Lithiation mechanism of antimony chalcogenides ( Sb ₂ X ₃ ; X = S, Se, Te) electrodes for high‐capacity all‐solid‐state Li‐ion battery

Abstract

Summary All‐solid‐state Li‐ion batteries are considered as next‐generation batteries, which provide safer operation by replacing the flammable liquid electrolyte by solid electrolyte. Developing these batteries using high capacity anode materials is warranted with the increasing demand of the energy sector. Among all the anode materials, alloying‐type anode materials are very attractive due to their high gravimetric as well as volumetric capacities, but they show large volume expansion which can be buffered by mixing different materials. Herein, all‐solid‐state Li‐ion batteries were prepared using Sb chalcogenide composites as electrode materials, and the detailed electrochemical reaction mechanism for the lithiation/delithiation has been established using cyclic voltammetry (CV), electrochemical charge–discharge profiling, electrochemical impedance spectroscopy (EIS), X‐ray diffraction (XRD), and scanning electron microscopy (SEM). The lithiation reaction for all the composites was found to be conversion reaction in the first step (Sb↔ Li2X and Sb) followed by alloying reaction in the second step (Sb ↔ Li3Sb), which is similar to that for liquid electrolyte case. All the composites showed the high volumetric capacity of >4000 mAh/cm3 in the first cycle, which reduced down to ~1500‐2000 mAh/cm3 after 100 cycles. This 50% retained capacity is higher in comparison to conventional carbon electrode as well as previously reported works on similar materials. The coulombic efficiency for all the composites was found nearly 99% after initial 10 cycles. The highest energy density was found as 344 Wh/kg for Sb2S3 composite after 100 cycles (765 Wh/kg in the first cycle), which nearly equals to the target values and makes these composites suitable for the future Li‐ion battery.

A review of all‐solid‐state lithium‐selenium batteries

“…(E) Cyclic stability of Sb 2 Se 3 ‐LiBH 4 ‐AB composite electrodes as shown by Coulombic efficiency and the discharge/charge capacity vs cycle number. Reproduced with permission 71 . Copyright 2021, Wiley‐VCH.…”

“…In the pursuit of advancing ASSLSeBs systems, Jain et al 71 developed a composite cathode composed of Sb 2 Se 3 , LiBH 4 , and AB (4:3:3). The ASSLSeBs with Sb 2 Se 3 composite cathode (Figure 7D) demonstrated a significant capacity decay during the first five cycles and the capacity was quite stable up to 100 cycles.…”

Exploring Cobalt Phosphide Nanoparticles Sheathed within N-Rich Carbon Polyhedra as High-Capacity Anode for All-Solid-State Lithium-Ion Batteries

“…Moreover, features like Li transference number close to one (t Li+ ∼ 1), which is relatively higher than liquid electrolytes (∼0.5), and electrochemical stability over a wide potential window (0−5 V) make LiBH 4 a suitable candidate for ASSLIBs. 15 Besides, in existing LIBs, despite being advantageous in terms of conductivity and cycling stability, graphite suffers from exfoliation. It is also poor in terms of theoretical capacity (372 mA h/g) when compared with other pseudocapacitivetype conversion electrodes based upon transition metal-based oxides (TMOs), 16 chalcogenides (TMCs), 17 and phosphides (TMPs, 500−2000 mA h/g).…”

“…Presence of highly reductive H – makes it compatible with metal electrodes or leads to more appropriate interphases. Moreover, features like Li transference number close to one ( t Li+ ∼ 1), which is relatively higher than liquid electrolytes (∼0.5), and electrochemical stability over a wide potential window (0–5 V) make LiBH 4 a suitable candidate for ASSLIBs …”

Layered K0.37MnO2·0.25H2O as cathode material for potassium ion batteries

“…Lithium-ion batteries (LIBs) are widely utilized in commercial applications by virtue of the high energy densities and superior cycle lives [1][2][3][4][5]. Nevertheless, the widespread lithium supply shortage (the content of lithium in the crust of Earth is only 0.0017% [6][7][8][9]), combined with the high cost and safety issues of LIBs, severely limit their expansion in large-scale energy storage devices [10,11].…”