Long-Life, High-Rate Rechargeable Lithium Batteries Based on Soluble Bis(2-pyrimidyl) Disulfide Cathode.

Organosulfides are promising candidates as cathode materials for the development of electric vehicles and energy storage systems due to their low-cost and high capacity properties. However, they generally suffer from slow kinetics because of the large rearrangement of S-S bonds and structural degradation upon cycling in batteries. In this paper, we reveal that soluble bis(2-pyrimidyl) disulfide (Pym2 S2 ) can be a high-rate cathode material for rechargeable lithium batteries. Benefiting from the superdelocalization of pyrimidyl group, the extra electrons prefer to be localized on the π* (pyrimidyl group) than σ* (S-S bond) molecular orbitals initially, generating the anion-like intermedia of [Pym2 S2 ]2- and thus decreasing the dissociation energy of the S-S bond. It makes the intrinsic energy barrier of dissociative electron transfer depleted, therefore the lithium half cell exhibits 2000 cycles at 5 C. This study provides a distinct pathway for the design of high-rate, long-cycle-life organic cathode materials.

Dynamic 1T-2H Mixed-Phase MoS2 Enables High-Performance Li-Organosulfide Battery.

Achieving high energy density and long cycle life in realistic batteries is still an unmet need, which has triggered research into the discoveries of new electrode materials as well as new storage mechanisms. As a kind of new cathode materials for rechargeable lithium batteries, organosulfide compounds R-Sn -R (n = 3-6) based on conversion chemistries of SS bonds have many advantages and promising prospects; however, poor electric/ionic conductivity and sluggish redox kinetics is a major hinder for their applications. Here an organic-inorganic hybrid cathode by introducing 1T MoS2 grown on reduced graphene oxide to hybridize with phenyl tetrasulfide (Ph-S4 -Ph, theoretical specific capacity 570 mAh g-1 ), enhancing the battery performance is reported. This includes the improved charge transfer, stable long cycles, and close-to-practical energy density in coin cells and pouch cells, which also show high mass loadings and contents, and low electrolyte dependence. Furthermore, the dynamic 1T-2H mixed-phase during the charge/discharge is revealed to be critical for the improved performance. This study proves the hybrid nanomaterials as a promising solution to address the challenges facing lithium-organosulfide batteries.

Acceleration of Cathode Interfacial Kinetics by Liquid Organosulfides in Lithium Metal Batteries.

Great efforts have been made to tackle the issues of the shuttle effect and kinetics hysteresis in lithium-sulfur (Li-S) battery, but few on tuning the reaction path of sulfur cathode. Herein, we report a strategy to replace inorganic sulfur with liquid organosulfide and construct a novel liquid-liquid interface between cathode and electrolyte, which effectively inhibits the shuttle effect and simplifies the solid-liquid-solid conversion reaction to only liquid-solid process, thus greatly improving the reaction kinetics. The Li|PTS half-cell exhibits excellent cycling stability at 0.5 C, with a capacity retention of 64.9 % after 750 cycles. The Li|PTS pouch cell with a high PTS loading of 3.1 g delivers a maximum capacity of 997 mAh and maintains 82.1 % of initial capacity after 50 cycles at the current of 100 mA. This work enriches the reaction mechanism of Li-S batteries and provides new insights for the development of interphase chemistry in the design of cathodes.

Organosulfide-Based Deep Eutectic Electrolyte for Lithium Batteries.

Deep eutectic electrolytes (DEEs) are a new class of electrolytes with unique properties. However, the intermolecular interactions of DEEs are mostly dominated by Li⋅⋅⋅O interactions, limiting the diversity of chemical space and material constituents. Herein, we report a new class of DEEs induced by Li⋅⋅⋅N interactions between 2,2'-dipyridyl disulfide (DpyDS) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The strong ion-dipole interaction triggers the deep eutectic phenomenon, thus liberating the Li+ from LiTFSI and endowing the DEEs with promising ionic conductivity. These DEEs show admirable intrinsic safety, which cannot be ignited by flame. The DEE at the molar ratio of DpyDS:LiTFSI=4:1 (abbreviated as DEE-4:1) is electrochemically stable between 2.1 and 4.0 V vs. Li/Li+ , and exhibits an ionic conductivity of 1.5×10-4  S cm-1 at 50 °C. The Li/LiFePO4 half cell with DEE-4:1 can provide a reversible capacity of 130 mAh g-1 and Coulombic efficiency above 98 % at 50 °C.