Nature of Li2O2 and its relationship to the mechanisms of discharge/charge reactions of lithium–oxygen batteries

Abstract

Lithium–air batteries (LABs) are considered one of the most promising energy storage devices because of their large theoretical energy density. However, low cyclability caused by battery degradation prevents its practical use. Thus, to realize practical LABs, it is essential to improve cyclability significantly by understanding how the degradation processes proceed. Here, we used online mass spectrometry for real-time monitoring of gaseous products generated during charging of lithium–oxygen batteries (LOBs), which was operated with pure oxygen not air, with 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) tetraethylene glycol dimethyl ether (TEGDME) electrolyte solution. Linear voltage sweep (LVS) and voltage step modes were employed for charge instead of constant current charge so that the energetics of the product formation during the charge process can be understood more quantitatively. The presence of two distinctly different types of Li₂O₂, one being decomposed in a wide range of relatively low cell voltages (2.8–4.16 V) (l-Li₂O₂) and the other being decomposed at higher cell voltages than ca. 4.16 V (h-Li₂O₂), was confirmed by both LVS and step experiments. H₂O generation started when the O₂ generation rate reached a first maximum and CO₂ generation took place accompanied by the decomposition of h-Li₂O₂. Based on the above results and the effects of discharge time and the use of isotope oxygen during discharge on product distribution during charge, the generation mechanism of O₂, H₂O, and CO₂ during charging is discussed in relation to the reactions during discharge.