Chemical Interactions between Dissolved Polysulfides and Potential Catalytic Host Materials for Li-S Batteries.

Given that both elemental sulfur (S8) and lithium sulfide (Li2S) exhibit insulating properties, the involvement of conductive host materials becomes crucial for facilitating charge transfer in sulfur cathodes within lithium-sulfur (Li-S) batteries. Furthermore, there has been a recent surge in the exploration of host materials for sulfur cathodes to address the "polysulfide shuttle" effect. This effect arises from the formation of polysulfide species during the charge-discharge cycles of the Li-S batteries and can be mitigated through physical or chemical interactions with specific materials. To qualitatively and accurately assess the interactions between polysulfides and the potential host materials, this study utilized a well-established high-performance liquid chromatography method for polysulfide analysis. The objective was to monitor the changes in polysulfide solutions after contact with 44 different carbon and inorganic materials. Based on both qualitative and quantitative chromatographic results, it was determined that 20 out of the 44 materials exhibit significant interactions with polysulfides. The primary form of interaction observed is the irreversible disproportionation reaction with elemental sulfur being one of the resulting products.

High-Performance Li-S Batteries with a Minimum Shuttle Effect: Disproportionation of Dissolved Polysulfide to Elemental Sulfur Catalyzed by a Bifunctional Carbon Host.

A long cycle-life Li-S battery (both the coin cell and pouch cell) is reported with minimum shuttle effect. The performance was achieved with a bifunctional carbon material with three unique features. The carbon can catalyze the disproportionation of dissolved long-chain polysulfide ions to elemental sulfur; the carbon can ensure homogeneous precipitation of Li sulfide on the host carbon, and the carbon has a honeycomb porous structure, which can store sulfur better. All the features are demonstrated experimentally and reported in this paper. Few dissolved polysulfides are found by high-performance liquid chromatography in the electrolyte of the Li-S batteries during cycling, and only dissolved elemental sulfur is detected. The unique porous structure of the carbon made from raw silk is revealed by scanning electron microscopy. The N-containing functionalities that were introduced to carbon from the amino acids of raw silk can catalyze the disproportionation of the dissolved Sn2- to solid S8 at the cathode side, thereby mitigating the shuttle effect. In addition, the hierarchical honeycomb porous structures generated by a carbonization process can physically trap high-order lithium polysulfides and sustain the volume change of sulfur. With the synergistic effects of the unique structures and characteristics of the carbon prepared at 800 °C, the sulfur/carbon composite delivers a high reversible capacity of over 1000 mAh g-1 after 100 cycles with a sulfur content of 1.2 mg cm-2 in a pouch cell.

Impedance investigation of the high temperature performance of the solid-electrolyte-interface of a wide temperature electrolyte.

The high temperature cycling performance of a wide temperature electrolyte and the solid electrolyte interphase (SEI) along the cycling were investigated using a three-electrode pouch cell. The electrolyte developed in our lab demonstrated outstanding low temperature performance. The electrolyte was found to have a good and stable cycling performance at a high temperature in comparison with a state-of-the-art baseline electrolyte. Electrochemical impedance spectroscopy (EIS) was conducted on the anode, the cathode and the full cell independently with a reference embedded pouch cell. The distribution of relaxation times (DRT) transformation was calculated from the EIS spectrum. An equivalent circuit model was used to fit the anode EIS data and the electrochemical process on the anode was revealed. We concluded that a denser SEI layer was built on the anode of the improved electrolyte.

Electrode Architecture Design to Promote Charge-Transport Kinetics in High-Loading and High-Energy Lithium-Based Batteries.

Rechargeable lithium-ion batteries have built much of our modern society. Developing high-loading and high-energy batteries have become an inevitable trend to satisfy the ever-growing demand of energy consumption. However, issues related to mechanical instability and electrochemical polarization have become more prominent accompanying the increase of electrode thickness. How to establish a robust and rapid charge transport network within the electrode architecture plays a vital role for the mechanical property and the reaction dynamics of thick electrodes. In this review, principles of charge transport mechanism and challenges of thick electrode development are elaborated. Next, recent progress on advanced electrode architecture design focused on structural engineering is summarized. Finally, a transmission line model is proposed as an effective tool to guide the engineering of thick electrodes.

Controlled Prelithiation of SnO2/C Nanocomposite Anodes for Building Full Lithium-Ion Batteries.

SnO2 is an attractive anodic material for advanced lithium-ion batteries (LIBs). However, its low electronic conductivity and large volume change in lithiation/delithiation lead to a poor rate/cycling performance. Moreover, the initial Coulombic efficiencies (CEs) of SnO2 anodes are usually too low to build practical full LIBs. Herein, a two-step hydrothermal synthesis and pyrolysis method is used to prepare a SnO2/C nanocomposite, in which aggregated SnO2 nanosheets and a carbon network are well-interpenetrated with each other. The SnO2/C nanocomposite exhibits a good rate/cycling performance in half-cell tests but still shows a low initial CE of 45%. To overcome this shortage and realize its application in a full-cell assembly, the SnO2/C anode is controllably prelithiated by the lithium-biphenyl reagent and then coupled with a LiCoO2 cathode. The resulting full LIB displays a high capacity of over 98 mAh g-1LCO in 300 cycles at 1 C rate.

Fast and Controllable Prelithiation of Hard Carbon Anodes for Lithium-Ion Batteries.

Hard carbon has been extensively investigated as anode materials for high-energy lithium-ion batteries owing to its high capacity, long cycle life, good rate capability, and low cost of production. However, it suffers from a large irreversible capacity and thus low initial coulombic efficiency (ICE), which hinders its commercial use. Here, we developed a fast and controllable prelithiation method based on a chemical reaction using a lithium-containing reagent (1 M lithium biphenylide dissolved in tetrahydrofuran). The prelithiation extent can be easily controlled by tuning the reaction time. An SEI layer is formed during chemical prelithiation, and the ICE of prelithiated hard carbon in half-cell format can be increased to ∼106% in 30 s. When matched with a LiNi1/3Co1/3Mn1/3O2 cathode, the full cell with the prelithiated hard carbon anode exhibits a much improved ICE (90.2 vs 75%) and cycling performance than those of the pristine full cell. This facile prelithiation method is proved to be a practical solution for the commercial application of hard carbon materials.