The electrical impedance of carbon xerogel hierarchical electrodes

Desolvation; Donnan model; Electrical double layer; Electrical impedance; Hierarchical materials; Porous electrodes; Warburg impedance; Carbon xerogels; Electrical double layers; Hierarchical structures; Micropores; Chemical Engineering (all); Electrochemistry; General Chemical Engineering

Abstract :

[en] Many electrodes used in energy storage devices are produced by grinding a micro- and meso- or macro-porous material into a powder and depositing it on a flat substrate, which leads to a hierarchical structure. At the largest scale the structure is that of a flat layer; the intermediate structure is that of porous grains; the smallest scale is that of the microporous skeleton that makes up the grains. The paper uses electrical impedance spectroscopy to investigate both experimentally and through mathematical modelling how electric charges are stored and transported in such structure. The paper focuses on electrodes produced with a variety of carbon xerogels soaked with KCl solutions. Nonane adsorption is used during the electrode preparation to selectively block the micropores, and discriminate their contribution from that of larger pores. The impedance data are analysed with a mathematical model built on the Poisson–Boltzmann equation for charge storage and on the Nernst–Planck equation for ion transport, which accounts for the hierarchical structure of the electrodes. The equilibrium charge storage in large pores is found to be quantitatively described by the classical electric double layer. In micropores, however, non-ideality of the electrolyte has to be invoked to account for the measured capacitance, hinting at ion desolvation. As for the charge transport, each structural level is found to have a characteristic frequency, above which the storage of electric charges is transport-limited at the considered scale. The hierarchical structure of the electrode is responsible for salient characteristics of the impedance. In particular the Warburg regime, with impedance proportional to (iω)−1/2, is observed when transport is rate-limiting at one scale only. In hierarchical electrodes, an additional regime is observed with impedance proportional to (iω)−1/4 when transport limitations are present at two scales simultaneously.

Disciplines :

Physics
Materials science & engineering

Author, co-author :

Gommes, Cédric ; Université de Liège - ULiège > Department of Chemical Engineering

Chaltin, François ; Université de Liège - ULiège > Chemical engineering

Language :

English

Title :

The electrical impedance of carbon xerogel hierarchical electrodes

Publication date :

20 November 2022

Journal title :

Electrochimica Acta

ISSN :

0013-4686

Publisher :

Elsevier Ltd

Volume :

433

Pages :

141203

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://api.elsevier.com/content/article/PII:S0013468622013603?httpAccept=text/xml

Funders :

ULiège - Université de Liège [BE]
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]

Funding text :

CJG is grateful to the Funds for Scientific Research (F.R.S.-FNRS, Belgium) for a Research Associate position, and for supporting this work through grant J.0075.19-CDR . The authors are grateful to Nathalie Job and Alexandre Léonard (University of Liège) for helpful and stimulating discussions.CJG is grateful to the Funds for Scientific Research (F.R.S.-FNRS, Belgium) for a Research Associate position, and for supporting this work through grant J.0075.19-CDR. The authors are grateful to Nathalie Job and Alexandre Léonard (University of Liège) for helpful and stimulating discussions.

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since 18 January 2023

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