A lithium-oxygen battery with a long cycle life in an air-like atmosphere.

Lithium-air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy. So far, however, such systems have been largely restricted to pure oxygen environments (lithium-oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium-oxygen systems may be too small for practical applications. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium-air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium-oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.

Ultralow-Temperature Li/CFx Batteries Enabled by Fast-Transport and Anion-Pairing Liquefied Gas Electrolytes.

Lithium fluorinated-carbon (Li/CFx ) is one of the most promising chemistries for high-energy-density primary energy-storage systems in applications where rechargeability is not required. Though Li/CFx demonstrates high energy density (>2100 Wh kg-1 ) under ambient conditions, achieving such a high energy density when exposed to subzero temperatures remains a challenge, particularly under high current density. Here, a liquefied gas electrolyte with an anion-pair solvation structure based on dimethyl ether with a low melting point (-141 °C) and low viscosity (0.12 mPa s, 20 °C), leading to high ionic conductivity (>3.5 mS cm-1 ) between -70 and 60 °C is reported. Besides that, through systematic X-ray photoelectron spectroscopy integrated with transmission electron microscopy characterizations, the interface of CFx is evaluated for low-temperature performance. The fast transport and anion-pairing solvation structure of the electrolyte are concluded to bring about reduced charge-transfer resistance at low temperatures, which results in significantly enhanced performance of Li/CFx cells (1690 Wh kg-1 , -60 °C based on active materials). Utilizing 50 mg cm-2 loading electrodes, the Li/CFx still displays 1530 Wh kg-1 at -60 °C. This work provides insights into the electrolyte design that may overcome the operational limits of batteries in extreme environments.

Evaluating Electrolyte-Anode Interface Stability in Sodium All-Solid-State Batteries.

All-solid-state batteries have recently gained considerable attention due to their potential improvements in safety, energy density, and cycle-life compared to conventional liquid electrolyte batteries. Sodium all-solid-state batteries also offer the potential to eliminate costly materials containing lithium, nickel, and cobalt, making them ideal for emerging grid energy storage applications. However, significant work is required to understand the persisting limitations and long-term cyclability of Na all-solid-state-based batteries. In this work, we demonstrate the importance of careful solid electrolyte selection for use against an alloy anode in Na all-solid-state batteries. Three emerging solid electrolyte material classes were chosen for this study: the chloride Na2.25Y0.25Zr0.75Cl6, sulfide Na3PS4, and borohydride Na2(B10H10)0.5(B12H12)0.5. Focused ion beam scanning electron microscopy (FIB-SEM) imaging, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS) were utilized to characterize the evolution of the anode-electrolyte interface upon electrochemical cycling. The obtained results revealed that the interface stability is determined by both the intrinsic electrochemical stability of the solid electrolyte and the passivating properties of the formed interfacial products. With appropriate material selection for stability at the respective anode and cathode interfaces, stable cycling performance can be achieved for Na all-solid-state batteries.

Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes.

The development of silicon anodes for lithium-ion batteries has been largely impeded by poor interfacial stability against liquid electrolytes. Here, we enabled the stable operation of a 99.9 weight % microsilicon anode by using the interface passivating properties of sulfide solid electrolytes. Bulk and surface characterization, and quantification of interfacial components, showed that such an approach eliminates continuous interfacial growth and irreversible lithium losses. Microsilicon full cells were assembled and found to achieve high areal current density, wide operating temperature range, and high areal loadings for the different cells. The promising performance can be attributed to both the desirable interfacial property between microsilicon and sulfide electrolytes and the distinctive chemomechanical behavior of the lithium-silicon alloy.

A Long-Cycle-Life Lithium-CO2 Battery with Carbon Neutrality.

Lithium-CO2 batteries are attractive energy-storage systems for fulfilling the demand of future large-scale applications such as electric vehicles due to their high specific energy density. However, a major challenge with Li-CO2 batteries is to attain reversible formation and decomposition of the Li2 CO3 and carbon discharge products. A fully reversible Li-CO2 battery is developed with overall carbon neutrality using MoS2 nanoflakes as a cathode catalyst combined with an ionic liquid/dimethyl sulfoxide electrolyte. This combination of materials produces a multicomponent composite (Li2 CO3 /C) product. The battery shows a superior long cycle life of 500 for a fixed 500 mAh g-1 capacity per cycle, far exceeding the best cycling stability reported in Li-CO2 batteries. The long cycle life demonstrates that chemical transformations, making and breaking covalent CO bonds can be used in energy-storage systems. Theoretical calculations are used to deduce a mechanism for the reversible discharge/charge processes and explain how the carbon interface with Li2 CO3 provides the electronic conduction needed for the oxidation of Li2 CO3 and carbon to generate the CO2 on charge. This achievement paves the way for the use of CO2 in advanced energy-storage systems.

New Class of Electrocatalysts Based on 2D Transition Metal Dichalcogenides in Ionic Liquid.

The optimization of traditional electrocatalysts has reached a point where progress is impeded by fundamental physical factors including inherent scaling relations among thermokinetic characteristics of different elementary reaction steps, non-Nernstian behavior, and electronic structure of the catalyst. This indicates that the currently utilized classes of electrocatalysts may not be adequate for future needs. This study reports on synthesis and characterization of a new class of materials based on 2D transition metal dichalcogenides including sulfides, selenides, and tellurides of group V and VI transition metals that exhibit excellent catalytic performance for both oxygen reduction and evolution reactions in an aprotic medium with Li salts. The reaction rates are much higher for these materials than previously reported catalysts for these reactions. The reasons for the high activity are found to be the metal edges with adiabatic electron transfer capability and a cocatalyst effect involving an ionic-liquid electrolyte. These new materials are expected to have high activity for other core electrocatalytic reactions and open the way for advances in energy storage and catalysis.

Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide.

Electrocatalytic conversion of carbon dioxide (CO2) into energy-rich fuels is considered to be the most efficient approach to achieve a carbon neutral cycle. Transition-metal dichalcogenides (TMDCs) have recently shown a very promising catalytic performance for CO2 reduction reaction in an ionic liquid electrolyte. Here, we report that the catalytic performance of molybdenum disulfide (MoS2), a member of TMDCs, can be significantly improved by using an appropriate dopant. Our electrochemical results indicate that 5% niobium (Nb)-doped vertically aligned MoS2 in ionic liquid exhibits 1 order of magnitude higher CO formation turnover frequency (TOF) than pristine MoS2 at an overpotential range of 50-150 mV. The TOF of this catalyst is also 2 orders of magnitude higher than that of Ag nanoparticles over the entire range of studied overpotentials (100-650 mV). Moreover, the in situ differential electrochemical mass spectrometry experiment shows the onset overpotential of 31 mV for this catalyst, which is the lowest onset potential for CO2 reduction reaction reported so far. Our density functional theory calculations reveal that low concentrations of Nb near the Mo edge atoms can enhance the TOF of CO formation by modifying the binding energies of intermediates to MoS2 edge atoms.