ABSTRACT
Lithium metal batteries face problems from sluggish charge transfer at interfaces, as well as parasitic reactions between lithium metal anodes and electrolytes, due to the strong electronegativity of oxygen donor solvents. These factors constrain the reversibility and kinetics of lithium metal batteries at low temperatures. Here, a nonsolvating cosolvent is applied to weaken the electronegativity of donor oxygen in ether solvents, enabling the participation of anionic donors in the solvation structure of Li+. This strategy significantly accelerates the desolvation process of Li+ and reduces the side effects of solvents on interfacial transport and stability. The designed anion-aggregated electrolyte has a unique temperature-insensitive solvation structure and enables lithium metal anodes to achieve a high average Coulombic efficiency at room temperature and -20 °C. A high-loading LiFePO4||Li cell exhibited high reversibility with a 100% capacity retention after 150 cycles at room temperature, -20, and -40 °C. The practical 1 Ah-level LiFePO4||Li pouch-cell delivered 81% and 61% of the capacity at room temperature when charged and discharged at -20 and -40 °C, respectively. This strategy of constructing temperature-insensitive solvation by electronegativity regulation offers a novel approach for developing electrolytes of low-temperature batteries.
ABSTRACT
The unstable electrode-electrolyte interface and the narrow electrochemical window of normal electrolytes hinder the potential application of high-voltage sodium metal batteries. These problems are actually related to the solvation structure of the electrolyte, which is determined by the competition between cations coordinated with anions or solvent molecules. Herein, we design an electrolyte incorporating ethyl (2,2,2-trifluoroethyl) carbonate and fluoroethylene carbonate, which facilitates a pronounced level of cation-anion coordination within the solvation sheath by enthalpy changes to reduce the overall coordination of cation-solvents and increase sensitivity to salt concentration. Such an electrolyte regulated by competitive coordination leads to highly reversible sodium plating/stripping with extended cycle life and a high Coulombic efficiency of 98.0%, which is the highest reported so far in Na||Cu cells with ester-based electrolytes. Moreover, 4.5 V high-voltage Na||Na3V2(PO4)2F3 cells exhibit a high rate capability up to 20 C and an impressive cycling stability with an 87.1% capacity retention after 250 cycles with limited Na. The proposed strategy of solvation structure modification by regulating the competitive coordination of the cation provides a new direction to achieve stable sodium metal batteries with high energy density and can be further extended to other battery systems by controlling enthalpy changes of the solvation structure.
ABSTRACT
Although the rechargeable lithium-sulfur battery is an advanced energy storage system, its practical implementation has been impeded by many issues, in particular the shuttle effect causing rapid capacity fade and low Coulombic efficiency. Herein, we report a conductive porous vanadium nitride nanoribbon/graphene composite accommodating the catholyte as the cathode of a lithium-sulfur battery. The vanadium nitride/graphene composite provides strong anchoring for polysulfides and fast polysulfide conversion. The anchoring effect of vanadium nitride is confirmed by experimental and theoretical results. Owing to the high conductivity of vanadium nitride, the composite cathode exhibits lower polarization and faster redox reaction kinetics than a reduced graphene oxide cathode, showing good rate and cycling performances. The initial capacity reaches 1,471 mAh g-1 and the capacity after 100 cycles is 1,252 mAh g-1 at 0.2 C, a loss of only 15%, offering a potential for use in high energy lithium-sulfur batteries.
ABSTRACT
A sulfur-rich copolymer@carbon nanotubes hybrid cathode is introduced for lithium-sulfur batteries produced by combining the physical and chemical confinement of polysulfides. The binderfree and metal-current-collector-free cathode of dual confinement enables an efficient pathway for the fabrication of high-performance sulfur copolymer carbon matrix electrodes for lithium-sulfur batteries.
ABSTRACT
A 3D graphene-foam-reduced-graphene-oxide hybrid nested hierarchical network is synthesized to achieve high sulfur loading and content simultaneously, which solves the "double low" issues of Li-S batteries. The obtained Li-S cathodes show a high areal capacity two times larger than that of commercial lithium-ion batteries, and a good cycling performance comparable to those at low sulfur loading.
