Koffi P. C. Yao

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.

Rate-Dependent Nucleation and Growth of NaO2 in Na–O2 Batteries

Understanding the oxygen reduction reaction kinetics in the presence of Na ions and the formation mechanism of discharge product(s) is key to enhancing Na-O2 battery performance. Here we show NaO2 as the only discharge product from Na-O2 cells with carbon nanotubes in 1,2-dimethoxyethane from X-ray diffraction and Raman spectroscopy. Sodium peroxide dihydrate was not detected in the discharged electrode with up to 6000 ppm of H2O added to the electrolyte, but it was detected with ambient air exposure. In addition, we show that the sizes and distributions of NaO2 can be highly dependent on the discharge rate, and we discuss the formation mechanisms responsible for this rate dependence. Micron-sized (∼500 nm) and nanometer-scale (∼50 nm) cubes were found on the top and bottom of a carbon nanotube (CNT) carpet electrode and along CNT sidewalls at 10 mA/g, while only micron-scale cubes (∼2 μm) were found on the top and bottom of the CNT carpet at 1000 mA/g, respectively.

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.