Jonathon R. Harding

Lithium–oxygen batteries: bridging mechanistic understanding and battery performance

Rechargeable energy storage systems with high energy density and round-trip efficiency are urgently needed to capture and deliver renewable energy for applications such as electric transportation. Lithium–air/lithium–oxygen (Li–O2) batteries have received extraordinary research attention recently owing to their potential to provide positive electrode gravimetric energies considerably higher (∼3 to 5×) than Li-ion positive electrodes, although the packaged device energy density advantage will be lower (∼2×). In light of the major technological challenges of Li–O2 batteries, we discuss current understanding developed in non-carbonate electrolytes of Li–O2 redox chemistry upon discharge and charge, oxygen reduction reaction product characteristics upon discharge, and the chemical instability of electrolytes and carbon commonly used in the oxygen electrode. We show that the kinetics of oxygen reduction reaction are influenced by catalysts at small discharge capacities (Li2O2 thickness less than ∼1 nm), but not at large Li2O2 thicknesses, yielding insights into the governing processes during discharge. In addition, we discuss the characteristics of discharge products (mainly Li2O2) including morphological, electronic and surface features and parasitic reactivity with carbon. On charge, we examine the reaction mechanism of the oxygen evolution reaction from Li2O2 and the influence of catalysts on bulk Li2O2 decomposition. These analyses provide insights into major discrepancies regarding Li–O2 charge kinetics and the role of catalyst. In light of these findings, we highlight open questions and challenges in the Li–O2 field relevant to developing practical, reversible batteries that achieve the anticipated energy density advantage with a long cycle life.

The discharge rate capability of rechargeable Li–O2 batteries

The O2electrode in Li–O2cells was shown to exhibit gravimetric energy densities (considering the total weight of oxygen electrode in the discharged state) four times that of LiCoO2 with comparable gravimetric power. The discharge rate capability of Au-catalyzed Vulcan carbon and pure Vulcan carbon (VC) as the O2electrode was studied in the range of 100 to 2000 mA gcarbon−1. The discharge voltage and capacity of the Li−O2 cells were shown to decrease with increasing rates. Unlike propylene carbonate based electrolytes, the rate capability of Li−O2 cells tested with 1,2-dimethoxyethane was found not to be limited by oxygen transport in the electrolyte. X-Ray diffraction (XRD) showed lithium peroxide as the discharge product and no evidence of Li2CO3 and LiOH was found. It is hypothesized that higher discharge voltages of cells with Au/C than VC at low rates could have originated from higher oxygen reduction activity of Au/C. At high rates, higher discharge voltages with Au/C than VC could be attributed to faster lithium transport in nonstoichiometric and defective lithium peroxide formed upon discharge, which is supported by XRD and X-ray absorption near edge structure O and Li K edge data.

In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.

Solid-state activation of Li2O2 oxidation kinetics and implications for Li–O2 batteries

As one of the most theoretically promising next-generation chemistries, Li–O2 batteries are the subject of intense research to address their stability, cycling, and efficiency issues. The recharge kinetics of Li–O2 are especially sluggish, prompting the use of metal nanoparticles as reaction promoters. In this work, we probe the underlying pathway of kinetics enhancement by transition metal and oxide particles using a combination of electrochemistry, X-ray absorption spectroscopy, and thermochemical analysis in carbon-free and carbon-containing electrodes. We highlight the high activity of the group VI transition metals Mo and Cr, which are comparable to noble metal Ru and coincide with XAS measured changes in surface oxidation state matched to the formation of Li2MoO4 and Li2CrO4. A strong correlation between conversion enthalpies of Li2O2 with the promoter surface (Li2O2 + MaOb ± O2 → LixMyOz) and electrochemical activity is found that unifies the behaviour of solid-state promoters. In the absence of soluble species on charge and the decomposition of Li2O2 proceeding through solid solution, enhancement of Li2O2 oxidation is mediated by chemical conversion of Li2O2 with slow oxidation kinetics to a lithium metal oxide. Our mechanistic findings provide new insights into the selection and/or employment of electrode chemistry in Li–O2 batteries.