No abstract

Electrolyte is very critical to the performance of the high-voltage lithium (Li) metal battery (LMB), which is one of the most attractive candidates for the next-generation high-density energy-storage systems. Electrolyte formulation and structure determine the physical properties of the electrolytes and their interfacial chemistries on the electrode surfaces. Localized high-concentration electrolytes (LHCEs) outperform state-of-the-art carbonate electrolytes in many aspects in LMBs due to their unique solvation structures. Types of fluorinated cosolvents used in LHCEs are investigated here in searching for the most suitable diluent for high-concentration electrolytes (HCEs). Nonsolvating solvents (including fluorinated ethers, fluorinated borate, and fluorinated orthoformate) added in HCEs enable the formation of LHCEs with high-concentration solvation structures. However, low-solvating fluorinated carbonate will coordinate with Li+ ions and form a second solvation shell or a pseudo-LHCE which diminishes the benefits of LHCE. In addition, it is evident that the diluent has significant influence on the electrode/electrolyte interphases (EEIs) beyond retaining the high-concentration solvation structures. Diluent molecules surrounding the high-concentration clusters could accelerate or decelerate the anion decomposition through coparticipation of diluent decomposition in the EEI formation. The varied interphase features lead to significantly different battery performance. This study points out the importance of diluents and their synergetic effects with the conductive salt and the solvating solvent in designing LHCEs. These systematic comparisons and fundamental insights into LHCEs using different types of fluorinated solvents can guide further development of advanced electrolytes for high-voltage LMBs.

The lithium-sulfur (Li-S) battery is a promising next-generation energy storage technology because of its high theoretical energy and low cost. Extensive research efforts have been made on new materials and...

To enable next‐generation high‐power, high‐energy‐density lithium (Li) metal batteries (LMBs), an electrolyte possessing both high Li Coulombic efficiency (CE) at a high rate and good anodic stability on cathodes is critical. Acetonitrile (AN) is a well‐known organic solvent for high anodic stability and high ionic conductivity, yet its application in LMBs is limited due to its poor compatibility with Li metal anodes even at high salt concentration conditions. Here, a highly concentrated AN‐based electrolyte is developed with a vinylene carbonate (VC) additive to suppress Li+ depletion at high current densities. Addition of VC to the AN‐based electrolyte leads to the formation of a polycarbonate‐based solid electrolyte interphase, which minimizes Li corrosion and leads to a very high Li CE of up to 99.2% at a current density of 0.2 mA cm‐2. Using such an electrolyte, fast charging of Li||NMC333 cells is realized at a high current density of 3.6 mA cm‐2, and stable cycling of Li||NMC622 cells with a high cathode loading of 4 mAh cm‐2 is also demonstrated.

The renaissance of Li-S battery technology is evidenced by the intensive R&D efforts in recent years. Although the theoretical capacity and energy of a Li-S battery is theoretically very high, the projected usable energy is expected to be no more than twice that of state-of-the-art Li-ion batteries, or 500 Wh/kg. The recent "sulfur fever" has certainly gathered new knowledge on sulfur chemistry and electrochemistry, electrolytes, lithium metal, and their interactions in this "new" system; however, a real advance toward a practical Li-S battery is still missing. One of the main reasons behind this is the sensitivity of Li-S batteries to the experimental testing parameters. Sophisticated nanostructures are usually employed, while the practicality of these nanomaterials for batteries is rarely discussed. The sulfur electrode, usually engineered in a thin-film configuration, further poses uncertainties in the knowledge transfer from the lab to industry. This review article briefly overviews the recent research progress on Li-S batteries, followed by a discussion of the Li-S battery system from the authors' own understandings collected from their past few years of research. The critical findings, the unresolved issues, and the scientific gap between lab research and industrial application are discussed. The future work in Li-S battery research is also explored to propel relevant research efforts toward industrial applications.