Structural and ion‐ordering phase transitions limit the viability of sodium‐ion intercalation materials in grid scale battery storage by reducing their lifetime. However, the combination of phenomena in nanoparticulate electrodes creates complex behavior that is difficult to investigate, especially on the single‐nanoparticle scale under operating conditions. In this work, operando single‐particle X‐ray diffraction (oSP‐XRD) is used to observe single‐particle rotation, interlayer spacing, and layer misorientation in a functional sodium‐ion battery. oSP‐XRD is applied to Na2/3[Ni1/3Mn2/3]O2, an archetypal P2‐type sodium‐ion‐positive electrode material with the notorious P2‐O2 phase transition induced by sodium (de)intercalation. It is found that during sodium extraction, the misorientation of crystalline layers inside individual particles increases before the layers suddenly align just prior to the P2‐O2 transition. The increase in the long‐range order coincides with an additional voltage plateau signifying a phase transition prior to the P2‐O2 transition. To explain the layer alignment, a model for the phase evolution is proposed that includes a transition from localized to correlated Jahn–Teller distortions. The model is anticipated to guide further characterization and engineering of sodium‐ion intercalation materials with P2‐O2 type transitions. oSP‐XRD, therefore, opens a powerful avenue for revealing complex phase behavior in heterogeneous nanoparticulate systems.
The emergence of ferromagnetism in materials where the bulk phase does not show any magnetic order demonstrates that atomically precise films can stabilize distinct ground states and expands the phase space for the discovery of materials. Here, the emergence of long-range magnetic order is reported in ultrathin (111) LaNiO3(LNO) films, where bulk LNO is paramagnetic, and the origins of this phase are explained. Transport and structural studies of LNO(111) films indicate that NiO6octahedral distortions stabilize a magnetic insulating phase at the film/substrate interface and result in a thickness-dependent metal–insulator transition at
- NSF-PAR ID:
- 10227677
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- npj Quantum Materials
- Volume:
- 6
- Issue:
- 1
- ISSN:
- 2397-4648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
The temperature-dependent layer-resolved structure of 3 to 44 unit cell thick SrRuO 3 (SRO) films grown on Nb-doped SrTiO 3 substrates is investigated using a combination of high-resolution synchrotron x-ray diffraction and high-resolution electron microscopy to understand the role that structural distortions play in suppressing ferromagnetism in ultra-thin SRO films. The oxygen octahedral tilts and rotations and Sr displacements characteristic of the bulk orthorhombic phase are found to be strongly dependent on temperature, the film thickness, and the distance away from the film–substrate interface. For thicknesses, t, above the critical thickness for ferromagnetism ( t > 3 uc), the orthorhombic distortions decrease with increasing temperature above T C . Below T C , the structure of the films remains constant due to the magneto-structural coupling observed in bulk SRO. The orthorhombic distortions are found to be suppressed in the 2–3 interfacial layers due to structural coupling with the SrTiO 3 substrate and correlate with the critical thickness for ferromagnetism in uncapped SRO films.more » « less
-
more » « less
Abstract The manipulation of charge and lattice degrees of freedom in atomically precise, low‐dimensional ferroelectric superlattices can lead to exotic polar structures, such as a vortex state. The role of interfaces in the evolution of the vortex state in these superlattices (and the associated electrostatic and elastic boundary conditions they produce) has remained unclear. Here, the toroidal state, arranged in arrays of alternating clockwise/counterclockwise polar vortices, in a confined SrTiO3/PbTiO3/SrTiO3trilayer is investigated. By utilizing a combination of transmission electron microscopy, synchrotron‐based X‐ray diffraction, and phase‐field modeling, the phase transition as a function of layer thickness (number of unit cells) demonstrates how the vortex state emerges from the ferroelectric state by varying the thickness of the confined PbTiO3layer. Intriguingly, the vortex state arises at head‐to‐head domain boundaries in ferroelectric
a 1/a 2twin structures. In turn, by varying the total number of PbTiO3layers (moving from trilayer to superlattices), it is possible to manipulate the long‐range interactions among multiple confined PbTiO3layers to stabilize the vortex state. This work provides a new understanding of how the different energies work together to produce this exciting new state of matter and can contribute to the design of novel states and potential memory applications. -
more » « less
Abstract Understanding interfacial reactions that occur between the active layer and charge‐transport layers can extend the stability of perovskite solar cells. In this study, the exposure of methylammonium lead iodide (CH3NH3PbI3) thin films prepared on poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)‐coated glass to 70% relative humidity (R.H.) leads to a perovskite crystal structure change from tetragonal to cubic within 2 days. Interface‐sensitive photoluminescence measurements indicate that the structural change originates at the PEDOT:PSS/perovskite interface. During exposure to 30% R.H., the same structural change occurs over a much longer time scale (>200 days), and a reflection consistent with the presence of (CH3)2NH2PbI3is detected to coexist with the cubic phase by X‐ray diffraction pattern. The authors propose that chemical interactions at the PEDOT:PSS/perovskite interface, facilitated by humidity, promote the formation of dimethylammonium, (CH3)2NH2+. The partial A‐site substitution of CH3NH3+for (CH3)2NH2+to produce a cubic (CH3NH3)1−
x [(CH3)2NH2]x PbI3phase explains the structural change from tetragonal to cubic during short‐term humidity exposure. When (CH3)2NH2+content exceeds its solubility limit in the perovskite during longer humidity exposures, a (CH3)2NH2+‐rich, hexagonal phase of (CH3NH3)1−x [(CH3)2NH2]x PbI3emerges. These interfacial interactions may have consequences for device stability and performance beyond CH3NH3PbI3model systems and merit close attention from the perovskite research community. -
more » « less
Abstract The reactivity of water with Li‐rich layered Li2RuO3and partial exchange of Li2O with H2O within the structure is studied under aqueous (electro)chemical conditions. Upon slow delithiation in water over long time periods, micron‐sized Li2RuO3particles structurally transform from an O3 structure to an O1 structure with a corresponding loss of 1.25 Li ions per formula unit. The O1 stacking of the honeycomb Ru layers is imaged using high‐resolution high‐angle annular dark‐field scanning transmission electron microscopy, and the resulting structure is solved by X‐ray powder diffraction and electron diffraction. In situ X‐ray absorption spectroscopy suggests that reversible oxidation/reduction of bulk Ru sites is realized on potential cycling between 0.4 and 1.25 VRHEin basic solutions. In addition to surface redox pseudocapacitance, the partially delithiated phase of Li2RuO3shows high capacity, which can be attributed to bulk Ru redox in the structure. This work demonstrates that the interaction of aqueous electrolytes with Li‐rich layered oxides can result in the formation of new phases with (electro)chemical properties that are distinct from the parent material. This understanding is important for the design of aqueous batteries, electrochemical capacitors, and chemically stable cathode materials for Li‐ion batteries.
