ABSTRACT
Lithium metal batteries utilizing lithium metal as the anode can achieve a greater energy density. However, it remains challenging to improve low-temperature performance and fast-charging features. Herein, we introduce an electrolyte solvation chemistry strategy to regulate the properties of ethylene carbonate (EC)-based electrolytes through intermolecular interactions, utilizing weakly solvated fluoroethylene carbonate (FEC) to replace EC, and incorporating the low-melting-point solvent 1,2-difluorobenzene (2FB) as a diluent. We identified that the intermolecular interaction between 2FB and solvent can facilitate Li+ desolvation and lower the freezing point of the electrolyte effectively. The resulting electrolyte enables the LiNi0.8Co0.1Mn0.1O2||Li cell to operate at -30 °C for more than 100 cycles while delivering a high capacity of 154 mAh g-1 at 5.0C. We present a solvation structure and interfacial model to analyze the behavior of the formulated electrolyte composition, establishing a relationship with cell performance and also providing insights for the electrolyte design under extreme conditions.
ABSTRACT
Reversible lithium-ion (de)intercalation in the carbon-based anodes using ethylene carbonate (EC) based electrolytes has enabled the commercialization of lithium-ion batteries, allowing them to dominate the energy storage markets for hand-held electronic devices and electric vehicles. However, this issue always fails in propylene carbonate (PC) based electrolytes due to the cointercalation of Li+-PC. Herein, we report that a reversible Li+ (de)intercalation could be achieved by tuning the solvent-solvent interaction in a PC-based electrolyte containing a fluoroether. We study the existence of such previously unknown interactions mainly by nuclear magnetic resonance (NMR) spectroscopy, while the analysis reveals positive effects on the solvation structure and desolvation process. We have found that the fluoroether solvents interact with PC via their δ-F and δ+H atoms, respectively, leading to a reduced Li+-PC solvent interaction and effective Li+ desolvation followed by a successful Li+ intercalation at the graphite anodes. We also propose an interfacial model to interpret the varied electrolyte stability by the differences in the kinetic and thermodynamic properties of the Li+-solvent and Li+-solvent-anion complexes. Compared to the conventional strategies of tuning electrolyte concentration and/or adding additives, our discovery provides an opportunity to enhance the compatibility of PC-based electrolytes with the graphite anodes, which will enable the design of high-energy density batteries (e.g., Li-S battery) with better environmental adaptabilities.
