Graphic, Quantitation, Visualization, Standardization, Digitization, and Intelligence of Electrolyte and Electrolyte‐Electrode Interface

Abstract

Electrolytes have recently regained significant attention in rechargeable batteries due to the discovery that the electrolyte microstructures play a determinant role in battery performance. By adjusting the compositions of electrolytes to cater to various functionalities, such as high‐voltage, fast‐charging, wide‐temperature operation, and non‐flammable features, a diverse range of batteries can be developed to adapt to different environmental working conditions. Nevertheless, elucidating the electrolyte microstructures and understanding the associated electrode interfacial behaviors remain challenging. These challenges arise from the interdisciplinary nature of the research, encompassing subjects such as solution chemistry, interface chemistry, electrochemistry, and organic chemistry. This topic holds particular significance because solution chemistry and solution‐solid interface chemistry are ubiquitous in daily lives, yet their behaviors remain unclear due to their inherent complexity, dynamic nature, and rapid variability. In this context, electrolyte and electrolyte‐electrode interface research are used as an illustrative example and summarize their progress from six key perspectives of graphic, quantitation, visualization, standardization, digitization, and intelligence. It is aimed to provide a multi‐faceted understanding of electrolyte microstructures and their behaviors on the electrode interface. This comprehensive approach enables the effective design of electrolytes and enhances the accuracy of predicting battery performance, servicing the development of solution and solution‐solid interface.

Trace ethylene carbonate-mediated low-concentration ether-based electrolytes for high-voltage lithium metal batteries

“…We constructed the solvation structure and the derived electrode interfacial model based on the formula of Li + [solvent] x [anion] to interpret the battery performance at the molecular scale. 59,60 The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the solvent molecules and ion clusters were obtained through DFT simulations. Note that the LUMO and HOMO of the cationic clusters, such as the Li + -solvent cluster, have a trend to move to lower values compared to those of the solvent due to the decreased number of delocalized electrons caused by the polarization of Li + .…”

Low-Temperature and Fast-Charging Lithium Metal Batteries Enabled by Solvent–Solvent Interaction Mediated Electrolyte

“…Furthermore, some electrolyte formulations are not derived from commercialized carbonate-based electrolytes, posing challenges for practical applications . Similar challenges exist in ether-based electrolytes, including solvent volatility, increased cost of high concentration and/or new molecules, and difficulties in stable cycling at high-voltage operations, making commercialization challenging. − Thus, designing a compatible electrolyte that is readily commercializable while elucidating design principles and understanding the relationship between electrolyte composition and battery performance remains a significant challenge. − …”

Electrolyte Intermolecular Interaction Mediated Nonflammable Potassium-Ion Sulfur Batteries

“…Potassium-ion batteries (PIBs) offer several potential advantages compared to state-of-the-art lithium-ion batteries (LIBs), including highly abundant potassium sources worldwide, rapid ion diffusion in organic electrolytes, and a low standard electrode potential (−2.93 V vs E 0 ), which is close to that of LIBs (−3.04 V vs E 0 ). − These characteristics have garnered significant attention within the energy storage community. , In the pursuit of commercializing PIBs, substantial investigations have been concentrated on the development of superior electrode materials. The cathode materials for PIBs have been previously explored and can be categorized into three main groups: Prussian blue (PB) , and its analogues, , layered metal oxides, − and polyanion oxides. , As for the anode materials, various types, including carbon-based materials, , phosphorus-based materials, − and alloys, , have been extensively reported.…”