arXiv subjects

John Cattermull

Publications and source records attributed to John Cattermull.

3 recordsLinked to original sources

arXiv2026

Electrochemical and thermal control of continuous phase transitions in P2-NaxNi1/3Mn2/3O2

Sodium layered oxides often undergo phase transformations involving ordering or disordering of Na+ upon desodiation, i.e., when cycled as a battery electrode. Accurately characterizing these phases is crucial for understanding functional properties, such as chemical diffusivity. In this work, we reveal that Na+-vacancy (dis)ordering in a layered oxide is intrinsically coupled to symmetry-changing phase transformations of the host structure. We examine the low-symmetry orthorhombic unit cell of P2-NaxNi1/3Mn2/3O2 (NNM) using both neutron and X-ray diffraction. Specifically, special sodium stoichiometries (x = 2/3 and 1/2) exhibit concomitant Na+-vacancy ordering and an orthorhombic distortion from the parent hexagonal unit cell. We then demonstrate that electrochemical desodiation drives symmetry-changing transformations in NNM that are linked to Na+-vacancy (dis)ordering, with evidence of second-order behavior observed near x = 2/3. Variable-temperature synchrotron X-ray diffraction further clarifies the coupling between Na+-vacancy disordering and orthorhombic-to-hexagonal phase transitions in NNM. Surprisingly, the temperature-driven phase transitions at x = 2/3 and 1/2 differ in character, appearing second-order and first-order, respectively. Our analysis of the phase transitions in NNM has fundamental consequences for sodium chemical diffusivity in the vicinity of the ordered phases and leads to design principles for modifying phase transition behavior in the broader class of intercalation electrodes.

cond-mat.mtrl-sci↗

arXiv2024

Rules governing Jahn-Teller order in Prussian blue analogues

Jahn-Teller distortions of transition-metal coordination environments link orbital occupancies to structure. In the solid state, such distortions can be strongly correlated through the propagation of strain and/or through orbital interactions. Cooperative Jahn-Teller (CJT) order of this kind affects the electronic, magnetic, and structural properties of the materials in which it occurs. Conventionally studied in dense ceramics, CJT order also occurs in hybrid materials, albeit the underlying phenomenology is not well established. Here we use synchrotron powder X-ray diffraction measurements to identify the compositional factors governing cooperative Jahn-Teller order in a series of Prussian blue analogue (PBA) families. We develop a simple microscopic model based on the dual considerations of strain and crystal-field stabilisation that rationalises the stability, extent of CJT order, and crystallite strain measured experimentally. This model shows how PBA compositions might be tuned to control the emergence and nature of CJT effects, and predicts universal phase behaviour for JT-active PBAs more generally. Our results establish a microscopic framework for understanding and controlling CJT effects in PBAs, and reveal an interplay between compositional, structural, and orbital degrees of freedom closely analogous to that of the manganite perovskites.

cond-mat.mtrl-sci↗

arXiv2021

Structural complexity in Prussian blue analogues

We survey the most important kinds of structural complexity in Prussian blue analogues, their implications for materials function, and how they might be controlled through judicious choice of composition. We focus on six particular aspects: octahedral tilts, A-site `slides', Jahn--Teller distortions, A-site species and occupancy, hexacyanometallate vacancies, and framework hydration. The promising K-ion cathode material K$_x$Mn[Fe(CN)$_6$]$_y$ serves as a recurrent example that illustrates many of these different types of complexity. Our article concludes with a discussion of how the interplay of various distortion mechanisms might be exploited to optimise the performance of this and other related systems, so as to aid in the design of next-generation PBA materials.

cond-mat.mtrl-sci↗