Frederick Francois Chesneau

Understanding the behavior of Li–oxygen cells containing LiI

Mankind has been in an unending search for efficient sources of energy. The coupling of lithium and oxygen in aprotic solvents would seem to be a most promising direction for electrochemistry. Indeed, if successful, this system could compete with technologies such as the internal combustion engine and provide an energy density that would accommodate the demands of electric vehicles. All this promise has not yet reached fruition because of a plethora of practical barriers and challenges. These include solvent and electrode stability, pronounced overvoltage for oxygen evolution reactions, limited cycle life and rate capability. One of the approaches suggested to facilitate the oxygen evolution reactions and improve rate capability is the use of redox mediators such as iodine for the fast oxidation of lithium peroxide. In this paper we have examined LiI as an electrolyte and additive in Li oxygen cells with ethereal electrolyte solutions. At high concentrations of LiI, the presence of the salt promotes a side reaction that forms LiOH as a major product. In turn, the presence of oxygen facilitates the reduction of I3− to 3I− in these systems. At very low concentrations of LiI, oxygen is reduced to Li2O2. The iodine formed in the anodic reaction serves as a redox mediator for Li2O2 oxidation.

Catalytic Behavior of Lithium Nitrate in Li-O2 Cells.

The development of a successful Li-O2 battery depends to a large extent on the discovery of electrolyte solutions that remain chemically stable through the reduction and oxidation reactions that occur during cell operations. The influence of the electrolyte anions on the behavior of Li-O2 cells was thought to be negligible. However, it has recently been suggested that specific anions can have a dramatic effect on the chemistry of a Li-O2 cell. In the present paper, we describe how LiNO3 in polyether solvents can improve both oxygen reduction (ORR) and oxygen evolution (OER) reactions. In particular, the nitrate anion can enhance the ORR by enabling a mechanism that involves solubilized species like superoxide radicals, which allows for the formation of submicronic Li2O2 particles. Such phenomena were also observed in Li-O2 cells with high donor number solvents, such as dimethyl sulfoxide dimethylformamide (DMF) and dimethylacetamide (DMA). Nevertheless, their instability toward oxygen reduction, lithium metals, and high oxidation potentials renders them less suitable than polyether solvents. In turn, using catalysts like LiI to reduce the OER overpotential might enhance parasitic reactions. We show herein that LiNO3 can serve as an electrolyte and useful redox mediator. NO2(-) ions are formed by the reduction of nitrate ions on the anode. Their oxidation forms NO2, which readily oxidizes to Li2O2. The latter process moves the OER overpotentials down into a potential window suitable for polyether solvent-based cells. Advanced analytical tools, including in situ electrochemical quartz microbalance (EQCM) and ESR plus XPS, HR-SEM, and impedance spectroscopy, were used for the studies reported herein.

Comparison between Na-Ion and Li-Ion Cells: Understanding the Critical Role of the Cathodes Stability and the Anodes Pretreatment on the Cells Behavior

The electrochemical behavior of Na-ion and Li-ion full cells was investigated, using hard carbon as the anode material, and NaNi0.5Mn0.5O2 and LiNi0.5Mn0.5O2 as the cathodes. A detailed description of the structure, phase transition, electrochemical behavior and kinetics of the NaNi0.5Mn0.5O2 cathodes is presented, including interesting comparison with their lithium analogue. The critical effect of the hard carbon anodes pretreatment in the total capacity and stability of full cells is clearly demonstrated. Using impedance spectroscopy in three electrodes cells, we show that the full cell impedance is dominated by the contribution of the cathode side. We discuss possible reasons for capacity fading of these systems, its connection to the cathode structure and relevant surface phenomena.

Enhanced capacity and lower mean charge voltage of Li-rich cathodes for lithium ion batteries resulting from low-temperature electrochemical activation

High capacity and high energy cathodes prepared from Li-rich 0.35Li2MnO3·0.65Li[Mn0.45Ni0.35Co0.20]O2 materials must be activated in Li-ion cells prior to normal cycling, in order to achieve their high discharge capacity of >250 mA h g−1. Activation is performed by charging the electrodes to potentials of 4.7–4.8 V vs. Li/Li+. This communication reports on the discovery that electrochemical activation of these cathode materials at low temperatures (0–15 °C) increases their discharge capacity, lowers average charge voltage, and diminishes voltage hysteresis. Work with the above mentioned material is reported as a representative example.