SIMES Publications

Abstract

Lithium-ion batteries have had a profound impact on our daily life, but inherent limitations make it difficult for Li-ion chemistries to meet the growing demands for portable electronics, electric vehicles and grid-scale energy storage. Therefore, chemistries beyond Li-ion are currently being investigated and need to be made viable for commercial applications. The use of metallic Li is one of the most favoured choices for next-generation Li batteries, especially Li–S and Li–air systems. After falling into oblivion for several decades because of safety concerns, metallic Li is now ready for a revival, thanks to the development of investigative tools and nanotechnology-based solutions. In this Review, we first summarize the current understanding on Li anodes, then highlight the recent key progress in materials design and advanced characterization techniques, and finally discuss the opportunities and possible directions for future development of Li anodes in applications.

Abstract

The refractory metal titanium nitride is promising for high-temperature nanophotonic and plasmonic applications, but its optical properties have not been studied at temperatures exceeding 400  ͦ C. Here, we perform in-situ high-temperature ellipsometry to quantify the permittivity of TiN films from room temperature to 1258  ͦ C. We find that the material becomes more absorptive at higher temperatures but maintains its metallic character throughout visible and near infrared frequencies. X-ray diffraction, atomic force microscopy, and mass spectrometry confirm that TiN retains its bulk crystal quality and that thermal cycling increases the surface roughness, reduces the lattice constant, and reduces the carbon and oxygen contaminant concentrations. The changes in the optical properties of the material are highly reproducible upon repeated heating and cooling, and the room-temperature properties are fully recoverable after cooling. Using the measured high-temperature permittivity, we compute the emissivity, surface plasmon polariton propagation length, and two localized surface plasmon resonance figures of merit as functions of temperature. Our results indicate that titanium nitride is a viable plasmonic material throughout the full temperature range explored.

Abstract

Rechargeable batteries based on lithium (sodium) metal anodes have been attracting increasing attention due to their high capacity and energy density, but the implementation of lithium (sodium) metal anode still faces many challenges, such as low Coulombic efficiency and dendrites growth. Layered materials have been used experimentally as protective films (PFs) to address these issues. In this work, the authors explore using first-principles computations the key factors that determine the properties and feasibility of various 2D layered PFs, including the defect pattern, crystalline structure, bond length, and metal proximity effect, and perform the simulations on both aspects of Li⁺ (Na⁺) ion diffusion property and mechanical stability. It is found that the introduction of defect, the increase in bond length, and the proximity effect by metal can accelerate the transfer of Li⁺ (Na⁺) ion and improve the ionic conductivity, but all of them make negative influences on the stiffness of materials against the suppression of dendrite growth and weaken both critical strains and critical stress. The results provide new insight into the interaction mechanism between Li⁺ (Na⁺) ions and PF materials at the atomic level and shed light onto exploring a variety of layered PF materials in metal anode battery systems.

Abstract

In total there is hundreds of times more uranium in sea water than on land, but extracting it for use in nuclear power generation is challenging due to its low concentration (∼3 ppb) and the high salinity background. Current approaches based on sorbent materials are limited due to their surface-based physicochemical adsorption nature. Here we use a half-wave rectified alternating current electrochemical (HW-ACE) method for uranium extraction from sea water based on an amidoximefunctionalized carbon electrode. The amidoxime functionalization enables surface specific binding to uranyl ions, while the electric field can migrate the ions to the electrode and induce electrodeposition of uranium compounds, forming charge-neutral species. Extraction is not limited by the electrode surface area, and the alternating manner of the applied voltage prevents unwanted cations from blocking the active sites and avoids water splitting. The HW-ACE method achieved a ninefold higher uranium extraction capacity (1,932 mg g−1 ) without saturation and fourfold faster kinetics than conventional physicochemical methods using uranium-spiked sea water

Abstract

The observation of replica bands in single-unit-cell FeSe on SrTiO3(STO)(001) by angle-resolved photoemission spectroscopy (ARPES) has led to the conjecture that the coupling between FeSe electrons and the STO phonons are responsible for the enhancement of Tc over other FeSe-based superconductors. However the recent observation of a similar superconducting gap in single-unit-cell FeSe/STO(110) raised the question of whether a similar mechanism applies. Here we report the ARPES study of the electronic structure of FeSe/STO(110). Similar to the results in FeSe/STO(001), clear replica bands are observed. We also present a comparative study of STO(001) and STO(110) bare surfaces, and observe similar replica bands separated by approximately the same energy, indicating this coupling is a generic feature of the STO surfaces and interfaces. Our findings suggest that the large superconducting gaps observed in FeSe films grown on different STO surface terminations are likely enhanced by a common mechanism.

