First-Principles Study of Amorphous Al2O3 ALD Coating in Li-S Battery Electrode Design

The Li-S battery is exceptionally appealing as an alternative candidate beyond Li-ion battery technology due to its promising high specific energy capacity. However, several obstacles (e.g., polysulfides’ dissolution, shuttle effect, high volume expansion of cathode, etc.) remain and thus hinder the commercialization of the Li-S battery. To overcome these challenges, a fundamental study based on atomistic simulation could be very useful. In this work, a comprehensive investigation of the adsorption of electrolyte (solvent and salt) molecules, lithium sulfide, and polysulfide (Li2Sx with 2 ≤x≤ 8) molecules on the amorphous Al2O3 atomic layer deposition (ALD) surface was performed using first-principles density functional theory (DFT) calculations. The DFT results indicate that the amorphous Al2O3 ALD surface is selective in chemical adsorption towards lithium sulfide and polysulfide molecules compared to electrolytes. Based on this work, it suggests that the Al2O3 ALD is a promising coating material for Li-S battery electrodes to mitigate the shuttling problem of soluble polysulfides.

N–Doped Porous Carbon Microspheres Derived from Yeast as Lithium Sulfide Hosts for Advanced Lithium-Ion Batteries

Lithium sulfide (Li2S) is considered to be the best potential substitution for sulfur-based cathodes due to its high theoretical specific capacity (1166 mAh g−1) and good compatibility with lithium metal-free anodes. However, the electrical insulation nature of Li2S and severe shuttling of lithium polysulfides lead to poor rate capability and cycling stability. Confining Li2S into polar conductive porous carbon is regarded as a promising strategy to solve these problems. In this work, N-doped porous carbon microspheres (NPCMs) derived from yeasts are designed and synthesized as a host to confine Li2S. Nano Li2S is successfully entered into the NPCMs’ pores to form N-doped porous carbon microspheres–Li2S composite (NPCMs–Li2S) by a typical liquid infiltration–evaporation method. NPCMs–Li2S not only delivers a high initial discharge capacity of 1077 mAh g−1 at 0.2 A g−1, but also displays good rate capability of 198 mAh g−1 at 5.0 A g−1 and long-term lifespan over 500 cycles. The improved cycling and high-rate performance of NPCMs–Li2S can be attributed to the NPCMs’ host, realizing the strong fixation of LiPSs and enhancing the electron and charge conduction of Li2S in NPCMs–Li2S cathodes.

Correlations between Precipitation Reactions and Electrochemical Performance of Lithium–Sulfur Batteries

A comprehensive description of the electrochemical processes in the positive electrode of lithium–sulfur batteries is crucial for the enhancement of sulfur utilization. However, the discharge mechanisms are complicated due to the various reactions in multiple phases and the tortuosity of the highly porous carbon matrix. While previous studies have focused on the precipitation of lithium sulfide, the effect of the limited mass transport inside the micropores and mesopores of an electrode with optimized surface area have largely been neglected. In this work, in-operando small-angle scattering with three different contrasts, and wide-angle scattering measurements are made while the internal and diffusion resistances are measured simultaneously. The results indicate that the precipitates grow mostly in number, not in size, and that the structure of the carbon matrix is not affected. The comparison of the small-angle and wide-angle scattering reveals the amorphous discharge products found at a low discharge rate. Further analyses demonstrate the correlation between the diffusion resistance and the composition of material in the mesopores at the end of discharge, which suggests that Li-ion deficiency is the limiting factor of sulfur utilization at a medium discharge rate.

Degradation mechanisms of lithium sulfide (Li2S) composite cathode in carbonate electrolyte and improvement by increasing electrolyte concentration

Lithium polysulfides (Li2Sn) react with carbonate solvents, forming organic polysulfides (R–Sn–R) and sulfides (R–S–R); the concentrated electrolyte suppresses these reactions.