Although the development of potassium−sulfur batteries (KSBs) is in the nascent stage, KSBs draw keen interest as they offer a few unique advantages over Li− and Na−sulfur battery systems, including lower cost and highest ionic mobility of K + ions. However, shuttling of intermediate polysulfides and the insulating nature of sulfur result in poor utilization of the active material and significant capacity loss during cycling. In this study, we overcome these critical issues of KSBs by developing an active cathode material as a covalently confined sulfur composite with carbon derived from a sustainable precursor (bacterial cellulose) (hereinafter referred to as CCS@CBC). The synthesis temperature of CCS@CBC is varied from 150 to 450 °C to achieve the optimal covalent fixing of sulfur in the carbon matrix verified by X-ray diffraction and infrared spectroscopy. The increase in the synthesis temperature of CCS@CBC ensures proper covalent confinement of sulfur with the carbon matrix that facilitates the relieving of the shuttle effect as revealed in the electrochemical performance of as-prepared KSBs. The CCS@CBC prepared at 450 °C delivers an impressive initial capacity of 615 mAh g −1 and retains 383 mAh g −1 after 250 cycles at a current density of 200 mA g −1 . Furthermore, the rate-capability and the self-discharge tests reveal the superior performance of CCS@CBC at 450 °C compared to lower synthesis temperature. A higher sulfur loading (2.5 mg cm −2 ) electrode is also tested to evaluate the commercial aspect. The first-principles calculations are also performed to investigate the interaction of the host material with polysulfides to better understand the experimental findings. The outcome of this study can be helpful in the future development of high-performance KSBs.

In search of improved advanced energy storage systems to meet our fast-growing energy demands for large-scale applications, potassium−sulfur batteries (KSBs) provide an essential alternative due to their high specific capacity apart from the low cost and abundance of potassium and sulfur. However, the insulating nature of sulfur, volume changes, and shuttle effect impede the development of these batteries. Further, the binder, carbon additives, and current collector used in the assembly of cells in a conventional approach decrease the energy density of cells. To overcome these challenges, we propose a binder-free and freestanding carbonized bacterial cellulose (CBC) as a cathode host that not only provides a conducting pathway but also has a porous network that is resilient to volume change. To ensure the uniform loading of sulfur, CBC was dipped into the sulfur/carbon disulfide solution, followed by melt diffusion at 160 °C to prepare a sulfur-infused CBC (S-CBC) cathode. This S-CBC cathode with an interconnected fiber network delivers a significantly high reversible capacity of 1311 mA h g −1 at a current density of 50 mA g −1 . While connected for long-term cycling, the potassium sulfur cell delivers an initial reversible capacity of 475 mA h g −1 at 100 mA g −1 .Once the cell is stabilized after 80 cycles, it maintains a capacity of 123 mA h g −1 with a capacity retention of 86% after 500 cycles. This enhanced electrochemical performance of flexible and free-standing S-CBC cathode is further analyzed using first-principles calculations. Moreover, the efficacy of the S-CBC cathode is also tested under high sulfur loading (1.6 and 2.4 mg cm −2 , respectively) for the practical development of KSBs.