Qiyang Lu

Resistive Switching Mechanisms on TaOx and SrRuO3 Thin-Film Surfaces Probed by Scanning Tunneling Microscopy.

The local electronic properties of tantalum oxide (TaOx, 2 ≤ x ≤ 2.5) and strontium ruthenate (SrRuO3) thin-film surfaces were studied under the influence of electric fields induced by a scanning tunneling microscope (STM) tip. The switching between different redox states in both oxides is achieved without the need for physical electrical contact by controlling the magnitude and polarity of the applied voltage between the STM tip and the sample surface. We demonstrate for TaOx films that two switching mechanisms operate. Reduced tantalum oxide shows resistive switching due to the formation of metallic Ta, but partial oxidation of the samples changes the switching mechanism to one mediated mainly by oxygen vacancies. For SrRuO3, we found that the switching mechanism depends on the polarity of the applied voltage and involves formation, annihilation, and migration of oxygen vacancies. Although TaOx and SrRuO3 differ significantly in their electronic and structural properties, the resistive switching mechanisms could be elaborated based on STM measurements, proving the general capability of this method for studying resistive switching phenomena in different classes of transition metal oxides.

A robust and active hybrid catalyst for facile oxygen reduction in solid oxide fuel cells

The sluggish oxygen reduction reaction (ORR) greatly reduces the energy efficiency of solid oxide fuel cells (SOFCs). Here we report our findings in dramatically enhancing the ORR kinetics and durability of the state-of-the-art La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode using a hybrid catalyst coating composed of a conformal PrNi0.5Mn0.5O3 (PNM) thin film with exsoluted PrOx nanoparticles. At 750 °C, the hybrid catalyst-coated LSCF cathode shows a polarization resistance of ∼0.022 Ω cm2, about 1/6 of that for a bare LSCF cathode (∼0.134 Ω cm2). Further, anode-supported cells with the hybrid catalyst-coated LSCF cathode demonstrate remarkable peak power densities (∼1.21 W cm−2) while maintaining excellent durability (0.7 V for ∼500 h). Near Ambient X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-Ray Absorption Fine Structure (NEXAFS) analyses, together with density functional theory (DFT) calculations, indicate that the oxygen-vacancy-rich surfaces of the PrOx nanoparticles greatly accelerate the rate of electron transfer in the ORR whereas the thin PNM film facilitates rapid oxide-ion transport while drastically enhancing the surface stability of the LSCF electrode.

Voltage-Controlled Topotactic Phase Transition in Thin-Film SrCoOx Monitored by In Situ X-ray Diffraction

Topotactic phase transition of functional oxides induced by changes in oxygen nonstoichiometry can largely alter multiple physical and chemical properties, including electrical conductivity, magnetic state, oxygen diffusivity, and electrocatalytic reactivity. For tuning these properties reversibly, feasible means to control oxygen nonstoichiometry-dependent phase transitions in functional oxides are needed. This paper describes the use of electrochemical potential to induce phase transition in strontium cobaltites, SrCoOx (SCO) between the brownmillerite (BM) phase, SrCoO₂.₅, and the perovskite (P) phase, SrCoO₃₋δ. To monitor the structural evolution of SCO, in situ X-ray diffraction (XRD) was performed on an electrochemical cell having (001) oriented thin-film SrCoOx as the working electrode on a single crystal (001) yttria-stabilized zirconia electrolyte in air. In order to change the effective pO₂ in SCO and trigger the phase transition from BM to P, external electrical biases of up to 200 mV were applied across the SCO film. The phase transition from BM to P phase could be triggered at a bias as low as 30 mV, corresponding to an effective pO₂ of 1 atm at 500 °C. The phase transition was fully reversible and the epitaxial film quality was maintained after reversible phase transitions. These results demonstrate the use of electrical bias to obtain fast and easily accessible switching between different phases as well as distinct physical and chemical properties of functional oxides as exemplified here for SCO.

Accelerated Oxygen Exchange Kinetics on Nd2NiO4+δ Thin Films with Tensile Strain along c-Axis

The influence of the lattice strain on the kinetics of the oxygen reduction reaction (ORR) was investigated at the surface of Nd2NiO4+δ (NNO). Nanoscale dense NNO thin films with tensile, compressive and no strain along the c-axis were fabricated by pulsed laser deposition on single-crystalline Y0.08Zr0.92O2 substrates. The ORR kinetics on the NNO thin film cathodes was investigated by electrochemical impedance spectroscopy at 360-420 °C in air. The oxygen exchange kinetics on the NNO films with tensile strain along the c-axis was found to be 2-10 times faster than that on the films with compressive strain along the c-axis. A larger concentration of oxygen interstitials (δ) is found in the tensile NNO films compared to the films with no strain or compressive strain, deduced from the measured chemical capacitance. This is consistent with the increase in the distance between the NdO rock-salt layers observed by transmission electron microscopy. The surface structure of the nonstrained and tensile strained films remained stable upon annealing in air at 500 °C, while a significant morphology change accompanied by the enrichment of Nd was found at the surface of the films with compressive strain. The faster ORR kinetics on the tensile strained NNO films was attributed to the ability of these films to incorporate oxygen interstitials more easily, and to the better stability of the surface chemistry in comparison to the nonstrained or compressively strained films.

