Electrochemical Investigation of the Reaction Mechanism in Lithium-Oxygen Batteries

Lithium-oxygen batteries, also known as Lithium-air batteries, could possibly revolutionize energy storage as we know. By letting lithium react with ambient oxygen gas very large theoretical energy densities are possible. However, there are several challenges remaining to be solved, such as finding suitable materials and understanding the reaction, before the lithium-oxygen battery could be commercialized. The scope of this thesis is focusing on the latter of these challenges. Efficient ion transport between the electrodes is imperative for all batteries that need high power density and energy efficiency. Here the mass transport properties of lithium ions in several different solvents was evaluated. The results showed that the lithium mass transport in electrolytes based on the commonly used lithium-oxygen battery solvent dimethyl sulfoxide (DMSO) was very similar to that of conventional lithium-ion battery electrolytes. However, when room temperature ionic liquids were used the performance severely decreased. Addition of Li salt will effect the oxygen concentration in DMSO-based electrolytes. The choice of lithium salt influenced whether the oxygen concentration increased or decreased. At one molar salt concentration the highest oxygen solubility was 68 % larger than the lowest one. Two model systems was used to study the electrochemical reaction: A quartz crystal microbalance and a cylindrical ultramicroelectrode. The combined usage of these systems showed that during discharge soluble lithium superoxide was produced. A consequence of this was that not all discharge product ended up on the electrode surface. During discharge the cylindrical ultramicroelectrodes displayed signs of passivation that previous theory could not adequately describe. Here the passivation was explained in terms of depletion of active sites. A mechanism was also proposed. The O2 and Li+ concentration dependencies of the discharge process were evaluated by determining the reactant reaction order under kinetic and mass transport control. Under kinetic control the system showed non-integer reaction orders with that