Defining Diffusion Pathways in Intercalation Cathode Materials: Some Lessons from V₂O₅ on Directing Cation Traffic

The invention of rechargeable batteries has dramatically changed our landscapes and lives, underpinning the explosive worldwide growth of consumer electronics, ushering in an unprecedented era of electric vehicles, and potentially paving the way for a much greener energy future. Unfortunately, current battery technologies suffer from a number of challenges, e.g., capacity loss and failure upon prolonged cycling, limited ion diffusion kinetics, and a rather sparse palette of high-performing electrode materials. Here, we discuss the origins of diffusion limitations in oxide materials using V₂O₅ as a model system. In particular, we discuss constrictions in ionic conduction pathways, narrow energy dispersion of conduction band states, and the stabilization and self-trapping of polarons as local phenomena that have substantial implications for introducing multiscale compositional and phase heterogeneities. Strategies for mitigating such limitations are discussed such as reducing diffusion path lengths and the design of metastable frameworks yielding frustrated coordination and decreased barriers for migration of polarons

Topochemically De-Intercalated Phases of V₂O₅ as Cathode Materials for Multivalent Intercalation Batteries: A First-Principles Evaluation

The scarce inventory of compounds that allow for diffusion of multivalent cations at reasonable rates poses a major impediment to the development of multivalent intercalation batteries. Here, we contrast the thermodynamics and kinetics of the insertion of Li, Na, Mg, and Al ions in two synthetically accessible metastable phases of V₂O₅, ζ- and ε-V₂O₅, with the relevant parameters for the thermodynamically stable α-phase of V₂O₅ using density functional theory calculations. The metastability of the frameworks results in a higher open circuit voltage for multivalent ions, exceeding 3 V for Mg-ion intercalation. Multivalent ions inserted within these structures encounter suboptimal coordination environments and expanded transition states, which facilitate easier ion diffusion. Specifically, a nudged elastic band examination of ion diffusion pathways suggests that migration barriers are substantially diminished for Na- and Mg-ion diffusion in the metastable polymorphs: the predicted migration barriers for Mg ions in ζ-V₂O₅ and ε-V₂O₅ are 0.62–0.86 and 0.21–0.24 eV, respectively. More generally, the results indicate that topochemically derived metastable polymorphs represent an interesting class of compounds for realizing multivalent cation diffusion because many such compounds place cations in “frustrated” coordination environments that are known to be useful for realizing low diffusion barriers

Inside and Outside: X‑ray Absorption Spectroscopy Mapping of Chemical Domains in Graphene Oxide

The oxidative chemistry of graphite has been investigated for over 150 years and has attracted renewed interest given the importance of exfoliated graphene oxide as a precursor to chemically derived graphene. However, the bond connectivities, steric orientations, and spatial distribution of functional groups remain to be unequivocally determined for this highly inhomogeneous nonstoichiometric material. Here, we demonstrate the application of principal component analysis to scanning transmission X-ray microscopy data for the construction of detailed real space chemical maps of graphene oxide. These chemical maps indicate very distinct functionalization motifs at the edges and interiors and, in conjunction with angle-resolved near-edge X-ray absorption fine structure spectroscopy, enable determination of the spatial location and orientations of functional groups. Chemical imaging of graphene oxide provides experimental validation of the modified Lerf–Klinowski structural model. Specifically, we note increased contributions from carboxylic acid moieties at edge sites with epoxide and hydroxyl species dominant within the interior domains

Intercalation-Induced Exfoliation and Thickness-Modulated Electronic Structure of a Layered Ternary Vanadium Oxide

Solid-state compounds wherein electrons cannot be described as noninteracting particles and instead show strongly correlated behavior are of interest both as systems manifesting novel quantum chemical phenomena as well as for electronic device applications. In the absence of predictive theoretical descriptors, modulation of the properties of these compounds tends to be challenging, and generalizable strategies for modulating closely coupled lattice, orbital, and spin degrees of freedom are exceedingly sparse. Here, it is shown that exfoliation mediated by cation intercalation can serve as a powerful means of modulating the electronic structure of layered correlated materials. Using a strongly correlated and charge-ordered layered compound, δ-Sr_0.50V₂O₅, as a model system, it is shown that the band gap can be drastically altered from ca. 1.07 to 2.32 eV and the electron correlation strength can be greatly modified by intercalation-driven exfoliation to 2D nanosheets upon elimination of structural coherence along one dimension. These findings suggest that intercalation chemistry and solution-phase exfoliation provide a versatile strategy for modulating the electronic structure of quantum materials with potential for realizing Mott and neuromorphic circuitry

Vanadium K‑Edge X‑ray Absorption Spectroscopy as a Probe of the Heterogeneous Lithiation of V₂O₅: First-Principles Modeling and Principal Component Analysis

