The need for both high electrical conductivity and low thermal conductivity creates a design conflict for thermoelectric systems, leading to the consideration of materials with complicated crystal structures. Rattling of ions in cages results in low thermal conductivity, but understanding the mechanism through studies of the phonon dispersion using momentum-resolved spectroscopy is made difficult by the complexity of the unit cells. We have performed inelastic X-ray and neutron scattering experiments that are in remarkable agreement with our first-principles density-functional calculations of the phonon dispersion for thermoelectric Na(0.8)CoO2, which has a large-period superstructure. We have directly observed an Einstein-like rattling mode at low energy, involving large anharmonic displacements of the sodium ions inside multi-vacancy clusters. These rattling modes suppress the thermal conductivity by a factor of six compared with vacancy-free NaCoO2. Our results will guide the design of the next generation of materials for applications in solid-state refrigerators and power recovery.

No abstract

No abstract

High performance batteries based on the movement of Li ions in LixCoO2 have made possible a revolution in mobile electronic technology, from laptops to mobile phones. However, the scarcity of Li and the demand for energy storage for renewables has led to intense interest in Na-ion batteries, including structurally-related NaxCoO2. Here we have determined the diffusion mechanism for Na0.8CoO2 using diffuse x-ray scattering, quasi-elastic neutron scattering and ab-initio molecular dynamics simulations, and we find that the sodium ordering provides diffusion pathways and governs the diffusion rate. Above T ~ 290 K the so-called partially disordered stripe superstructure provides channels for quasi-1D diffusion, and melting of the sodium ordering leads to 2D superionic diffusion above T ~ 370 K. We obtain quantitative agreement between our microscopic study of the hopping mechanism and bulk self-diffusion measurements. Our approach can be applied widely to other Na- or Li-ion battery materials.

In the present communication, a novel composite nanofibrous electrode is developed for the detection of superoxide anion (O(2)˙(-)) in phosphate buffered saline (PBS). The composite fiber electrode is fabricated by dispersing gold nanoparticles onto poly(methyl methacrylate) (PMMA)-polyaniline (PANI) core-shell electrospun nanofibers. The constructed architecture is proven to be a favorable environment for the immobilization of the enzyme, superoxide dismutase (SOD). Direct electron transfer is achieved between SOD and the electrode with an electron transfer rate constant of 8.93 s(-1). At an applied potential of +300 mV, PMMA/PANI-Au(nano)/SOD-ESCFM shows highly sensitive detection of O(2)˙(-). In addition to this, quantification of different activities of SOD is realized at PMMA/PANI-Au(nano)/SOD-ESCFM. These analytical features offer great potential for construction of the third-generation O(2)˙(-) biosensor.