title: Correlating Li/O2 cell capacity and product morphology with discharge current.
abstract: The discharge rate is critical to the performance of lithium/oxygen batteries: it impacts both cell capacity and discharge-phase morphology, and in so doing may also affect the efficiency of the oxygen-evolution reaction during recharging. First-discharge data from tens of Li/O2 cells discharged across four rates are analyzed statistically to inform these connections. In the practically significant superficial current-density range of 0.1 to 1 mA cm(-2), capacity is found to fall as a power law, with a Peukert's-law exponent of 1.6 ± 0.1. X-ray diffractometry confirms the dominant presence of crystalline Li2O2 in the discharged electrodes. A completely air-free sample-transfer technique was developed to implement scanning electron microscopy (SEM) of the discharge product. SEM imaging of electrodes with near-average capacities provides statistically significant measures of the shape and size variation of electrodeposited Li2O2 particles with respect to discharge current. At lower rates, typical "toroidal" particles are observed that are well approximated as cylindrical structures, whose average radii remain relatively constant as discharge rate increases, whereas their average heights decrease. At the highest rate studied, air-free SEM shows that particles take needle-like shapes rather than forming the nanosheets or compact films described elsewhere. Average particle volumes decrease with current while particle surface-to-volume ratios increase dramatically, supporting the notion that Li2O2 grows by a locally mass-transfer-limited nucleation and growth mechanism.
authors.affiliation: †Department of Chemical Engineering, 2300 Hayward St., University of Michigan, Ann Arbor Michigan 48109, United States.
authors.forename: Lucas D
authors.initials: LD
authors.lastname: Griffith
authors.affiliation: †Department of Chemical Engineering, 2300 Hayward St., University of Michigan, Ann Arbor Michigan 48109, United States.
authors.forename: Alice E S
authors.initials: AE
authors.lastname: Sleightholme
authors.affiliation: ‡Electron Microbeam Analysis Laboratory, 2800 Plymouth Road, University of Michigan, Ann Arbor, Michigan 48109, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Mansfield
authors.affiliation: §Department of Mechanical Engineering, 2350 Hayward St., University of Michigan, Ann Arbor, Michigan 48109, United States.
authors.forename: Donald J
authors.initials: DJ
authors.lastname: Siegel
authors.affiliation: †Department of Chemical Engineering, 2300 Hayward St., University of Michigan, Ann Arbor Michigan 48109, United States.
authors.forename: Charles W
authors.initials: CW
authors.lastname: Monroe
keywords: Peukert’s law; lithium−oxygen batteries; morphology; nucleation and growth; rate performance