Effects of interlayer confinement and hydration on capacitive charge storage in birnessite

Boyd, Shelby; Ganeshan, Karthik; Tsai, Wan-Yu; Wu, Tao; Saeed, Saeed; Jiang, De-en; Balke, Nina; van Duin, Adri T.; Augustyn, Veronica

doi:10.1038/s41563-021-01066-4

Effects of interlayer confinement and hydration on capacitive charge storage in birnessite

Journal Article · Mon Aug 02 00:00:00 EDT 2021 · Nature Materials

DOI:https://doi.org/10.1038/s41563-021-01066-4· OSTI ID:1813235

^[1]; ^[2]; ^[3]; Wu, Tao ^[4]; ^[1]; ^[4]; ^[3]; ^[3]; ^[1]

North Carolina State Univ., Raleigh, NC (United States)
Pennsylvania State Univ., University Park, PA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)

Nanostructured birnessite exhibits high specific capacitance and nearly ideal capacitive behaviour in aqueous electrolytes, rendering it an important electrode material for low-cost, high-power energy storage devices. The mechanism of electrochemical capacitance in birnessite has been described as both Faradaic (involving redox) and non-Faradaic (involving only electrostatic interactions). To clarify the capacitive mechanism, we characterized birnessite’s response to applied potential using ex situ X-ray diffraction, electrochemical quartz crystal microbalance, in situ Raman spectroscopy and operando atomic force microscope dilatometry to provide a holistic understanding of its structural, gravimetric and mechanical responses. These observations are supported by atomic-scale simulations using density functional theory for the cation-intercalated structure of birnessite, ReaxFF reactive force field-based molecular dynamics and ReaxFF-based grand canonical Monte Carlo simulations on the dynamics at the birnessite–water–electrolyte interface. We show that capacitive charge storage in birnessite is governed by interlayer cation intercalation. We conclude that the intercalation appears capacitive due to the presence of nanoconfined interlayer structural water, which mediates the interaction between the intercalated cation and the birnessite host and leads to minimal structural changes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1813235

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: NA Vol. NA; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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