Limitations in Rechargeability of Li-O2 Batteries and Possible Origins.

Quantitative differential electrochemical mass spectrometry (DEMS) is used to measure the Coulombic efficiency of discharge and charge [(e(-)/O2)dis and (e(-)/O2)chg] and chemical rechargeability (characterized by the O2 recovery efficiency, OER/ORR) for Li-O2 electrochemistry in a variety of nonaqueous electrolytes. We find that none of the electrolytes studied are truly rechargeable, with OER/ORR <90% for all. Our findings emphasize that neither the overpotential for recharge nor capacity fade during cycling are adequate to assess rechargeability. Coulometry has to be coupled to quantitative measurements of the chemistry to measure the rechargeability truly. We show that rechargeability in the various electrolytes is limited both by chemical reaction of Li2O2 with the solvent and by electrochemical oxidation reactions during charging at potentials below the onset of electrolyte oxidation on an inert electrode. Possible mechanisms are suggested for electrolyte decomposition, which taken together, impose stringent conditions on the liquid electrolyte in Li-O2 batteries.

Solvents' Critical Role in Nonaqueous Lithium-Oxygen Battery Electrochemistry.

Among the many important challenges facing the development of Li-air batteries, understanding the electrolyte's role in producing the appropriate reversible electrochemistry (i.e., 2Li(+) + O2 + 2e(-) ↔ Li2O2) is critical. Quantitative differential electrochemical mass spectrometry (DEMS), coupled with isotopic labeling of oxygen gas, was used to study Li-O2 electrochemistry in various solvents, including carbonates (typical Li ion battery solvents) and dimethoxyethane (DME). In conjunction with the gas-phase DEMS analysis, electrodeposits formed during discharge on Li-O2 cell cathodes were characterized using ex situ analytical techniques, such as X-ray diffraction and Raman spectroscopy. Carbonate-based solvents were found to irreversibly decompose upon cell discharge. DME-based cells, however, produced mainly lithium peroxide on discharge. Upon cell charge, the lithium peroxide both decomposed to evolve oxygen and oxidized DME at high potentials. Our results lead to two conclusions; (1) coulometry has to be coupled with quantitative gas consumption and evolution data to properly characterize the rechargeability of Li-air batteries, and (2) chemical and electrochemical electrolyte stability in the presence of lithium peroxide and its intermediates is essential to produce a truly reversible Li-O2 electrochemistry.

Scandium clusters in fullerene cages.

The production and spectroscopic characterization of fullerene-encapsulated metal-atom clusters is reported. In particular, both solution and solid-state electron paramagnetic resonance (EPR) spectra of Sc(3)C(82) have been obtained. ScC(82) also gives an EPR spectrum, but Sc2Cn species-the most abundant metallofullerenes in the mass spectrum-are EPR-silent even though Sc(2) is EPR-active in a rare-gas matrix at 4.2 K. The results suggest that the three scandium atoms in Sc(3)C(82) form an equilateral triangle-as was previously suggested for Sc(3) molecules isolated in a cryogenic rare-gas matrix. The spectrum of ScC(82) has features similar to those found earlier for LaC(82) and YC(82), suggesting that it can also be described as a +3 metal cation within a -3 fullerene radical anion. An implication of this work is that production of macroscopic quantities of clustercontaining fullerenes may make possible the fabrication of exotic new structures with regular arrays of metal-atom clusters isolated in fullerene molecules, resulting in a new type of host/guest nanostructured material.

C60 rotation in the solid state: dynamics of a faceted spherical top.

The rotational dynamics of C(60) in the solid state have been investigated with carbon-13 nuclear magnetic resonance ((13)C NMR). The relaxation rate due to chemical shift anisotropy (1/9T1(CSA)(1)) was precisely measured from the magnetic field dependence of T(1), allowing the molecular reorientational correlation time, tau, to be determined. At 283 kelvin, tau = 9.1 picoseconds; with the assumption of diffusional reorientation this implies a rotational diffusion constant D = 1.8 x 10(10) per second. This reorientation time is only three times as long as the calculated tau for free rotation and is shorter than the value measured for C(60) in solution (15.5 picoseconds). Below 260 kelvin a second phase with a much longer reorientation time was observed, consistent with recent reports of an orientational phase transition in solid C(60). In both phases tau showed Arrhenius behavior, with apparent activation energies of 1.4 and 4.2 kilocalories per mole for the high-temperature (rotator) and low-temperature (ratchet) phases, respectively. The results parallel those found for adamantane.

Bond lengths in free molecules of buckminsterfullerene, c60, from gas-phase electron diffraction.

Electron diffraction patterns of the fullerene C(60) in the gaseous state have been obtained by volatilizing it from a newly designed oven-nozzle at 730 degrees C. The many peaks of the experimental radial distribution curve calculated from the scattered intensity are completely consistent with icosahedral symmetry for the free molecule. On the basis of this symmetry assumption, least-squares refinement of a model incorporating all possible interatomic distances led to the values r(g)(C(1)-C(2)) = 1.458(6) angstroms (A) for the thermal average bond length within the five-member ring (that is, for the bond fusing five- and six-member rings) and r(g)(C(1)-C(6)) = 1.401(10) A for that connecting five-member rings (the bond fusing six-member rings). The weighted average of the two bond lengths and the difference between them are the values 1.439(2) A and 0.057(6) A, respectively. The diameter of the icosahedral sphere is 7.113(10) A. The uncertainties in parentheses are estimated 2sigma values.

Quadrupole second-harmonic generation for a focused beam of arbitrary transverse structure and polarization.

The theory of second-harmonic generation (SHG) that is due to quadrupole and magnetic-dipole second-order optical susceptibilities is developed for monochromatic, focused beams of arbitrary transverse mode structure and polarization character. The strength of SHG depends sensitively on the polarization character of the beam.

Time-resolved infrared spectral photography.

A new technique for time-resolved (5-nsec) recording of broadband infrared absorption spectra is demonstrated. Resonantly enhanced, third-order nonlinearities of metal vapors are used both to produce a pulsed infrared continuum that interrogates the sample and to upconvert this infrared continuum into the visible. Single-shot absorption spectra of CO(2) and H(2)O bands in the region 2.55-2.85 microm were obtained.