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Faster Intercalation Pseudocapacitance Enabled by Adjustable Amorphous Titania where Tunable Isomorphic Architectures Reveal Accelerated Lithium Diffusivity

van den Bergh, Wessel; Larison, Taylor; Jara Fornerod, Maximiliano Jesus; Guldin, Stefan; Stefik, Morgan; (2022) Faster Intercalation Pseudocapacitance Enabled by Adjustable Amorphous Titania where Tunable Isomorphic Architectures Reveal Accelerated Lithium Diffusivity. Batteries & Supercaps , 5 (7) , Article e202200122. 10.1002/batt.202200122. Green open access

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Abstract

Intercalation pseudocapacitance is a faradaic electrochemical phenomenon with high power and energy densities, combining the attractive features of capacitors and batteries, respectively. Intercalation pseudocapacitive responses exhibit surface-limited kinetics by definition, without restriction from the collective of diffusion-based processes. The surface-limited threshold (SLT) corresponds to the maximum voltage sweep rate (vSLT) exhibiting a predominantly surface-limited current response prior to the onset of diffusion-limitations. Prior studies showed increased lithium diffusivity for amorphous titania compared to anatase. Going beyond prior binary comparisons, here a continuum of amorphous titania configurations were prepared using a series of calcination temperatures to tailor both amorphous character and content. The corresponding amorphous-phase vSLT increased monotonically by 317 % with lowered calcination temperatures. Subsequent isomorphic comparisons varying a single transport parameter at a time identified solid-state lithium diffusion as the dominant diffusive constraint. Thus, performance improvements were linked to increasing the lithium diffusivity of the amorphous phase with decreased calcination temperature. This remarkably enabled 95 % capacity retention (483±17 C/g) with 30 s of delithiation (120 C equivalent). These results highlight how isomorphic sample series can reveal previously unidentified trends by reducing ambiguity and reiterate the potential of amorphization to realize increased performance in known materials.

Type: Article
Title: Faster Intercalation Pseudocapacitance Enabled by Adjustable Amorphous Titania where Tunable Isomorphic Architectures Reveal Accelerated Lithium Diffusivity
Open access status: An open access version is available from UCL Discovery
DOI: 10.1002/batt.202200122
Publisher version: https://doi.org/10.1002/batt.202200122
Language: English
Additional information: Copyright © 2022 The Authors. This is an open access article under the terms of the Creative Commons Attribution-Non Commercial License (http://creativecommons.org/licenses/by-nc/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
Keywords: amorphization, lithium-ion, nanomaterials, pseudocapacitance, titania
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL
URI: https://discovery.ucl.ac.uk/id/eprint/10147081
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