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Life of superoxide in aprotic Li-O-2 battery electrolytes: simulated solvent and counter-ion effects

Johan Scheers (Institutionen för fysik, Kondenserade materiens fysik (Chalmers)) ; David Lidberg (Institutionen för fysik (Chalmers)) ; K. Sodeyama ; Z. Futera ; Y. Tateyama
Physical Chemistry Chemical Physics - PCCP (1463-9076). Vol. 18 (2016), 15, p. 9961-9968.
[Artikel, refereegranskad vetenskaplig]

Li-air batteries ideally make use of oxygen from the atmosphere and metallic lithium to reversibly drive the reaction 2Li + O-2 <-> Li2O2. Conceptually, energy throughput is high and material use is efficient, but practically many material challenges still remain. It is of particular interest to control the electrolyte environment of superoxide (O-2(star-)) to promote or hinder specific reaction mechanisms. By combining density functional theory based molecular dynamics (DFT-MD) and DFT simulations we probe the bond length and the electronic properties of O-2(star-) in three aprotic solvents -in the presence of Li+ or the much larger cation alternative tetrabutylammonium (TBA(+)). Contact ion pairs, LiO2 star, are favoured over solvent-separated ion pairs in all solvents, but particularly in low permittivity dimethoxyethane (DME), which makes O-2(star-) more prone to further reduction. The Li+-O-2(star-) interactions are dampened in dimethyl sulfoxide (DMSO), in relation to those in DME and propylene carbonate (PC), which is reflected by smaller changes in the electronic properties of O-2(star-) in DMSO. The additive TBA+ offers an alternative, more weakly interacting partner to O-2(star-), which makes it easier to remove the unpaired electron and oxidation more feasible. In DMSO, TBA(+) has close to no effect on O-2(star-), which behaves as if no cation is present. This is contrasted by a much stronger influence of TBA(+) on O-2(star-) in DME -comparable to that of Li+ in DMSO. An important future goal is to compare and rank the effects of different additives beyond TBA(+). Here, the results of DFT calculations for small-sized cluster models are in qualitative agreement with those of the DFT-MD simulations, which suggests the cluster approach to be a cost-effective alternative to the DFT-MD simulations for a more extensive comparison of additive effects in future studies.

Nyckelord: space gaussian pseudopotentials, air batteries, molecular-dynamics, dimethyl-sulfoxide, stability, carbonate, anion, acetonitrile, instability, reduction

Denna post skapades 2016-06-10. Senast ändrad 2016-10-04.
CPL Pubid: 237565


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