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The momentum in developing next-generation high energy batteries calls for an electrolyte that is compatible with both lithium (Li) metal anodes and high-voltage cathodes, and is also capable of providing high power in a wide temperature range. Here, we present a fluoromethane-based liquefied gas electrolyte with acetonitrile cosolvent and a higher, yet practical, salt concentration. The unique solvation structure observed in molecular dynamics simulations and confirmed experimentally shows not only an improved ionic conductivity of 9.0 mS cm−1 at +20 °C but a high Li transference number (tLi+ = 0.72). Excellent conductivity (>4 mS cm−1) was observed from −78 to +75 °C, demonstrating operation above fluoromethane's critical point for the first time. The liquefied gas electrolyte also enables excellent Li metal stability with a high average coulombic efficiency of 99.4% over 200 cycles at the aggressive condition of 3 mA cm−2 and 3 mA h cm−2. Also, dense Li deposition with an ideal Li–substrate contact is seen in the liquefied gas electrolyte, even at −60 °C. Attributed to superior electrolyte properties and the stable interfaces on both cathode and anode, the performances of both Li metal anode and Li/NMC full cell (up to 4.5 V) are well maintained in a wide-temperature range from −60 to +55 °C. This study provides a pathway for wide-temperature electrolyte design to enable high energy density Li–metal battery operation between −60 to +55 °C.

Among the several challenges to enable next-generation batteries is the development of an electrolyte which compatible with both lithium (Li) metal anode and high-voltage cathode at wide temperature range. Liquefied gas electrolytes with a new cosolvent and higher salt concentration show improved ionic conductivity of > 4 mS/cm at wide temperature range from -80 to +70 °C. With a new solvation structure, the liquefied gas electrolytes demonstrated high-temperature operation of Li-metal batteries at 55°C, which is the operation above the electrolytes’ critical point for the first time. The electrolytes enable improved Li metal stability and coulombic efficiency at aggressive current and capacity of 3 mA·cm-2 and 3 mAh·cm-2 with average coulombic efficiency of 99%. The use of liquefied gas electrolytes presents stable cycling of Li/NMC (4.4 V) cell at all-temperature range between -60 and 55°C. This study opens up a promising avenue toward the applications of all-temperature high energy density Li-metal batteries.

Summary Among the several challenges to enable next-generation batteries is the development of an electrolyte that maintains a dendrite-free and high Coulombic efficiency lithium-metal anode over extended cell cycling. A new electrolyte solvation structure and transport mechanism is demonstrated in fluoromethane-based liquefied gas electrolytes with the introduction of additive amounts of tetrahydrofuran, which is shown to fully coordinate with the lithium cations and greatly enhance salt dissociation and transport. The resulting electrolyte shows a high conductivity and transference number (t+ > 0.79), which leads to a dramatic improvement of the cycling performance of the lithium-metal anode. Systems using the enhanced liquefied gas electrolytes demonstrate a long-term high average Coulombic efficiency of 99.6%, 99.4%, and 98.1% (± 0.3%) at capacities of 0.5, 1, and 3 mAh·cm−2, respectively, with dendrite-free morphology and remarkable rate capability. Both the rate and cycling performance are well maintained from +20°C to −60°C.

Batteries will play critical roles in modernizing energy grids, as they will allow a greater penetration of renewable energy and perform applications that better match supply with demand. Applying storage technology is a business decision that requires potential revenues to be accurately estimated to determine the economic viability, which requires models that consider market rules and prices, along with battery and application-specific constraints. Here we use models of storage connected to the California energy grid and show how the application-governed duty cycles (power profiles) of different applications affect different battery chemistries. We reveal critical trade-offs between battery chemistries and the applicability of energy content in the battery and show that accurate revenue measurement can only be achieved if a realistic battery operation in each application is considered. The findings in this work could call for a paradigm shift in how the true economic values of energy storage devices could be assessed. Large variations exist in the revenue prediction of grid-scale storage due to uncertainties in operations of storage technologies. Here the authors integrate the economic evaluation of energy storage with key battery parameters for a realistic measure of revenues.

When substituting excess lithium in the transition metal layer, oxygen extends its role as a framework in classical layered oxide cathodes, exhibiting electrochemical activity and enhancing the reversible capacities of layered oxides through anionic redox mechanisms. However, oxygen activity comes with instability in the form of oxygen loss, which is associated with irreversible voltage decay and capacity fade. To understand this irreversible loss and to increase the stability of lattice oxygen, density functional theory is applied to calculate oxygen vacancy formation energies in lithium rich transition metal layered oxides for a variety of dopants, noting increased stability upon doping with 4d elements Mo and Ru. Driven by these findings, Mo is co-doped with Co into Li[Li0.2Ni0.2Mn0.6]O2, showing notably reduced voltage decay and capacity fade without sacrificing energy density and cycle life, and the evidence of Mo incorporation is presented. Calculations suggest that this is due to a modified charge density distribution around anions upon incorporation of Mo, altering the local band structure and impeding oxygen vacancy formation, while maintaining the anionic activity available for redox.