New insight into the oxidation mechanism of solid Li 2 S is presented by investigating a specially designed cell in which the Li 2 S particles are electrically isolated from the carbon cathode. Surprisingly, the cell containing the isolated Li 2 S particles delivered considerable charge and discharge capacities despite the prevention of any charge transfer process between the Li 2 S particles and the carbon cathode. This fact directly indicates that the electrochemical oxidation of Li 2 S occurs not through a direct charge (electron) transfer between solid Li 2 S and conducting materials but through chemical reactions coupled with the charge transfer process. We believe that these unexpected results will greatly contribute to a deep understanding of the exact working mechanism of Li-S batteries and Li 2 S cathodes as well as a paradigm shift toward an innovative and rational design of Li-S batteries.
To investigate the effect of the electrode materials on the electrochemical performance of Li-S cells, sulfur cathodes were constructed using four types of carbon blacks: Ketjenblack EC-600JD (KB-600), Printex XE-2, Cabot BP-2000, and Super-P. It was found that the electrochemical performance of sulfur cathode was strongly dependent on the type of carbon black used. In the first discharge, the sulfur cathodes containing carbon blacks with a high surface area, KB-600 (SBET = 1270 m2/g), Printex XE-2 (SBET = 950 m2/g), or Cabot BP-2000 (SBET = 1487 m2/g), showed much higher discharge capacities (>1200 mA h/g) than the sulfur cathode (710 mA h/g) with Super-P (SBET = 62 m2/g). It was observed that the sulfur cathodes with KB-600, Printex XE-2, or Cabot BP-2000, which showed very similar discharge capacities one another at a low rate of 0.2 C, exhibited significantly different electrochemical behavior (the discharge capacity and midvoltage) at a high rate of 1.0 C. In particular, the sulfur cathode with KB-600 showed an extremely high capacity (831 mA h/g) with a midvoltage of 2.07 V at a 1.0 C rate, and excellent capacity retention (79%) after 50 cycles.
The electrochemical performance of Li-S cells was investigated in various ternary electrolyte solutions composed of 1,2-dimethoxyethane (DME), tetra(ethylene glycol) dimethyl ether (TGM), and 1,3-dioxolane (DOX). The discharge capacity values and cycle data obtained at each composition were statistically treated with the Minitab program to obtain mixture contour plots, from which the optimal composition of the ternary solvent systems was predicted. The discharge capacities and capacity retention were quite dependent on the electrolyte composition. It was estimated from the contour plots of the capacity at 1.0 C that the discharge capacity sharply increased with a decrease in the TGM content. High capacities greater than 900 mAh/g at 1.0 C were expected for the electrolyte composition with a volume ratio of DME/TGM/DOX = 1/0/1. In contrast, it was predicted from the mixture contour plot of the capacity retention that the cycle performance would significantly increase with an increase in the DME content.
To investigate the influence of the carbon matrix on the electrochemical performance of Si/C composites, four types of Si/C composites were prepared using graphite, petroleum coke, pitch and sucrose as carbon precursors. A ball mill was used to prepare Si/C blends from graphite and petroleum coke, whereas a dispersion technique was used to fabricate Si/C composites where Si was embedded in disordered carbon matrix derived from pitch or sucrose. The Si/pitch-based carbon composite showed superior Si utilization (96% in the first cycle) and excellent cycle retention (70% after 40 cycles), which was attributed to the effective encapsulation of Si and the buffering effect of the surrounding carbon matrix on the silicon particles.
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