Conrad L. Bender

A rechargeable room-temperature sodium superoxide (NaO2) battery

In the search for room-temperature batteries with high energy densities, rechargeable metal-air (more precisely metal-oxygen) batteries are considered as particularly attractive owing to the simplicity of the underlying cell reaction at first glance. Atmospheric oxygen is used to form oxides during discharging, which-ideally-decompose reversibly during charging. Much work has been focused on aprotic Li-O(2) cells (mostly with carbonate-based electrolytes and Li(2)O(2) as a potential discharge product), where large overpotentials are observed and a complex cell chemistry is found. In fact, recent studies evidence that Li-O(2) cells suffer from irreversible electrolyte decomposition during cycling. Here we report on a Na-O(2) cell reversibly discharging/charging at very low overpotentials (< 200 mV) and current densities as high as 0.2 mA cm(-2) using a pure carbon cathode without an added catalyst. Crystalline sodium superoxide (NaO(2)) forms in a one-electron transfer step as a solid discharge product. This work demonstrates that substitution of lithium by sodium may offer an unexpected route towards rechargeable metal-air batteries.

A comprehensive study on the cell chemistry of the sodium superoxide (NaO2) battery

This work reports on the cell chemistry of a room temperature sodium-oxygen battery using an electrolyte of diethylene glycol dimethyl ether (diglyme) and sodium trifluoromethanesulfonate (NaSO3CF3, sodium triflate). Different from lithium-oxygen cells, where lithium peroxide is found as the discharge product, sodium superoxide (NaO2) is formed in the present cell, with overpotentials as low as 100 mV during charging. Several analytical methods are used to follow the cell reaction during discharge and charge. Changes in structure and morphology are studied by SEM and XRD. It is found that NaO2 grows as cubic particles with feed sizes in the range of 10-50 μm; upon recharge the particles consecutively decompose. Pressure monitoring during galvanostatic cycling shows that the coulombic efficiency (e(-)/O2) for discharge and charge is approx. 1.0, the expected value for NaO2 formation. Also optical spectroscopy is identified as a convenient and useful tool to follow the discharge-charge process. The maximum discharge capacity is found to be limited by oxygen transport within the electrolyte soaked carbon fiber cathode and pore blocking near the oxygen interface is observed. Finally electrolyte decomposition and sodium dendrite growth are identified as possible reasons for the limited capacity retention of the cell. The occurrence of undesired side reactions is analyzed by DEMS measurements during cycling as well as by post mortem XPS investigations.

From lithium to sodium: cell chemistry of room temperature sodium–air and sodium–sulfur batteries

Summary Research devoted to room temperature lithium–sulfur (Li/S8) and lithium–oxygen (Li/O2) batteries has significantly increased over the past ten years. The race to develop such cell systems is mainly motivated by the very high theoretical energy density and the abundance of sulfur and oxygen. The cell chemistry, however, is complex, and progress toward practical device development remains hampered by some fundamental key issues, which are currently being tackled by numerous approaches. Quite surprisingly, not much is known about the analogous sodium-based battery systems, although the already commercialized, high-temperature Na/S8 and Na/NiCl2 batteries suggest that a rechargeable battery based on sodium is feasible on a large scale. Moreover, the natural abundance of sodium is an attractive benefit for the development of batteries based on low cost components. This review provides a summary of the state-of-the-art knowledge on lithium–sulfur and lithium–oxygen batteries and a direct comparison with the analogous sodium systems. The general properties, major benefits and challenges, recent strategies for performance improvements and general guidelines for further development are summarized and critically discussed. In general, the substitution of lithium for sodium has a strong impact on the overall properties of the cell reaction and differences in ion transport, phase stability, electrode potential, energy density, etc. can be thus expected. Whether these differences will benefit a more reversible cell chemistry is still an open question, but some of the first reports on room temperature Na/S8 and Na/O2 cells already show some exciting differences as compared to the established Li/S8 and Li/O2 systems.

One- or Two-Electron Transfer? The Ambiguous Nature of the Discharge Products in Sodium-Oxygen Batteries.

Rechargeable lithium-oxygen and sodium-oxygen cells have been considered as challenging concepts for next-generation batteries, both scientifically and technologically. Whereas in the case of non-aqueous Li/O2 batteries, the occurring cell reaction has been unequivocally determined (Li2O2 formation), the situation is much less clear in the case of non-aqueous Na/O2 cells. Two discharge products, with almost equal free enthalpies of formation but different numbers of transferred electrons and completely different kinetics, appear to compete, namely NaO2 and Na2O2. Cells forming either the superoxide or the peroxide have been reported, but it is unclear how the cell reaction can be influenced for selective one- or two-electron transfer to occur. In this Minireview, we summarize available data, discuss important control parameters, and offer perspectives for further research. Water and proton sources appear to play major roles.

Sodiated carbon: a reversible anode for sodium–oxygen batteries and route for the chemical synthesis of sodium superoxide (NaO2)

The common cell design of sodium/oxygen batteries is based on an alkali metal as the negative electrode and a carbon gas diffusion layer (GDL) as the positive (oxygen) electrode. The use of sodium metal anodes maximizes the energy capacity, but on the other hand induces undesired and often unpredictable side reactions that complicate investigations on the oxygen electrode and the overall cell chemistry. Therefore we demonstrate the function of a sodium-ion/oxygen battery by replacing sodium metal with a sodiated carbon electrode that is able to reversibly store up to q = 125 mA h g−1. We use a symmetric “all GDL” arrangement, i.e. the same carbon gas diffusion layer is used as the positive and negative electrode. Overall, this approach increases the cycle life by a factor of 5 and further decreases the sum of the charge and discharge overpotentials (η = 150 mV @ j = 200 μA cm−2), proving that current limitations of the sodium–oxygen battery are mainly determined by the metal anode rather than by the oxygen cathode. We find that sodium storage in the GDL proceeds by at least two different mechanisms which can be distinguished by their different chemical stabilities against oxygen and water. Another important finding is that NaO2 can be also synthesized chemically (rather than electrochemically) under ambient conditions from sodiated carbon and gaseous oxygen – which is interesting with respect to the competition between NaO2 and Na2O2 as discharge products.

Visualizing Current-Dependent Morphology and Distribution of Discharge Products in Sodium-Oxygen Battery Cathodes.

Synchrotron X-ray tomography and scanning electron microscopy were applied to elucidate the spatial distribution of discharge product (NaO2) in the carbon cathode of sodium-oxygen batteries. Various batteries were discharged galvanostatically and their cathodes were analyzed. We observe a particle density gradient along the cathode that scales with the current density applied. Besides, we show that the particle size and shape of discharge product strongly depend on current density, and on whether the particles are deposited close to the oxygen reservoir or near the separator. We correlate our findings to transport limitations for the supplied oxygen and gain crucial information for optimal operation of sodium-oxygen batteries. Our findings imply that for low current densities pore clogging might occur, and that for elevated current densities small high surface area particles with limited electric conductivity form; both phenomena can decrease the available discharge and charge capacity significantly.