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. Systematic comparison of different molecular derivatives provides an atomic-scale understanding of the unique solvent structure-dependent reactivity. The interaction between Li+ and the monofluoro (-CH2F) group significantly influences the electrolyte solvation structure and promotes the monofluoro-ether-based interfacial reactions over the anion chemistry. With in-depth analyses of the compositions, charge transfer, and ion transport at interfaces, we demonstrated the essential role of the monofluoro-ether solvent chemistry in tailoring highly protective and conductive interphases (with enriched LiF at full depths) on both electrodes, as opposed to the anion-derived ones in typical concentrated electrolytes. As a result, the solvent-dominant electrolyte chemistry enables a high Li Coulombic efficiency (∼99.4%) and stable Li anode cycling at a high rate (10 mA cm-2), together with greatly improved cycling stability of 4.7 V-class nickel-rich cathodes. This work illustrates the underlying mechanism of the competitive solvent and anion interfacial reaction schemes in Li-metal batteries and offers fundamental insights into the rational design of electrolytes for future high-energy batteries.

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. Studies of ether electrolytes have been focusing on the archetype glyme structure with ethylene oxide moieties. Herein, we unveil the crucial effect of ion coordination configuration on oxidation stability by varying the ether backbone structure. The designed 1,3-dimethoxypropane (DMP, C3) forms a unique six-membered chelating complex with Li+ , whose stronger solvating ability suppresses oxidation side reactions. In addition, the favored hydrogen transfer reaction between C3 and anion induces a dramatic enrichment of LiF (a total atomic ratio of 76.7 %) on the cathode surface. As a result, the C3-based electrolyte enables greatly improved cycling of nickel-rich cathodes under 4.7 V. This study offers fundamental insights into rational electrolyte design for developing high-energy-density batteries.

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. In contrast to previous designs of weakly solvating solvents for enhanced anion reactivities, the triglyme (G3)-based electrolyte with the largest Li+ solvation energy among different linear ethers demonstrates greatly improved stability on Ni-rich cathodes under an ultrahigh voltage of 4.7 V (93% capacity retention after 100 cycles). Ether electrolytes with a stronger Li+ solvating ability could greatly suppress deleterious oxidation side reactions by decreasing the lifetime of free labile ether molecules. This study provides critical insights into the dynamics of the solvation structure and its significant influence on the interfacial stability for future development of high-efficiency electrolytes for high-energy-density LMBs.

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 (4.6 V-class) LIBs using flame-retarding ethoxy(pentafluoro) cyclotriphosphazene (PFPN) as a non-solvating diluent for the high-concentration carbonate-ether hybrid electrolyte. In contrast to conventional nonflammable additives with restricted dosage, the high level of PFPN (69% mass ratio in our electrolyte design) could significantly increase the electrolyte flash point and protect the favored anion-rich inner solvation sheath because of its non-solvating feature, thus preventing solvent co-intercalation and structural damage to the Gr anode. The nonflammable electrolyte could also form a stable LiF-rich cathode electrolyte interphase (CEI), which enables superior electrochemical performances of Gr‖LiNi0.8Mn0.1Co0.1O2 (NMC811) full cells at high voltages (∼82.0% capacity retention after 1000 cycles at 4.5 V; 89.8% after 300 cycles at 4.6 V) and high temperatures (50 °C). This work sheds light on the electrolyte design and interphase engineering for developing practical safe high-energy-density LIBs.

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 99.2 % and a high capacity retention >88 % over 200 cycles for Ni-rich cathodes at an ultrahigh cut-off voltage of 4.6 V (stable even up to 4.7 V). The chloroether-based electrolyte not only greatly improves electrochemical stabilities of Ni-rich cathodes under ultrahigh voltages with interphases riched in LiF and LiCl, but possesses the intrinsic nonflammable safety feature owing to the flame-retarding ability of chlorine functional groups. This study offers a new approach to enable ether-based electrolytes for high energy density, long-life and safe Li metal batteries.