Batteries for Large Scale Applications: A Review on Anode Materials and Solid Electrolyte Interphase Formation

“…ZnSb/C composite was successfully prepared by HEMM [226] ; however, this method was proven to be unsuccessful for milling Zn and Sb alone. [237] In the development of MSb alloys with M being an active element toward Na, bismuth (Bi) has been recently studied by Zhao et al [228] BiSb alloys with different compositions were prepared by HEMM from the metals and acetylene black. Better results were obtained for crystalline Zn 4 Sb 3 films prepared by Jackson et al [227] by electrodeposition.…”