Chemomechanics of ionically conductive ceramics for electrical energy conversion and storage

Functional materials for energy conversion and storage exhibit strong coupling between electrochemistry and mechanics. For example, ceramics developed as electrodes for both solid oxide fuel cells and batteries exhibit cyclic volumetric expansion upon reversible ion transport. Such chemomechanical coupling is typically far from thermodynamic equilibrium, and thus is challenging to quantify experimentally and computationally. In situ measurements and atomistic simulations are under rapid development to explore how this coupling can be used to potentially improve both device performance and durability. Here, we review the commonalities of coupling between electrochemical and mechanical states in fuel cell and battery materials, illustrating with specific cases the progress in materials processing, in situ characterization, and computational modeling and simulation. We also highlight outstanding questions and opportunities in these applications – both to better understand the limiting mechanisms within the materials and to significantly advance the durability and predictability of device performance required for renewable energy conversion and storage.

Self-Arranged Misfit Dislocation Network Formation upon Strain Release in La0.7Sr0.3MnO3/LaAlO3(100) Epitaxial Films under Compressive Strain.

Lattice-mismatched epitaxial films of La0.7Sr0.3MnO3 (LSMO) on LaAlO3 (001) substrates develop a crossed pattern of misfit dislocations above a critical thickness of 2.5 nm. Upon film thickness increases, the dislocation density progressively increases, and the dislocation spacing distribution becomes narrower. At a film thickness of 7.0 nm, the misfit dislocation density is close to the saturation for full relaxation. The misfit dislocation arrangement produces a 2D lateral periodic structure modulation (Λ ≈ 16 nm) alternating two differentiated phases: one phase fully coherent with the substrate and a fully relaxed phase. This modulation is confined to the interface region between film and substrate. This phase separation is clearly identified by X-ray diffraction and further proven in the macroscopic resistivity measurements as a combination of two transition temperatures (with low and high Tc). Films thicker than 7.0 nm show progressive relaxation, and their macroscopic resistivity becomes similar than that of the bulk material. Therefore, this study identifies the growth conditions and thickness ranges that facilitate the formation of laterally modulated nanocomposites with functional properties notably different from those of fully coherent or fully relaxed material.

Dislocations Accelerate Oxygen Ion Diffusion in La0.8Sr0.2MnO3 Epitaxial Thin Films

Revealing whether dislocations accelerate oxygen ion transport is important for providing abilities in tuning the ionic conductivity of ceramic materials. In this study, we report how dislocations affect oxygen ion diffusion in Sr-doped LaMnO3 (LSM), a model perovskite oxide that serves in energy conversion technologies. LSM epitaxial thin films with thicknesses ranging from 10 nm to more than 100 nm were prepared by pulsed laser deposition on single-crystal LaAlO3 and SrTiO3 substrates. The lattice mismatch between the film and substrates induces compressive or tensile in-plane strain in the LSM layers. This lattice strain is partially reduced by dislocations, especially in the LSM films on LaAlO3. Oxygen isotope exchange measured by secondary ion mass spectrometry revealed the existence of at least two very different diffusion coefficients in the LSM films on LaAlO3. The diffusion profiles can be quantitatively explained by the existence of fast oxygen ion diffusion along threading dislocations that is faster by up to 3 orders of magnitude compared to that in LSM bulk.

Strongly correlated perovskite lithium ion shuttles

Significance Designing solid-state ion conductors is of broad interest to energy conversion, bioengineering, and information processing. Here, we demonstrate a new class of Li-ion conducting quantum materials in the perovskite family. Rare-earth perovskite nickelate films of the chemical formula SmNiO3 are shown to exhibit high Li-ion conductivity while minimizing their electronic conductivity. This process occurs by electron injection into Ni orbitals when the Li ions are inserted from a reservoir. The mechanism of doping is studied by high-resolution experimental and first-principles theoretical methods to provide evidence for ion shuttling in the lattice and the atomistic pathways. The experiments are then extended to other small ions such as Na+, demonstrating the generality of the approach. Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO3 (Li-SNO) contains a large amount of mobile Li+ located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li+ conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na+. The results highlight the potential of quantum materials and emergent physics in design of ion conductors.