The role of oxygen in automotive grade lithium-ion battery cathodes: an atomistic survey of ageing.

The rising demand for high-performance lithium-ion batteries, pivotal to electric transportation, hinges on key materials like the Ni-rich layered oxide LiNixCoyAlzO2 (NCA) used in cathodes. The present study investigates the redox mechanisms, with particular focus on the role of oxygen in commercial NCA electrodes, both fresh and aged under various conditions (aged cells have performed >900 cycles until a cathode capacity retention of ∼80%). Our findings reveal that oxygen participates in charge compensation during NCA delithiation, both through changes in transition metal (TM)-O bond hybridization and formation of partially reversible O2, the latter occurs already below 3.8 V vs. Li/Li+. Aged NCA material undergoes more significant changes in TM-O bond hybridization when cycling above 50% SoC, while reversible O2 formation is maintained. Nickel is found to be redox active throughout the entire delithiation and shows a more classical oxidation state change during cycling with smaller changes in the Ni-O hybridization. By contrast, Co redox activity relies on a stronger change in Co-O hybridization, with only smaller Co oxidation state changes. The Ni-O bond displays an almost twice as large change in its bond length on cycling as the Co-O bond. The Ni-O6 octahedra are similar in size to the Co-O6 octahedra in the delithiated state, but are larger in the lithiated state, a size difference that increases with battery ageing. These contrasting redox activities are reflected directly in structural changes. The NCA material exhibits the formation of nanopores upon ageing, and a possible connection to oxygen redox activity is discussed. The difference in interaction of Ni and Co with oxygen provides a key understanding of the mechanism and the electrochemical instability of Ni-rich layered transition metal oxide electrodes. Our research specifically highlights the significance of the role of oxygen in the electrochemical performance of electric-vehicle-grade NCA electrodes, offering important insights for the creation of next-generation long-lived lithium-ion batteries.

Momentum-resolved spin-conserving two-triplon bound state and continuum in a cuprate ladder.

Studying multi-particle elementary excitations has provided unique access to understand collective many-body phenomena in correlated electronic materials, paving the way towards constructing microscopic models. In this work, we perform O K-edge resonant inelastic X-ray scattering (RIXS) on the quasi-one-dimensional cuprate Sr14Cu24O41 with weakly-doped spin ladders. The RIXS signal is dominated by a dispersing sharp mode ~ 270 meV on top of a damped incoherent component ~ 400-500 meV. Comparing with model calculations using the perturbative continuous unitary transformations method, the two components resemble the spin-conserving ΔS = 0 two-triplon bound state and continuum excitations in the spin ladders. Such multi-spin response with long-lived ΔS = 0 excitons is central to several exotic magnetic properties featuring Majorana fermions, yet remains unexplored given the generally weak cross-section with other experimental techniques. By investigating a simple spin-ladder model system, our study provides valuable insight into low-dimensional quantum magnetism.

Modulation of New Excitons in Transition Metal Dichalcogenide-Perovskite Oxide System.

The exciton, a quasi-particle that creates a bound state of an electron and a hole, is typically found in semiconductors. It has attracted major attention in the context of both fundamental science and practical applications. Transition metal dichalcogenides (TMDs) are a new class of 2D materials that include direct band-gap semiconductors with strong spin-orbit coupling and many-body interactions. Manipulating new excitons in semiconducting TMDs could generate a novel means of application in nanodevices. Here, the observation of high-energy excitonic peaks in the monolayer-MoS2 on a SrTiO3 heterointerface generated by a new complex mechanism is reported, based on a comprehensive study that comprises temperature-dependent optical spectroscopies and first-principles calculations. The appearance of these excitons is attributed to the change in many-body interactions that occurs alongside the interfacial orbital hybridization and spin-orbit coupling brought about by the excitonic effect propagated from the substrate. This has further led to the formation of a Fermi-surface feature at the interface. The results provide an atomic-scale understanding of the heterointerface between monolayer-TMDs and perovskite oxide and highlight the importance of spin-orbit-charge-lattice coupling on the intrinsic properties of atomic-layer heterostructures, which open up a way to manipulate the excitonic effects in monolayer TMDs via an interfacial system.

Direct Observation of Room-Temperature Stable Magnetism in LaAlO3/SrTiO3 Heterostructures.

Along with an unexpected conducting interface between nonmagnetic insulating perovskites LaAlO3 and SrTiO3 (LaAlO3/SrTiO3), striking interfacial magnetisms have been observed in LaAlO3/SrTiO3 heterostructures. Interestingly, the strength of the interfacial magnetic moment is found to be dependent on oxygen partial pressures during the growth process. This raises an important, fundamental question on the origin of these remarkable interfacial magnetic orderings. Here, we report a direct evidence of room-temperature stable magnetism in a LaAlO3/SrTiO3 heterostructure prepared at high oxygen partial pressure by using element-specific soft X-ray magnetic circular dichroism at both Ti L3,2 and O K edges. By combining X-ray absorption spectroscopy at both Ti L3,2 and O K edges and first-principles calculations, we qualitatively ascribe that this strong magnetic ordering with dominant interfacial Ti3+ character is due to the coexistence of LaAlO3 surface oxygen vacancies and interfacial (TiAl-AlTi) antisite defects. On the basis of this new understanding, we revisit the origin of the weak magnetism in LaAlO3/SrTiO3 heterostructures prepared at low oxygen partial pressures. Our calculations show that LaAlO3 surface oxygen vacancies are responsible for the weak magnetism at the interface. Our result provides direct evidence on the presence of room-temperature stable magnetism and a novel perspective to understand magnetic and electronic reconstructions at such strategic oxide interfaces.

The Mechanism of Electrolyte Gating on High-Tc Cuprates: The Role of Oxygen Migration and Electrostatics.

