Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu; Wang, Hsiu-Wen; Mamontov, Eugene; Heller, William T.; Zhang, Pengfei; Rother, Gernot; Cummings, Peter T.; Wesolowski, David J.; Gogotsi, Yury

doi:10.1016/j.carbon.2017.12.001

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

Journal Article · Tue Dec 05 00:00:00 EST 2017 · Carbon

DOI:https://doi.org/10.1016/j.carbon.2017.12.001· OSTI ID:1432166

^[1]; Osti, Naresh C. ^[2]; Zhang, Yu ^[3]; Wang, Hsiu-Wen ^[4]; Mamontov, Eugene ^[2]; Heller, William T. ^[2]; Zhang, Pengfei ^[4]; Rother, Gernot ^[4]; Cummings, Peter T. ^[3]; Wesolowski, David J. ^[4]; ^[1]

Drexel Univ., Philadelphia, PA (United States). A.J. Drexel Nanomaterials Inst. Dept. of Materials Science and Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Vanderbilt Univ., Nashville, TN (United States). Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysis shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.

View Accepted Manuscript (DOE)

Research Organization:: Drexel Univ., Philadelphia, PA (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1432166

Alternate ID(s):: OSTI ID: 1576053

Journal Information:: Carbon, Journal Name: Carbon Vol. 129; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbide-derived carbon
energy storage
interface
ionic liquid
molecular dynamics
neutron scattering
pair distribution function
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supercapacitor
surface chemistry

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

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