Role of Ferroelectric In₂Se₃ in Polysulfide Shuttling and Charging/Discharging Kinetics in Lithium/Sodium–Sulfur Batteries

Abstract

Lithium–sulfur (Li–S) and sodium–sulfur (Na–S) batteries, with the advantages of ultrahigh energy density, natural abundance, and ecofriendliness, are regarded as next-generation rechargeable batteries. However, polysulfide shuttling and sluggish charging/discharging kinetics in sulfur cathodes severely hamper their practical applications. In this study, via employing first-principles calculations, we investigate two-dimensional ferroelectric In2Se3 as a promising additive to overcome these obstacles. Our studies reveal the following findings: (1) the In2Se3 monolayer has a modest adsorption strength to soluble polysulfides, which not only eliminates the notorious shuttle effect but also prevents polysulfide dissolution; (2) In2Se3 is able to significantly reduce the free energy barriers of sulfur reduction reaction and the decomposition barriers of Li2S and Na2S, thus greatly enhancing the charging and discharging efficiency; and (3) due to the strong binding ability, the polarization downward (P↓) surface always outperforms the polarization upward (P↑) surface during charging/discharging processes, enabling the effective control of battery performance by ferroelectric switching. Given these advantages, it is expected that ferroelectric In2Se3 and similar ferroelectric additives will open a new route to enhance Li–S and Na–S battery performance.

S-doped Ti3C2F2 MXene as an ideal sulfur cathode host for high-performance rechargeable lithium–sulfur batteries

“…, where E(Li 2 S@MXene), E(Li 2 S) and E(MXene) denote the electric energies of Li 2 S adsorbed MXene, the Li 2 S molecule and MXene, respectively. The free energy change during the discharging process is evaluated using our previous method: 32…”

Energy Storage Mechanism of C12-3-3 with High-Capacity and High-Rate Performance for Li/Mg Batteries

“…With the continuous development of human society, new energy materials, especially electronic consumables and power electric vehicles, have made amazing achievements over the past decade. As an important part of the secondary battery family, Li-ion batteries (LIBs) have been successfully used in commercial applications. , Unfortunately, their commercial anode is mainly focused on stable graphite-like materials due to the issues of Li dendrites and short circuits in lithium metal batteries. However, graphite materials have no satisfactory energy density owing to the limited capacity.…”

Surface Film Formation from Sodium Polysulfide Decomposition on Sodium-Metal Anode Surface

“…Moreover, using the DFT-PBE method, computations revealed that As 2 S 3 can reduce the NaPS shuttling and improve the cathode conductivity, leading to enhanced cycling and Coulombic efficiency . The ferroelectric In 2 Se 3 cathode was also computationally proposed to effectively decrease the kinetic barrier of the Na 2 S decomposition reaction …”

“…26 The ferroelectric In 2 Se 3 cathode was also computationally proposed to effectively decrease the kinetic barrier of the Na 2 S decomposition reaction. 27 Apart from cathode engineering, various strategies for strengthening the sodium anode are introduced to prevent the decomposition of NaPS, where long-chain NaPS are highly soluble in carbonate-based electrolytes and can diffuse through the electrolyte to deposit on the sodium-metal anode surface and undergo redox reactions to form short-chain NaPS films. 19 The cyclability and wettability can be enhanced by the alloying of Na anode.…”