Electrolyte gating is widely used to induce large carrier density modulation on solid surfaces to explore various properties. Most of past works have attributed the charge modulation to electrostatic field effect. However, some recent reports have argued that the electrolyte gating effect in VO2, TiO2, and SrTiO3 originated from field-induced oxygen vacancy formation. This gives rise to a controversy about the gating mechanism, and it is therefore vital to reveal the relationship between the role of electrolyte gating and the intrinsic properties of materials. Here, we report entirely different mechanisms of electrolyte gating on two high-Tc cuprates, NdBa2Cu3O7-δ (NBCO) and Pr2-xCexCuO4 (PCCO), with different crystal structures. We show that field-induced oxygen vacancy formation in CuO chains of NBCO plays the dominant role, while it is mainly an electrostatic field effect in the case of PCCO. The possible reason is that NBCO has mobile oxygen in CuO chains, while PCCO does not. Our study helps clarify the controversy relating to the mechanism of electrolyte gating, leading to a better understanding of the role of oxygen electro migration which is very material specific.

Tunable and low-loss correlated plasmons in Mott-like insulating oxides.

Plasmonics has attracted tremendous interests for its ability to confine light into subwavelength dimensions, creating novel devices with unprecedented functionalities. New plasmonic materials are actively being searched, especially those with tunable plasmons and low loss in the visible-ultraviolet range. Such plasmons commonly occur in metals, but many metals have high plasmonic loss in the optical range, a main issue in current plasmonic research. Here, we discover an anomalous form of tunable correlated plasmons in a Mott-like insulating oxide from the Sr1-xNb1-yO3+δ family. These correlated plasmons have multiple plasmon frequencies and low loss in the visible-ultraviolet range. Supported by theoretical calculations, these plasmons arise from the nanometre-spaced confinement of extra oxygen planes that enhances the unscreened Coulomb interactions among charges. The correlated plasmons are tunable: they diminish as extra oxygen plane density or film thickness decreases. Our results open a path for plasmonics research in previously untapped insulating and strongly-correlated materials.

Electronic defect states at the LaAlO3/SrTiO3 heterointerface revealed by O K-edge X-ray absorption spectroscopy.

Interfaces of two dissimilar complex oxides exhibit exotic physical properties that are absent in their parent compounds. Of particular interest is insulating LaAlO3 films on an insulating SrTiO3 substrate, where transport measurements have shown a metal-insulator transition as a function of LaAlO3 thickness. Their origin has become the subject of intense research, yet a unifying consensus remains elusive. Here, we report evidence for the electronic reconstruction in both insulating and conducting LaAlO3/SrTiO3 heterointerfaces revealed by O K-edge X-ray absorption spectroscopy. For the insulating samples, the O K-edge XAS spectrum exhibits features characteristic of electronically active point defects identified as noninteger valence states of Ti. For conducting samples, a new shape-resonance at ∼540.5 eV, characteristic of molecular-like oxygen (empty O-2p band), is observed. This implies that the concentration of electronic defects has increased in proportion with LaAlO3 thickness. For larger defect concentrations, the electronic defect states are no longer localized at the Ti orbitals and exhibit pronounced O 2p-O 2p character. Our results demonstrate that, above a critical thickness, the delocalization of O 2p electronic states can be linked to the presence of oxygen vacancies and is responsible for the enhancement of conductivity at the oxide heterointerfaces.

Coexistence of Midgap Antiferromagnetic and Mott States in Undoped, Hole- and Electron-Doped Ambipolar Cuprates.

We report the first observation of the coexistence of a distinct midgap state and a Mott state in undoped and their evolution in electron and hole-doped ambipolar Y_{0.38}La_{0.62}(Ba_{0.82}La_{0.18})_{2}Cu_{3}O_{y} films using spectroscopic ellipsometry and x-ray absorption spectroscopies at the O K and Cu L_{3,2} edges. Supported by theoretical calculations, the midgap state is shown to originate from antiferromagnetic correlation. Surprisingly, while the magnetic state collapses and its correlation strength weakens with dopings, the Mott state in contrast moves toward a higher energy and its correlation strength increases. Our result provides important clues to the mechanism of electronic correlation strengths and superconductivity in cuprates.

Tuning the interface conductivity of LaAlO3/SrTiO3 using ion beams: implications for patterning.

Patterning of the two-dimensional electron gas formed at the interface of two band insulators such as LaAlO3/SrTiO3 is one of the key challenges in oxide electronics. The use of energetic ion beam exposure for engineering the interface conductivity has been investigated. We found that this method can be utilized to manipulate the conductivity at the LaAlO3/SrTiO3 interface by carrier localization, arising from the defects created by the ion beam exposure, eventually producing an insulating ground state. This process of ion-beam-induced defect creation results in structural changes in SrTiO3 as revealed by the appearance of first-order polar TO2 and TO4 vibrational modes which are associated with Ti-O bonds in the Raman spectra of the irradiated samples. Furthermore, significant observation drawn from the magnetotransport measurements is that the irradiated (unirradiated) samples showed a negative (positive) magnetoresistance along with simultaneous emergence of first-order (only second order) Raman modes. In spectroscopic ellipsometry measurements, the optical conductivity features of the irradiated interface are broadened because of the localization effects, along with a decrease of spectral weight from 4.2 to 5.4 eV. These experiments allow us to conclude that the interface ground state (metallic/insulating) at the LaAlO3/SrTiO3 can be controlled by tailoring the defect structure of the SrTiO3 with ion beam exposure. A resist-free, single-step direct patterning of a conducting LaAlO3/SrTiO3 interface has been demonstrated. Patterns with a spatial resolution of 5 µm have been fabricated using a stencil mask, while nanometer scale patterns may be possible with direct focused ion beam writing.