A combined SECM and electrochemical AFM approach to probe interfacial processes affecting molecular reactivity at redox flow battery electrodes

Watkins, Tylan S.; Sarbapalli, Dipobrato; Counihan, Michael J.; Danis, Andrew S.; Zhang, Jingjing; Zhang, Lu; Zavadil, Kevin R.; Rodríguez-López, Joaquín

doi:10.1039/d0ta00836b

A combined SECM and electrochemical AFM approach to probe interfacial processes affecting molecular reactivity at redox flow battery electrodes

Journal Article · Wed Mar 04 00:00:00 EST 2020 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d0ta00836b· OSTI ID:1639081

Watkins, Tylan S. ^[1]; ^[2]; Counihan, Michael J. ^[2]; Danis, Andrew S. ^[2]; ^[3]; ^[3]; ^[1]; ^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Univ. of Illinois at Urbana-Champaign, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Argonne National Lab. (ANL), Argonne, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Redox flow batteries are attractive technologies for grid energy storage since they use solutions of redox-active molecules that enable a superior scalability and the decoupling of power and energy density. However, the reaction mechanisms of the redox active components at RFB electrodes are complex, and there is currently a pressing need to understand how interfacial processes impact the kinetics and operational reversibility of RFB systems. Here, we developed a combined electrochemical imaging methodology rooted in scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM) for exploring the impact of electrode structure and conditioning on the electron transfer properties of model redox-active dialkoxybenzene derivatives, 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (C1) and 2,3-dimethyl-1,4-dialkoxybenzene (C7). Using AFM and secondary-ion mass spectrometry (SIMS), we observed the formation of interfacial films with distinct mechanical properties compared to those of cleaved graphitic surfaces, and exclusively during reduction of electrogenerated radical cations. These films had an impact on the median rate and distribution of the electron transfer rate constant at the basal plane of multilayer and single layer graphene electrodes, displaying kinetically-limited values that did not yield the activation expected per the Butler–Volmer model with a transfer coefficient ~0.5. These changes were dependent on redoxmer structure: furthermore, SECM showed strong attenuation of C7 kinetics by a surface layer on MLG and SLG, while C1 kinetics were only affected by SLG. SECM and AFM results together show that these limiting films operate exclusively on the basal plane of graphite, with the edge plane showing a relative insensitivity to cycling and operation potential. Ultimately, this integrated electrochemical imaging methodology creates new opportunities to understand the unique role of interfacial processes on the heterogeneous reactivity of redoxmers at electrodes for RFBs, with a future role in elucidating phenomena at high active concentrations and spatiotemporal variations in electrode dynamics.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; AC04-94AL85000; NA0003525

OSTI ID:: 1639081

Alternate ID(s):: OSTI ID: 1604244
OSTI ID: 1756172

Report Number(s):: SAND--2020-6648J; 687019

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 31 Vol. 8; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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