Understanding the diffusion mechanisms of Li ions through host materials and the resulting phase evolution of intercalated phases is of paramount importance for designing electrode materials of rechargeable batteries. The formation of lithiation gradients and discrete domains during intercalation leads to the development of strain within the host material and is responsible for the observed capacities of most cathode materials being well below theoretically predicted values. Such mesoscale heterogeneity has also been implicated in the loss of capacity upon cycling. Due to their inherent complexity, the analysis of such heterogeneity is rather complex and precise understanding of the evolution of metal sites remains underexplored. In this work, we use phase-pure, single-crystalline V₂O₅ nanowires with dimensions of 183 ± 50 nm and lengths spanning tens of microns as a model cathode material and demonstrate that V K-edge X-ray absorption near-edge structure can be used as an effective probe of the local valence and geometry of vanadium sites upon lithiation. We demonstrate that a highly lithiated phase is nucleated and grows at the expense of a homogeneous low-lithium-content α-phase without mediation of a solid-solution with intermediate lithium content. Density functional theory calculations allow for assignment of the pre-edge feature to dipolar transitions that are particularly sensitive to the V 3d–O 2p hybridization of the vanadyl bond and the local geometry of the distorted [VO₅] square pyramid. The quantitative analysis of multiple vanadium sites and their evolution as a function of Li-ion content provides insight into the mechanism of phase evolution and the nature of lithiation gradients. The phase coexistence and segregation is further observed in scanning transmission X-ray microscopy images of individual lithiated V₂O₅ nanowires. The mechanisms and the dynamics of nucleation and growth unraveled here are of great importance for the design and discovery of Li-ion cathode materials

Mapping Catalytically Relevant Edge Electronic States of MoS₂

Molybdenum disulfide (MoS₂) is a semiconducting transition metal dichalcogenide that is known to be a catalyst for both the hydrogen evolution reaction (HER) as well as for hydro-desulfurization (HDS) of sulfur-rich hydrocarbon fuels. Specifically, the edges of MoS₂ nanostructures are known to be far more catalytically active as compared to unmodified basal planes. However, in the absence of the precise details of the geometric and electronic structure of the active catalytic sites, a rational means of modulating edge reactivity remain to be developed. Here we demonstrate using first-principles calculations, X-ray absorption spectroscopy, as well as scanning transmission X-ray microscopy (STXM) imaging that edge corrugations yield distinctive spectroscopic signatures corresponding to increased localization of hybrid Mo 4d states. Independent spectroscopic signatures of such edge states are identified at both the S L_2,3 and S K-edges with distinctive spatial localization of such states observed in S L_2,3-edge STXM imaging. The presence of such low-energy hybrid states at the edge of the conduction band is seen to correlate with substantially enhanced electrocatalytic activity in terms of a lower Tafel slope and higher exchange current density. These results elucidate the nature of the edge electronic structure and provide a clear framework for its rational manipulation to enhance catalytic activity

Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V₂O₅

The design of cathodes for intercalation batteries requires consideration of both atomistic and electronic structure to facilitate redox at specific transition metal sites along with the concomitant diffusion of cations and electrons. Cation intercalation often brings about energy dissipative phase transformations that give rise to substantial intercalation gradients as well as multiscale phase and strain inhomogeneities. The layered α-V₂O₅ phase is considered to be a classical intercalation host but is plagued by sluggish diffusion kinetics and a series of intercalation-induced phase transitions that require considerable lattice distortion. Here, we demonstrate that a 1D tunnel-structured ζ-phase polymorph of V₂O₅ provides a stark study in contrast and can reversibly accommodate Li-ions without a large distortion of the structural framework and with substantial mitigation of polaronic confinement. Entirely homogeneous lithiation is evidenced across multiple cathode particles (in contrast to α-V₂O₅ particles wherein lithiation-induced phase transformations induce phase segregation). Barriers to Li-ion as well as polaron diffusion are substantially diminished for metastable ζ-V₂O₅ in comparison to the thermodynamically stable α-V₂O₅ phase. The rigid tunnel framework, relatively small changes in coordination environment of intercalated Li-ions across the diffusion pathways defined by the 1D tunnels, and degeneracy of V 3d states at the bottom of the conduction band reduce electron localization that is a major impediment to charge transport in α-V₂O₅. The 1D ζ-phase thus facilitates a continuous lithiation pathway that is markedly different from the successive intercalation-induced phase transitions observed in α-V₂O₅. The results here illustrate the importance of electronic structure in mediating charge transport in oxide cathode materials and demonstrates that a metastable polymorph with higher energy bonding motifs that define frustrated coordination environments can serve as an attractive intercalation host

Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V₂O₅

The design of cathodes for intercalation batteries requires consideration of both atomistic and electronic structure to facilitate redox at specific transition metal sites along with the concomitant diffusion of cations and electrons. Cation intercalation often brings about energy dissipative phase transformations that give rise to substantial intercalation gradients as well as multiscale phase and strain inhomogeneities. The layered α-V₂O₅ phase is considered to be a classical intercalation host but is plagued by sluggish diffusion kinetics and a series of intercalation-induced phase transitions that require considerable lattice distortion. Here, we demonstrate that a 1D tunnel-structured ζ-phase polymorph of V₂O₅ provides a stark study in contrast and can reversibly accommodate Li-ions without a large distortion of the structural framework and with substantial mitigation of polaronic confinement. Entirely homogeneous lithiation is evidenced across multiple cathode particles (in contrast to α-V₂O₅ particles wherein lithiation-induced phase transformations induce phase segregation). Barriers to Li-ion as well as polaron diffusion are substantially diminished for metastable ζ-V₂O₅ in comparison to the thermodynamically stable α-V₂O₅ phase. The rigid tunnel framework, relatively small changes in coordination environment of intercalated Li-ions across the diffusion pathways defined by the 1D tunnels, and degeneracy of V 3d states at the bottom of the conduction band reduce electron localization that is a major impediment to charge transport in α-V₂O₅. The 1D ζ-phase thus facilitates a continuous lithiation pathway that is markedly different from the successive intercalation-induced phase transitions observed in α-V₂O₅. The results here illustrate the importance of electronic structure in mediating charge transport in oxide cathode materials and demonstrates that a metastable polymorph with higher energy bonding motifs that define frustrated coordination environments can serve as an attractive intercalation host