Interactions of Dimethoxy Ethane with Li2O2 Clusters and Likely Decomposition Mechanisms for Li-O2 Batteries

摘要

One of the major problems facing the successful development of Li-O2 batteries is the decomposition of nonaqueous electrolytes, where the decomposition can be chemical or electrochemical during discharge or charge. In this paper, the decomposition pathways of dimethoxy ethane (DME) by the chemical reaction with the major discharge product, Li2O2, are investigated using theoretical methods. The computations were carried out using small Li2O2 clusters as models for potential sites on Li2O2 surfaces. Both hydrogen and proton abstraction mechanisms were considered. The computations suggest that the most favorable decomposition of ether solvents occurs on certain sites on the lithium peroxide surfaces involving hydrogen abstraction followed by reaction with oxygen, which leads to oxidized species such as aldehydes and carboxylates as well as LiOH on the surface of the lithium peroxide. The most favorable site is a Li-O-Li site that may be present on small nanoparticles or as a defect site on a surface. The decomposition route initiated by the proton abstraction from the secondary position of DME by the singlet cluster (O-O site) requires a much larger enthalpy of activation, and subsequent reactions may require the presence of oxygen or superoxide. Thus, pathways involving proton abstraction are less likely than that involving hydrogen abstraction. This type of electrolyte decomposition (electrolyte with hydrogen atoms) may influence the cell performance including the crystal growth, nanomorphologies of the discharge products, and charge overpotential.