Title: Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential

Abstract

Transport of electrolytes in nanoporous carbon-based electrodes largely defines the function and performance of energy storage devices. Here, using molecular dynamics simulation and quasielastic neutron scattering, we investigate the microscopic dynamics of a prototypical ionic liquid electrolyte, [emim][Tf₂N], under applied electric potential in carbon materials with 6.7 nm and 1.5 nm pores. The simulations demonstrate the formation of dense layers of counter-ions near the charged surfaces, which is reversible when the polarity is reversed. In the experiment, the ions immobilized near the surface manifest themselves in the elastic scattering signal. The experimentally observed ion immobilization near the wall is fully reversible as a function of the applied electric potential in the 6.7 nm, but not in the 1.5 nm nanopores. In the latter case, remarkably, the first application of the electric potential leads to apparently irreversible immobilization of cations or anions, depending on the polarity, near the carbon pore walls. This unexpectedly demonstrates that in carbon electrode materials with the small pores, which are optimal for energy storage applications, the polarity of the electrical potential applied for the first time after the introduction of an ionic liquid electrolyte may define the decoration of the small pore walls with ions formore » prolonged periods of time and possibly for the lifetime of the electrode.« less

Authors:

Mahurin, Shannon M. ^[1]; Mamontov, Eugene ^[2]; Thompson, Matthew W. ^[3]; Zhang, Pengfei ^[1]; Turner, C. Heath ^[4]; Cummings, Peter T. ^[3]; Dai, Sheng ^[5]

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+ Show Author Affiliations

1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
3. Vanderbilt Univ., Nashville, TN (United States). Dept. of Chemical and Biomolecular Engineering
4. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemical and Biological Engineering
5. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA; Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, USA

Publication Date:

Tue Oct 04 00:00:00 EDT 2016

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)

Sponsoring Org.:

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

OSTI Identifier:

1328320

Alternate Identifier(s):

OSTI ID: 1420531

Grant/Contract Number:  

AC05-00OR22725

Resource Type:

Accepted Manuscript

Journal Name:

Applied Physics Letters

Additional Journal Information:

Journal Volume: 109; Journal Issue: 14; Journal ID: ISSN 0003-6951

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 25 ENERGY STORAGE; carbon; electrolytes; molecular dynamic