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Accurately predicting the oxidative stability of battery electrolytes is crucial for improving our understanding of high-voltage behavior and rational design of next-generation systems employing novel chemistries. However, commonly applied strategies based on evaluation of orbital occupancies of isolated molecules within density functional theory techniques neglect many-body solvation and interfacial effects that govern the electro-thermodynamics in real systems. Here, we advance a computational methodology that integrates molecular dynamics sampling of local solvation environments with explicit vertical ionization potential (IP) calculations to account for such effects. Our approach allows for both statistical accounting of IP distributions as well as prediction of the oxidized species (e.g., solvent vs anion decomposition). Application of this method to a matrix of electrolytes based on common lithium salts and solvents yields more detailed conclusions that often disagree with those gained through conventional calculations. We also demonstrate that this methodology can capture variations in IP associated with increased salt concentrations as well as the speciation and stability next to electrified model interfaces. This work offers a comprehensive accounting of the microscopic factors and electronic structure considerations that stabilize molecules and their unique solvation environment in modern electrochemical systems. 

The physical and chemical properties of electrolytes have significant impacts on battery performance. The concept of nanoconfinement has been proposed as an innovative modification strategy to address challenges related to the thermal stability, ion transport efficiency, and electrochemical stability of electrolytes. This involves confining electrolytes within nanoscale or sub-nanoscale spaces, leading to improvements in their physicochemical properties, such as increased boiling points, optimized ion migration, regulated ion concentration gradients, effective ion sieving, accelerated charge transfer, and suppressed side reactions. In this perspective article, we highlight the substantial potential of these approaches for extending the cycle life, broadening operational conditions, and enhancing the safety of lithium-based batteries. Additionally, the challenges and future research directions in this area are discussed. 

Abstract Matching the capacity of the anode and cathode is essential for maximizing electrochemical cell performance. This study presents two strategies to balance the electrode utilization in zinc ion supercapacitors, by decreasing dendritic loss in the zinc anode while increasing the capacity of the activated carbon cathode. The anode current collector was modified with copper nanoparticles to direct zinc plating orientation and minimize dendrite formation, improving the Coulombic efficiency and cycle life. The cathode was activated by an electrolyte reaction to increase its porosity and gravimetric capacity. The full cell delivered a specific energy of 192 ± 0.56 Wh kg⁻¹at a specific power of 1.4 kW kg⁻¹, maintaining 84% capacity after 50,000 full charge-discharge cycles up to 2 V. With a cumulative capacity of 19.8 Ah cm⁻²surpassing zinc ion batteries, this device design is particularly promising for high-endurance applications, including un-interruptible power supplies and energy-harvesting systems that demand frequent cycling.