Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry

TLDR

Understanding the electrolyte’s role in enabling reversible Li‑O₂ electrochemistry is a key challenge for Li‑air batteries. The authors used quantitative differential electrochemical mass spectrometry with isotopic O₂ labeling, together with ex‑situ X‑ray diffraction and Raman spectroscopy, to probe Li‑O₂ electrochemistry in carbonate and DME solvents. Carbonate solvents irreversibly decompose during discharge, whereas DME cells mainly form lithium peroxide that decomposes to O₂ during charge but also oxidizes DME; thus, accurate rechargeability assessment requires coulometry coupled with gas data, and electrolyte stability with lithium peroxide intermediates is essential for true reversibility.

Abstract

Among the many important challenges facing the development of Li-air batteries, understanding the electrolyte's role in producing the appropriate reversible electrochemistry (i.e., 2Li(+) + O2 + 2e(-) ↔ Li2O2) is critical. Quantitative differential electrochemical mass spectrometry (DEMS), coupled with isotopic labeling of oxygen gas, was used to study Li-O2 electrochemistry in various solvents, including carbonates (typical Li ion battery solvents) and dimethoxyethane (DME). In conjunction with the gas-phase DEMS analysis, electrodeposits formed during discharge on Li-O2 cell cathodes were characterized using ex situ analytical techniques, such as X-ray diffraction and Raman spectroscopy. Carbonate-based solvents were found to irreversibly decompose upon cell discharge. DME-based cells, however, produced mainly lithium peroxide on discharge. Upon cell charge, the lithium peroxide both decomposed to evolve oxygen and oxidized DME at high potentials. Our results lead to two conclusions; (1) coulometry has to be coupled with quantitative gas consumption and evolution data to properly characterize the rechargeability of Li-air batteries, and (2) chemical and electrochemical electrolyte stability in the presence of lithium peroxide and its intermediates is essential to produce a truly reversible Li-O2 electrochemistry.