Susan Odom - Department of Chemistry

Study small heteroaromatic and aromatic molecules for use as redox shuttles in lithium ion batteries

In our research group, we study small heteroaromatic and aromatic molecules for use as redox shuttles in lithium ion batteries. In addition to testing potential redox shuttles via battery cycling, we are interested in synthesizing new compounds to propose as redox shuttle candidates. Since synthesis is costly and time-consuming, we use computational techniques to predict a compound’s redox properties, geometry and electron densities in the frontier orbitals. We are also interested in radical cations (oxidized state). Redox shuttles are compounds that can be reversibly oxidized in battery electrolyte. Thus the more stable the radical cation of the redox shuttle, the more overcharge protection can be performed.
Density Functional Theory (DFT) is used in order to perform calculation with Gaussian. Molecular geometries are optimized first by the semi-empirical quantum chemical method PM3. Then DFT is used for further optimization of geometry using Becke’s three parameter exchange functional (B3) in combination with Lee, Yang, and Parr’s (LYP) correlation functions on the basis set of 6-31G with polarization and or diffusion functions. Calculations are performed in the gas phase for neutrals (B3LYP) and for radical cations (UB3LYP) where unrestricted formalism is applied. Using computational output, we compute the energies, ionization potentials and electron densities in neutral and charged states. Even though the calculations are performed in the gas phase, we are also interested in including the solvents’ effects to our study since properties of the compounds can vary considerably between gas phase and solution. Gaussian software is capable of modeling systems in solution but its computational cost might increase.

Currently, we are writing a paper to demonstrate the correlation between experimental and computational results for new redox shuttle candidates.

Research Personell:

Edward Loya, Grad
Stephen Jeffrey Chapman, UGrad

Removed from Odom Research Group
Matthew D Casselman (postdoc)
Selin Ergun (postdoc)
Subrahmanyam Modekrutti

Presently Selin Ergun (postdoc) is registered and is performing calculations in DLX cluster. However, Corrine F. Elliott (undergraduate) will also start to perform calculations in server.

Software:

Gaussian is available on HPC server, but it should be noted that the software CD is rarely available. This CD is required in order to generate the input files for submitting calculations and to generate checkpoint files, which allow us to visualize geometry of the optimized molecules and frontier orbitals in Windows.

Funding:

We received funding for a National Science Foundation grant titled “Understanding the Stability and Reactivity of Radical Cations for Improved Overcharge Performance in Lithium-Ion Batteries.” http://www.nsf.gov/awardsearch/showAward?AWD_ID=1300653

Publications

2019 - 2016

1. “A Stable Two-Electron-Donating Phenothiazine for Application in Nonaqueous Redox Flow Batteries.” Kowalski, J.A.; Casselman, M.D.; Kaur, A.P.; Milshtein, J.D.; Elliott, C.F.; Modekrutti, S.; Attanayake, N.H.; Zhang, N.; Parkin, S.R.; Risko, C.; Brushett, F.R.;* Odom, S.A.* Journal of Materials Chemistry A, 2017, 5, 24371-24379. DOI 10.1039/C7TA05883G
2. “Beyond the Hammett Effect: Using Strain to Alter the Landscape of Electrochemical Potentials.” Casselman, M.D.; Elliott, C.F.; Modekrutti, S.; Zhang, P.; Parkin, S.R.; Risko, C.;* Odom, S.A.* ChemPhysChem, 2017, 18, 2142–2146. DOI: 10.1002/cphc.201700607
3. “High-Current-Density, Long-Duration Cycling of Soluble Organic Active Species for Non-Aqueous Redox Flow Batteries.” Milshtein, J.D.; Kaur, A.P.; Casselman, M.D.; Kowalski, J.A.; Modekrutti, S.; Zhang, P.; Attanayake, N.H.; Elliott, C.F.; Parkin, S.R.; Risko, C.; Brushett, F.R.;* Odom, S.A.* Energy and Environmental Science, 2016, 9, 3531–3543. DOI: 10.1039/C6EE02027E

2014

“Zn-Sn Electrochemical Cells with Molten Salt Eutectic Electrolytes and Their Potential for Energy Storage Applications.” Holubowitch, N.; Manek, S.; Landon, J.; Lippert, C.; Odom, S.A.; Liu, K.* ECS Transactions, 2014, 64, 439–452.
“Improving Carbon Capture from Power Plant Emissions with Zinc- and Cobalt-based Catalysts.” Lippert, C.A.; Liu, K.; Sharma, M.; Parkin, S.R.; Remias, J.E.; Brandewie, C. M.; Odom, S.A.;* Liu, K.* Catalysis Science & Technology, 2014, 4, 3620–3625. DOI: 10.1039/C4CY00766B
“Controlling Oxidation Potentials in Redox Shuttle Candidates for Lithium-Ion Batteries.” