Ceramic Fillers for Improved Lithium-Sulfur Batteries
Authors: Jahan Georgina , Motevalian Saeme , Hamal Dambar , Awadallah Osama , El-Zahab Bilal 
Published: September 2023

With the decarbonization of transportation, the demand for electric vehicles (EVs) and batteries that can power these EVs has been increasing. Lithium-ion-based batteries are already well-established and are considered the main chemistries to power current EVs. However, limited specific energy (< 300 Wh/kg) prevents these batteries from having high mileage vehicles. Lithium-sulfur batteries are considered the most promising next-generation energy storage system as they high theoretical capacity (~1675 mAhg-1), low cathode materials cost, and cell energy densities that can exceed 700 Wh/kg [1,2]. However, some major drawbacks prevent the Li-S battery system from being applicable in energy devices and hinder its commercialization, that include low power density and rapid capacity degradation during their cycling life. In addition, the lithium metal anode in Li-S batteries bring various issues to the forefront such as continuous solid electrolyte interface growth, dendrite formation, and loss of active lithium and electrolyte. These issues are further exacerbated at high C-rates which increases the possibility of an internal short-circuit and sudden cell failure [3]. In order to promote longer life cycles and prevent sudden cell failure, a thorough understanding of the cell’s electrochemical behavior is crucial for the development of a stable and practical Li-S battery system. The introduction of oxide fillers such TiO2, Al2O3, SiO2, etc. has been previously studied in various lithium-ion systems and has been shown to improve the cell’s lithium-ion transport properties, which in turn improve the performance of Li-S cells [4]. When used as interlayers they can also trap soluble polysulfides diffusing out of the cathode and reduce their crossover to the anode which helps reduce the shuttle effect of said polysulfides.
In the present study, the use of a polysulfide immobilizing system to reduce sulfur loss and improve capacity retention has been demonstrated. The galvanostatic charge-discharge cycling study shows that cells retain higher capacity during the course of cycling. The initial capacity for Li-S cells with the filler average 1300+ mAh/g (C/10) while the capacity stabilizes around 1000 mAh/g after 3 cycles (C/5). The capacity retention at C/5 after 75 cycles was approximately 875 mAh/g which represents a rate 0.17% drop per cycle. When compared to control cells, the cells containing no fillers had lower initial capacity that averaged 1050 mAh/g and that rapidly declined to stabilize around 650 mAh/g. However, after this major drop, the cells remained stable no with measurable drop after 75 cycles. The behavior indicates that the cells with fillers delayed the effect of sulfur loss experienced in cells without fillers; however, the slow capacity drop that ensued, indicates that while polysulfide trapping was efficient it was unable to fully prevent it. The effect of fillers on the Coulombic efficiency (CE) also supports the polysulfide “trapping” mechanism and shows the ability of the cell to reduce the shuttle effect that contributes to lower CE values. Further electrochemical studies have been performed to understand the mechanisms of the improvement of the cell.
References:
[1] A. Manthiram, Y. Fu, S.-H. Chung, C. Zu, Y.-S. Su, Rechargeable lithium–sulfur batteries, Chem Rev. 114 (2014) 11751–11787.
[2] Y. Yang, G. Zheng, Y. Cui, Nanostructured sulfur cathodes, Chem Soc Rev. 42 (2013) 3018–3032.
[3] X. Yu, A. Manthiram, A class of polysulfide catholytes for lithium–sulfur batteries: energy density, cyclability, and voltage enhancement, Physical Chemistry Chemical Physics. 17 (2015) 2127–2136.
[4] Liu, X.; Huang, J.-Q.; Zhang, Q.; Mai, L.; Liu, X.; Mai, L.; Huang, J.; Zhang, Q. Nanostructured Metal Oxides and Sulfides for Lithium–Sulfur Batteries. Adv. Mater.
2017, 29, 1601759.

Figure 1