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The characteristic metal–insulator phase transition (MIT) in vanadium dioxide results in nonlinear electrical transport behavior, allowing VO₂devices to imitate the complex functions of neurological behavior. Chemical doping is an established method for varying the properties of the MIT, and interstitial dopant boron has been shown to generate a unique dynamic relaxation effect in individual B‐VO₂particles. This paper describes the first demonstration of an electrically stimulated B‐VO₂proto‐device which manifests a time‐dependent critical transformation temperature and switching voltage derived from the coupling of dopant diffusion dynamics and the metal–insulator transition of VO₂. During quasi‐steady current‐driven transitions, the electrical responses of B‐VO₂proto‐devices show a step‐by‐step progression through the phase transformation, evidencing domain transformations within individual particles. The dynamic relaxation effect is shown to increase the critical switching voltage by up to 41% (ΔV_crit =0.13 V) and also to increase the resistivity of the M1 phase of B‐VO₂by 14%, imbuing a memristive response derived from intrinsic material properties. These observations demonstrate the dynamic relaxation effect in B‐VO₂proto‐devices whose electrical transport responses can be adjusted by electronic phase transitions triggered by temperature but also by time as a result of intrinsic dynamics of interstitial dopants.

 

The diffusion pathways of Li‐ions as they traverse cathode structures in the course of insertion reactions underpin many questions fundamental to the functionality of Li‐ion batteries. Much current knowledge derives from computational models or the imaging of lithiation behavior at larger length scales; however, it remains difficult to experimentally image Li‐ion diffusion at the atomistic level. Here, by using topochemical Li‐ion insertion and extraction to induce single‐crystal‐to‐single‐crystal transformations in a tunnel‐structured V₂O₅polymorph, coupled with operando powder X‐ray diffraction, we leverage single‐crystal X‐ray diffraction to identify the sequence of lattice interstitial sites preferred by Li‐ions to high depths of discharge, and use electron density maps to create a snapshot of ion diffusion in a metastable phase. Our methods enable the atomistic imaging of Li‐ions in this cathode material in kinetic states and provide an experimentally validated angstrom‐level 3D picture of atomic pathways thus far only conjectured through DFT calculations.

 

Despite their rapid emergence as the dominant paradigm for electrochemical energy storage, the full promise of lithium-ion batteries is yet to be fully realized, partly because of challenges in adequately resolving common degradation mechanisms. Positive electrodes of Li-ion batteries store ions in interstitial sites based on redox reactions throughout their interior volume. However, variations in the local concentration of inserted Li-ions and inhomogeneous intercalation-induced structural transformations beget substantial stress. Such stress can accumulate and ultimately engender substantial delamination and transgranular/intergranular fracture in typically brittle oxide materials upon continuous electrochemical cycling. This perspective highlights the coupling between electrochemistry, mechanics, and geometry spanning key electrochemical processes: surface reaction, solid-state diffusion, and phase nucleation/transformation in intercalating positive electrodes. In particular, we highlight recent findings on tunable material design parameters that can be used to modulate the kinetics and thermodynamics of intercalation phenomena, spanning the range from atomistic and crystallographic materials design principles (based on alloying, polymorphism, and pre-intercalation) to emergent mesoscale structuring of electrode architectures (through control of crystallite dimensions and geometry, curvature, and external strain). This framework enables intercalation chemistry design principles to be mapped to degradation phenomena based on consideration of mechanics coupling across decades of length scales. Scale-bridging characterization and modeling, along with materials design, holds promise for deciphering mechanistic understanding, modulating multiphysics couplings, and devising actionable strategies to substantially modify intercalation phase diagrams in a manner that unlocks greater useable capacity and enables alleviation of chemo-mechanical degradation mechanisms.