Monolayer MSi₂P₄ (M = V, Nb, and Ta) as Highly Efficient Sulfur Host Materials for Lithium–Sulfur Batteries

Abstract

Despite the high capacity and low cost of lithium–sulfur (Li–S) batteries, their commercialization is greatly blocked by multiple bottlenecks including the shuttle effect of lithium polysulfides (LiPSs), poor conductivity of sulfur, and sluggish reaction kinetics. Herein, we propose novel two-dimensional MSi2P4 (M = V, Nb, and Ta) monolayers as promising sulfur hosts to improve the Li–S battery performance. Our calculations show that MSi2P4 monolayers offer moderate binding strengths to the polysulfides, which are expected to effectively inhibit the LiPS shuttling and dissolution. Moreover, the conductive properties of the MSi2P4 systems are well maintained after LiPS adsorption, eliminating the insulating nature of sulfur species. Remarkably, MSi2P4 monolayers exhibit superior electrocatalytic activity for the sulfur reduction reaction and the Li2S decomposition reaction, which considerably lowers the energy barriers of LiPS conversions during discharge and charge, thus ensuring the fast redox kinetics and high sulfur utilization of Li–S batteries. This study pioneers the application of MSi2P4 monolayers as highly efficient sulfur host materials for Li–S batteries and affords insights for further development of advanced Li–S batteries.

Cataloguing MoSi2N4 and WSi2N4 van der Waals Heterostructures: An Exceptional Material Platform for Excitonic Solar Cell Applications

“…[44] Beyond MoSi 2 N 4 and WSi 2 N 4 monolayers, the family of MA 2 Z 4 monolayers [32] also exhibit enormously rich physical and chemical behaviors, including nontrivial topological phases, [32] valley-contrasting physics, [45][46][47][48] nonlinear optical response, [49] hydrogen (oxygen) evolution catalytic performance, [50,51] and superior electrocatalytic activity for energy storage application. [52] Driven by the success of vdWH material engineering, MoSi 2 N 4 -based vdWHs have also been intensively studied recently. For example, MoSi 2 N 4 interfaced with InSe, [53] blue phosphorus, [54] C 2 N, [55] CrCl 3 , [56] C 3 N 4 , [57] MoS 2 , [58] graphene, [59] NbS 2 , [59] GaN, [60] ZnO, [60] MoSe 2 , [61] Cs 3 Bi 2 I 9 , [62] MoGe 2 N 4 , [63] MoGeSiN 4 , [64] and MoSH [65] have been computationally predicted to exhibit efficient photocatalytic water splitting, [53][54][55] strain-tunable valley splitting effect, [56] strong optical absorption in the visible light regime with strain, and field-effect tunable band structures.…”

Identification of linear scaling relationships in polysulfide conversion on α-In2Se3-supported single-atom catalysts

“…Our calculations show that the adsorption energies of soluble Li 2 S n on TM@In 2 Se 3 range from −3.64 to −2.23 eV, which are significantly lower than the range of adsorption energies calculated on electrolyte molecules (DOL and DME), which vary from 0 to 1.00 eV. 50–52 This means that the TM@In 2 Se 3 is capable of immobilizing the Li 2 S n species and effectively suppress the LiPSs dissolution. In this sense, the strong adsorption strength for Li 2 S n species adsorbed on TM@In 2 Se 3 indicates that engineering In 2 Se 3 via 3d TM atom adsorption can suppress the shuttle effect.…”

Theoretical Study on the Role of Solvents in Lithium Polysulfide Anchoring on Vanadium Disulfide Facets for Lithium–Sulfur Batteries

“…Owing to their exceptional electronic conductivity and distinctive electronic structure, transition metal sulfides (TMSs) can be used to effectively trap LiPS clusters and prevent them from shuttling. , Recently, vanadium disulfide (VS 2 ) has gained much attention as an anchoring material for LiPSs due to its excellent conductivity and surface activity. − After a comparative study of the anchoring effects of VO 2 and VS 2 nano-sheets, Wang et al concluded that VS 2 contains more favorable properties in hosting the sulfur cathode in Li–S batteries . In a similar study, Chen et al proposed an analogous periodic law for first-row TMSs and claimed that VS has the strongest anchoring on LiPSs with a relatively low lithium-ion diffusion barrier .…”