Surface-redox sodium-ion storage in anatase titanium oxide.

Sodium-ion storage technologies are promising candidates for large-scale grid systems due to the abundance and low cost of sodium. However, compared to well-understood lithium-ion storage mechanisms, sodium-ion storage remains relatively unexplored. Herein, we systematically determine the sodium-ion storage properties of anatase titanium dioxide (TiO2(A)). During the initial sodiation process, a thin surface layer (~3 to 5 nm) of crystalline TiO2(A) becomes amorphous but still undergoes Ti4+/Ti3+ redox reactions. A model explaining the role of the amorphous layer and the dependence of the specific capacity on the size of TiO2(A) nanoparticles is proposed. Amorphous nanoparticles of ~10 nm seem to be optimum in terms of achieving high specific capacity, on the order of 200 mAh g-1, at high charge/discharge rates. Kinetic studies of TiO2(A) nanoparticles indicate that sodium-ion storage is due to a surface-redox mechanism that is not dependent on nanoparticle size in contrast to the lithiation of TiO2(A) which is a diffusion-limited intercalation process. The surface-redox properties of TiO2(A) result in excellent rate capability, cycling stability and low overpotentials. Moreover, tailoring the surface-redox mechanism enables thick electrodes of TiO2(A) to retain high rate properties, and represents a promising direction for high-power sodium-ion storage.

Mechanistic Insight and Local Structure Evolution of NiPS3 upon Electrochemical Lithiation.

Transition metal phosphorus trisulfide materials have received considerable research interest since the 1980-1990s as they exhibit promising energy conversion and storage properties. However, the mechanistic insights into Li-ion storage in these materials are poorly understood to date. Here, we explore the lithiation of NiPS3 material by employing in situ pair-distribution function analysis, Monte Carlo molecular dynamics calculations, and a series of ex situ characterizations. Our findings elucidate complex ion insertion and storage dynamics around a layered polyanionic compound, which undergoes intercalation and conversion reactions in a sequential manner. This study of NiPS3 material exemplifies the Li-ion storage mechanism in transition metal phosphorus sulfide materials and provides insights into the challenges associated with achieving reliable, high-energy phosphorus trisulfide systems.

Transparent silica aerogel slabs synthesized from nanoparticle colloidal suspensions at near ambient conditions on omniphobic liquid substrates.

This paper presents a novel sol-gel method to synthesize large and thick silica aerogel monoliths at near ambient conditions using a commercial aqueous solution of colloidal silica nanoparticles as building blocks. To achieve slabs with high visible transmittance and low thermal conductivity, the method combines the strategies of (i) synthesizing gels on an omniphobic perfluorocarbon liquid substrate, (ii) aging at temperatures above room temperature, and (iii) performing solvent exchange with a low-surface-tension organic solvent prior to ambient drying. The omniphobic liquid substrates were used to prevent cracking and ensure an optically-smooth surface, while nanoparticle building blocks were small (<10 nm) to limit volumetric light scattering. Gels were aged at temperatures between 25 and 80 °C for up to 21 days to make them stronger and stiffer and to reduce shrinkage and cracking during ambient drying. Ambient drying was achieved by first exchanging water in the gel pores for octane, followed by drying in an octane-rich atmosphere to decrease capillary forces. The synthesized nanoparticle-based silica aerogel monoliths had thicknesses up to 5 mm, diameters up to 10 cm, porosities exceeding 80%, and thermal conductivities as low as 0.08 W m-1 K-1. Notably, the slabs featured visible transmittance exceeding 75% even for slabs as thick as 5 mm. The as-synthesized aerogel monoliths were exposed to TMCS vapor to induce hydrophobic properties resulting in a water contact angle of 140° that prevented water infiltration into the pores and protected the aerogels from water damage. This simple synthesis route conducted at near ambient conditions produces hydrophobic aerogel monoliths with promising optically transparent and thermally insulating properties that can be adhered to glass panes for window insulation and solar-thermal energy conversion applications.

Degradation of (La(0.8)Sr(0.2))(0.98)MnO(3-δ)-Zr(0.84)Y(0.16)O(2-γ) composite electrodes during reversing current operation.

Reversing-current operation of solid oxide cell (La(0.8)Sr(0.2))(0.98)MnO(3-δ)-Zr(0.84)Y(0.16)O(2-γ) (LSM-YSZ) oxygen electrodes is described. Degradation was characterized by impedance spectroscopy in symmetric cells tested at 800 °C in air with a symmetric current cycle with a period of 12 hours. No change in cell resistance could be detected, in 1000 h tests with a sensitivity of ∼1% per kh, at a current density of 0.5 A cm(-2) corresponding to an overpotential of 0.18 V. At a current density to 0.6 A cm(-2) (0.33 V overpotential) measurable resistance degradation at a rate of 3% per kh was observed, while higher current/overpotential values led to faster degradation. Degradation was observed mainly in the ohmic resistance for current densities of 0.6, 0.8 and 0.9 A cm(-2), with little change in the polarization resistance. Polarization degradation, mainly observed at higher current density, was present as an increase in an impedance response at ∼30 kHz, apparently associated with the resistance of YSZ grain boundaries within the electrode. Microstructural and chemical analysis showed significant changes in electrode structure after the current cycling, including an increase in LSM particle size and a reduction in the amount of YSZ and LSM at the electrode/electrolyte interface - the latter presumably a precursor to delamination.