Decoupling Proton and Cation Contributions to Capacitive Charge Storage in Birnessite in Aqueous Electrolytes

Saeed, Saeed; Fortunato, Jenelle; Ganeshan, Karthik; van Duin, Adri C. T.; Augustyn, Veronica

doi:10.1002/celc.202100992

Decoupling Proton and Cation Contributions to Capacitive Charge Storage in Birnessite in Aqueous Electrolytes

Journal Article · Wed Nov 24 00:00:00 EST 2021 · ChemElectroChem

DOI:https://doi.org/10.1002/celc.202100992· OSTI ID:1832655

Saeed, Saeed ^[1]; Fortunato, Jenelle ^[1]; Ganeshan, Karthik ^[2]; van Duin, Adri C. T. ^[2]; ^[1]

Dept. of Materials Science &, Engineering North Carolina State University Raleigh NC 27695 USA
Department of Mechanical Engineering Pennsylvania State University University Park PA 16803 USA

Abstract

Nanostructured birnessite is of interest as an electrode material for aqueous high power electrochemical energy storage as well as desalination devices. In neutral pH aqueous electrolytes, birnessite exhibits a capacitive response attributed to the adsorption of cations and protons at the outer surface and within the hydrated interlayer. Here, we utilize the understanding of proton‐coupled electron transfer (PCET) in buffered electrolytes to decouple the role of protons and cations in the capacitive charge storage mechanism of birnessite at neutral pH. We find that without buffer, birnessite exhibits primarily potential‐independent (capacitive) behavior with excellent cycling stability. Upon the addition of buffer, the capacity initially increases and the cyclic voltammograms become more potential‐dependent, features attributed to the presence of PCET with the birnessite. However, long‐term cycling in the buffered electrolyte leads to significant capacity fade and dissolution, which is corroborated through ex situ characterization. ReaxFF atomistic scale simulations support the observations that proton adsorption leads to birnessite degradation and that capacitive charge storage in birnessite is primarily attributed to cation adsorption at the outer surface and within the interlayer.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1832655

Journal Information:: ChemElectroChem, Journal Name: ChemElectroChem Journal Issue: 22 Vol. 8; ISSN 2196-0216

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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