Implementation of Bismuth Chalcogenides as an Efficient Anode: A Journey from Conventional Liquid Electrolyte to an All-Solid-State Li-Ion Battery

Abstract

Bismuth chalcogenide (Bi2X3; X = sulfur (S), selenium (Se), and tellurium (Te)) materials are considered as promising materials for diverse applications due to their unique properties. Their narrow bandgap, good thermal conductivity, and environmental friendliness make them suitable candidates for thermoelectric applications, photodetector, sensors along with a wide array of energy storage applications. More specifically, their unique layered structure allows them to intercalate Li+ ions and further provide conducting channels for transport. This property makes these suitable anodes for Li-ion batteries. However, low conductivity and high-volume expansion cause the poor electrochemical cyclability, thus creating a bottleneck to the implementation of these for practical use. Tremendous endeavors have been devoted towards the enhancement of cyclability of these materials, including nanostructuring and the incorporation of a carbon framework matrix to immobilize the nanostructures to prevent agglomeration. Apart from all these techniques to improve the anode properties of Bi2X3 materials, a step towards all-solid-state lithium-ion batteries using Bi2X3-based anodes has also been proven as a key approach for next-generation batteries. This review article highlights the main issues and recent advances associated with Bi2X3 anodes using both solid and liquid electrolytes.

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

“…In the case of Sb 2 Se 3 and Sb 2 Te 3 composites, the first plateaus are observed around 1.6 and 1.4 V, respectively (Figure 2B). The XRD profiles at point 2 for these composites (Figure 3B, C) confirm this plateau corresponding to the conversion reaction Sb 2 Se 3 ➔Li 2 Se and Sb and Sb 2 Te 3 ➔Sb 2 Te and Sb, respectively, which agrees well with the reports by Tian et al 32 and Wei et al 33 The second discharge plateaus for these composites overlapped with the plateau of Sb 2 S 3 composite at around 0.9 V which is obvious as it corresponds to the alloying reaction of metallic Sb and formation of Li 3 Sb phase (Figure 3B, C: point 3) 37 . Thus, according to the above results, a generalized discharge (lithiation) reaction can be represented by the following Equations ) and (): During the charging process, the first reaction takes place at around 0.97 V as evidenced by the plateau at this potential.…”

“…Thus, according to the above results, a generalized discharge (lithiation) reaction can be represented by the following Equations ) and (): During the charging process, the first reaction takes place at around 0.97 V as evidenced by the plateau at this potential. The XRD profile suggests the presence of Sb phase in addition to Li 2 X and LiBH 4 phases as a result of dealloying reaction of Li 3 Sb to Sb phase (Figure 3B, C, point 4) and agrees well with the literature 21,22,32‐34 . The long length of the plateau around 1.7 V corresponds to the transformation of Li 2 X to X through electrochemical reaction as well as X and/or Sb to Li 2 X/Li 3 Sb again through the thermochemical reaction as described previously.…”

“…During the reverse scan, that is, charging process, the oxidation peak at 1.05 V corresponds to Li 3 Sb → Sb conversion, whereas a broad peak in the potential range 1.7‐2.7 V can be expected due to simultaneous electrochemical and thermochemical reactions. Similar to Bi 2 X 3 /LiBH 4 /AB composites, 10,12,13,31‐34 Li 2 S might be converted to S electrochemically at this potential and the generated S as well as Sb reacted with LiBH 4 thermochemically to form Li 2 S and Li 3 Sb, which again converted to S and Sb immediately. This process continues until the consumption of LiBH 4 (act as a source of Li) in composite material.…”

Epitaxial Engineering Strategy to Amplify Localized Surface Plasmon Resonance and Electrocatalytic Activity Enhancement in Layered Bismuth Selenide by Phosphorus Functionalization

“…Layered architectures can be epitaxially engineered in several ways such as by doping and intercalation to alter their structure along c axis. The interlayer space available in layered materials provides space for intercalation of guest atoms and eventually facilitated the route for the charge transport [22] . Similar to graphene, the 2D surface states of 3D bulk Bi 2 Se 3 do have massless Dirac fermions to behave metallic with band gap between 0.3–0.35 eV, which otherwise be an insulator as bulk [23,24] .…”

“…P incorporated Bi 2 Se 3 can benefit combinedly from Se and P, therefore P can be a perfect replacement for precious catalysts. Bismuth selenide (Bi 2 Se 3 ) is a semiconducting metal chalcogenide belonging to V–VI groups, [18,30] but least investigated due to its low electrochemical reversibility from poor conductivity and high‐volume expansion in spite of its merits such as appreciable thermal conductivity and narrow bandgap [22] . In order to improve the cyclability of Bi 2 Se 3 , several measures can be adopted and one such is intercalation of metal atom in between the individual Bi 2 Se 3 layers.…”