Selective Methylation of Cyclic Ether Towards Highly Elastic Solid Electrolyte Interphase for Silicon-based Anodes.

Silicon (Si)-based anodes offer high theoretical capacity for lithium-ion batteries but suffer from severe volume changes and continuous solid electrolyte interphase (SEI) degradation. Here, we address these challenges by selective methylation of 1,3-dioxolane (DOL), thus shifting the unstable bulk polymerization to controlled interfacial reactions and resulting in a highly elastic SEI. Comparative studies of 2-methyl-1,3-dioxolane (2MDOL) and 4-methyl-1,3-dioxolane (4MDOL) reveal that 4MDOL, with its larger ring strain and more stable radical intermediates due to hyperconjugation effect, promotes the formation of high-molecular-weight polymeric species at the electrode-electrolyte interface.

Push-Pull Electrolyte Design Strategy Enables High-Voltage Low-Temperature Lithium Metal Batteries.

Lithium (Li) metal batteries hold significant promise in elevating energy density, yet their performance at ultralow temperatures remains constrained by sluggish charge transport kinetics and the formation of unstable interphases. In conventional electrolyte systems, lithium ions are tightly locked in the solvation structure, thereby engendering difficulty in the desolvation process and further exacerbating solvent decomposition. Herein, we propose a new push-pull electrolyte design strategy, utilizing molecular electrostatic potential (ESP) screening to identify 2,2-difluoroethyl trifluoromethanesulfonate (DTF) as an optimal cosolvent.

Highly reversible zinc metal anode enabled by strong Brønsted acid and hydrophobic interfacial chemistry.

Uncontrollable zinc (Zn) plating and hydrogen evolution greatly undermine Zn anode reversibility. Previous electrolyte designs focus on suppressing HO reactivity, however, the accumulation of alkaline byproducts during battery calendar aging and cycling still deteriorates the battery performance. Here, we present a direct strategy to tackle such problems using a strong Brønsted acid, bis(trifluoromethanesulfonyl)imide (HTFSI), as the electrolyte additive.

Recent advances in electrolyte molecular design for alkali metal batteries.

In response to societal developments and the growing demand for high-energy-density battery systems, alkali metal batteries (AMBs) have emerged as promising candidates for next-generation energy storage. Despite their high theoretical specific capacity and output voltage, AMBs face critical challenges related to high reactivity with electrolytes and unstable interphases. This review, from the perspective of electrolytes, analyzes AMB failure mechanisms, including interfacial side reactions, active materials loss, and metal dendrite growth.

Molecular anchoring of free solvents for high-voltage and high-safety lithium metal batteries.

Constraining the electrochemical reactivity of free solvent molecules is pivotal for developing high-voltage lithium metal batteries, especially for ether solvents with high Li metal compatibility but low oxidation stability ( <4.0 V vs Li/Li). The typical high concentration electrolyte approach relies on nearly saturated Li coordination to ether molecules, which is confronted with severe side reactions under high voltages ( >4.

Unveiling the Critical Role of Ion Coordination Configuration of Ether Electrolytes for High Voltage Lithium Metal Batteries.

Albeit ethers are favorable electrolyte solvents for lithium (Li) metal anode, their inferior oxidation stability (<4.0 V vs. Li/Li ) is problematic for high-voltage cathodes.

Solvent versus Anion Chemistry: Unveiling the Structure-Dependent Reactivity in Tailoring Electrochemical Interphases for Lithium-Metal Batteries.

Electrolytes are critical for the reversibility of various electrochemical energy storage systems. The recent development of electrolytes for high-voltage Li-metal batteries has been counting on the salt anion chemistry for building stable interphases. Herein, we investigate the effect of the solvent structure on the interfacial reactivity and discover profound solvent chemistry of designed monofluoro-ether in anion-enriched solvation structures, which enables enhanced stabilization of both high-voltage cathodes and Li-metal anodes.

Localized Alkaline Environment via In Situ Electrostatic Confinement for Enhanced CO-to-Ethylene Conversion in Neutral Medium.

Electrocatalytic CO reduction reaction (CORR) is one of the most promising routes to facilitate carbon neutrality. An alkaline electrolyte is typically needed to promote the production of valuable multi-carbon molecules (such as ethylene). However, the reaction between CO and OH consumes a significant quantity of CO/alkali and causes the rapid decay of CORR selectivity and stability.

Strongly Solvating Ether Electrolytes for High-Voltage Lithium Metal Batteries.

Ethers are promising electrolytes for lithium (Li) metal batteries (LMBs) because of their unique stability with Li metal. Although intensive research on designing anion-enriched electrolyte solvation structures has greatly improved their electrochemical stabilities, ether electrolytes are approaching an anodic bottleneck. Herein, we reveal the strong correlation between electrolyte solvation structure and oxidation stability.

High-safety and high-efficiency electrolyte design for 4.6 V-class lithium-ion batteries with a non-solvating flame-retardant.

Nonflammable electrolytes are critical for the safe operation of high-voltage lithium-ion batteries (LIBs). Although organic phosphates are effective flame retardants, their poor electrochemical stability with a graphite (Gr) anode and Ni-rich cathodes would lead to the deterioration of electrode materials and fast capacity decay. Herein, we develop a safe and high-performance electrolyte formulation for high-voltage (4.

Regulating Frozen Electrolyte Structure with Colloidal Dispersion for Low Temperature Aqueous Batteries.

Electrolyte freezing under low temperatures is a critical challenge for the development of aqueous batteries (ABs). While lowering the freezing point of the electrolyte has caught major research efforts, limited attention has been paid to the structural evolution during the electrolyte freezing process and regulating the frozen electrolyte structure for low temperature ABs. Here, we reveal the formation process of interconnected liquid regions for ion transport in frozen electrolytes with various in situ variable-temperature technologies.

Intrinsic Nonflammable Ether Electrolytes for Ultrahigh-Voltage Lithium Metal Batteries Enabled by Chlorine Functionality.

The issues of inherent low anodic stability and high flammability hinder the deployment of the ether-based electrolytes in practical high-voltage lithium metal batteries. Here, we report a rationally designed ether-based electrolyte with chlorine functionality on ether molecular structure to address these critical challenges. The chloroether-based electrolyte demonstrates a high Li Coulombic efficiency of 99.