Abstract

To elucidate the mechanisms behind the enhanced $T_c$ in monolayer (1 ML) FeSe on ${\mathrm{SrTiO}}_3$ (STO), we grew highly strained 1 ML FeSe on the rectangular (100) face of rutile ${\mathrm{TiO}}_2$, and observed the coexistence of replica bands and superconductivity with a $T_c$ of 63 K. From the similar $T_c$ between this system and 1ML FeSe on STO (001), we conclude that strain and dielectric constant are likely unimportant to the enhanced $T_c$ in these systems. A systematic comparison of 1 ML FeSe on ${\mathrm{TiO}}_2$ with other systems in the FeSe family shows that while charge transfer alone can enhance $T_c$, it is only with the addition of interfacial electron-phonon coupling that $T_c$ can be increased to the level seen in 1 ML FeSe on STO.

Abstract

Study of the combined effects of strong electronic correlations with spin-orbit coupling (SOC) represents a central issue in quantum materials research. Predicting emergent properties represents a huge theoretical problem since the presence of SOC implies that the spin is not a good quantum number. Existing theories propose the emergence of a multitude of exotic quantum phases, distinguishable by either local point symmetry breaking or local spin expectation values, even in materials with simple cubic crystal structure such as Ba₂NaOsO₆. Experimental tests of these theories by local probes are highly sought for. Our local measurements designed to concurrently probe spin and orbital/lattice degrees of freedom of Ba₂NaOsO₆ provide such tests. Here we show that a canted ferromagnetic phase which is preceded by local point symmetry breaking is stabilized at low temperatures, as predicted by quantum theories involving multipolar spin interactions.

Abstract

Color center-containing nanodiamonds have many applications in quantum technologies and biology. Diamondoids, molecular-sized diamonds have been used as seeds in chemical vapor deposition (CVD) growth. However, optimizing growth conditions to produce high crystal quality nanodiamonds with color centers requires varying growth conditions that often leads to ad-hoc and time-consuming, one-at-a-time testing of reaction conditions. In order to rapidly explore parameter space, we developed a microwave plasma CVD technique using a vertical, rather than horizontally oriented stage-substrate geometry. With this configuration, temperature, plasma density, and atomic hydrogen density vary continuously along the vertical axis of the substrate. This variation allowed rapid identification of growth parameters that yield single crystal diamonds down to 10 nm in size and 75 nm diameter optically active center silicon-vacancy (Si-V) nanoparticles. Furthermore, this method may provide a means of incorporating a wide variety of dopants in nanodiamonds without ion irradiation damage.

Abstract

Lithium metal based batteries represent a major challenge and opportunity in enabling a variety of devices requiring high-energy-density storage. However, dendritic lithium growth has limited the practical application of lithium metal anodes. Here we report a nanoporous, flexible and electrochemically stable coating of silica@poly(methyl methacrylate) (SiO2@ PMMA) core−shell nanospheres as an interfacial layer on lithium metal anode. This interfacial layer is capable of inhibiting Li dendrite growth while sustaining ionic flux through it, which is attributed to the nanoscaled pores formed among the nanospheres. Enhanced Coulombic efficiencies during lithium charge/ discharge cycles have been achieved at various current densities and areal capacities.

Abstract

Inelastic neutron scattering measurements have been performed to investigate the spin waves of the quasione-dimensional antiferromagnetic ladder compound BaFe₂S₃, where a superconducting transition was observed under pressure [H. Takahashi et al., Nat. Mater. 14, 1008 (2015); T. Yamauchi et al., Phys. Rev. Lett. 115, 246402 (2015)]. By fitting the spherically averaged experimental data collected on a powder sample to a Heisenberg Hamiltonian, we find that the one-dimensional antiferromagnetic ladder exhibits a strong nearest-neighbor ferromagnetic exchange interaction (SJ_R = −71 ± 4 meV) along the rung direction, an antiferromagnetic SJ_L = 49 ± 3 meV along the leg direction, and a ferromagnetic SJ₂ = −15 ± 2 meV along the diagonal direction. Our data demonstrate that the antiferromagnetic spin excitations are a common characteristic for the iron-based superconductors, while specific relative values for the exchange interactions do not appear to be unique for the parent states of the superconducting materials.