New understanding of the role of lithium nitrate additivesin lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries are considered to be one of the next-generation battery candidates and have been widely studied. Despite the obvious advantages of Li-S batteries, there are still many serious problems with sulfur electrode: The active material sulfur (S) and the final product lithium sulfide (Li₂S) are both insulators, and the electronic conductivity is poor, so that a large amount of conductive agent must be added to the sulfur electrode; the large difference in density between S and Li₂S makes the electrode undergo a huge volume change (about 80%) during the charge and discharge process, which easily leads to the collapse of the sulfur electrode structure, which leads to the degradation of the Li-S batteries performance; the lithium polysulfide produced during charge and discharge has extremely high solubility in ether electrolytes, resulting in the "shuttle effect". Especially, the "shuttle effect" of lithium polysulfide has caused problems such as poor battery cycle performance, rapid capacity decay and overcharge, which severely restricted the further development and commercial application of Li-S batteries. As a key component of Li-S batteries, electrolyte not only plays a role in transmitting lithium cation (Li⁺) and conducting internal circuits, but also one of the main factors that determine the overall performance of the battery capacity and cycle stability. Lithium nitrate (LiNO₃) has received widespread attention as an electrolyte additive for Li-S batteries, and its mechanism of action has also been studied in depth. However, this article provides a new understanding of the mechanism of LiNO₃ additives through deep study and new experimental schemes. In this experimental scheme, the Li metal anode recycled by electrolyte containing LiNO₃ additive and fresh sulfur electrode was used to reassemble the battery with the electrolyte without the LiNO₃ additive; the sulfur electrode recycled by electrolyte containing LiNO₃ additive and fresh Li metal anod were used to reassemble the battery with the electrolyte without the LiNO₃ additive; both batteries have serious overcharging during the charging process, and the shuttle of polysulfide anions occurs. This shows that the mechanism of LiNO₃ inhibiting the "shuttle effect" is not just to form SEI film. Through the ion migration number test, it is found that after adding LiNO₃ additive, the migration number of Li⁺ increases, resulting in a significant decrease in the migration of polysulfide anions. It can be concluded that another effect of adding LiNO₃ additives is to increase the migration number of Li⁺, thereby reducing the migration number of anions and effectively inhibiting the "shuttle effect". At present, the components of gunpowder (sulfur, nitrate, carbon) are concentrated in Li-S batteries, which may be potentially dangerous during commercial use. According to the new discovery of the role of LiNO₃ additives in Li-S batteries in this work, future research work can be based on the migration number theory to find other electrolyte additives that can promote the migration number of lithium ions and interact with polysulfide anions. LiNO₃ additives, thereby reducing the potential dangers of Li-S batteries in use.