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Tailoring Porosity in Carbon Nanospheres for Lithium–Sulfur Battery Cathodes

Porous hollow carbon spheres with different tailored pore structures have been designed as conducting frameworks for lithium-sulfur battery cathode materials that exhibit stable cycling capacity. By deliberately creating shell porosity and utilizing the interior void volume of the carbon spheres, sufficient space for sulfur storage as well as electrolyte pathways is guaranteed. The effect of different approaches to develop shell porosity is examined and compared in this study. The most highly optimized sulfur-porous carbon nanosphere composite, created using pore-formers to tailor shell porosity, exhibits excellent cycling performance and rate capability. Sulfur is primarily confined in 4-5 nm mesopores in the carbon shell and inner lining of the shells, which is beneficial for enhancing charge transfer and accommodating volume expansion of sulfur during redox cycling. Little capacity degradation (∼0.1% /cycle) is observed over 100 cycles for the optimized material.

Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries

Combination of a solvent–salt complex [acetonitrile(ACN)2–LiTFSI] with a hydrofluoroether (HFE) co-solvent unveil a new class of Li–S battery electrolytes. They possess stability against Li metal and viscosities which approach that of conventional ethers, but they have the benefit of low volatility and minimal solubility for lithium polysulphides while exhibiting an uncharacteristic sloping voltage profile. In the optimal system, cells can be discharged to full theoretical capacity under quasi-equilibrium conditions while sustaining high reversible capacities (1300–1400 mA h g−1) at moderate rates, and capacities of 1000 mA h g−1 with almost no capacity fade at fast discharge rates under selected cycling protocols. A combination of operando X-ray absorption spectroscopy at the S K-edge, and electrochemical studies demonstrate that lithium polysulphides are indeed formed in these ACN-complexed systems. Their limited dissolution and mobility in the electrolyte strongly affect the speciation and polysulphide equilibria, leading to controlled precipitation of Li2S.