TY - JOUR AU - Kristian B Knudsen AU - Pedro L Arrechea AU - Rocco P Viggiano AU - Donald A Dornbusch AU - J. Wayne Mullinax AU - Charles W Bauschlicher AU - Justin B Haskins AU - Baochau Nguyen AU - John W Lawson AU - Bryan D McCloskey AB -

Nonaqueous Li–O2 batteries have the potential to aid in the electrification of our society due to their relatively high theoretical energy density. Unfortunately, the technology suffers from large degrees of irreversibility due to the aggressive chemical environment associated with the oxidation of the discharge product lithium peroxide. Herein, we present a study of a range of linear and cyclic amides and ureas as aprotic electrolyte solvents for the Li–O2 battery, some of which show slight increases in reversibility relative to the well-established pseudo-stable glymes, although we find that none provide reversibility necessary to enable a rechargeable system. Using quantitative differential electrochemical mass spectrometry, acid titrations, and isotopic labeling of O2 and carbon in the positive electrode, we provide insight into the degradation pathways for these solvents. In the companion article, we compare our experimental results presented here to solvent decomposition pathways including a Baeyer–Villiger oxidation mechanism.

BT - The Journal of Physical Chemistry C DA - 04/2023 DO - 10.1021/acs.jpcc.2c08941 IS - 15 LA - eng N2 -

Nonaqueous Li–O2 batteries have the potential to aid in the electrification of our society due to their relatively high theoretical energy density. Unfortunately, the technology suffers from large degrees of irreversibility due to the aggressive chemical environment associated with the oxidation of the discharge product lithium peroxide. Herein, we present a study of a range of linear and cyclic amides and ureas as aprotic electrolyte solvents for the Li–O2 battery, some of which show slight increases in reversibility relative to the well-established pseudo-stable glymes, although we find that none provide reversibility necessary to enable a rechargeable system. Using quantitative differential electrochemical mass spectrometry, acid titrations, and isotopic labeling of O2 and carbon in the positive electrode, we provide insight into the degradation pathways for these solvents. In the companion article, we compare our experimental results presented here to solvent decomposition pathways including a Baeyer–Villiger oxidation mechanism.

PY - 2023 SP - 7037 EP - 7042 ST - J. Phys. Chem. C T2 - The Journal of Physical Chemistry C TI - Amide- and Urea-Based Solvents for Li–O2Batteries. Part I: Experimental Evaluation UR - https://pubs.acs.org/doi/10.1021/acs.jpcc.2c08941 VL - 127 SN - 1932-7447 ER -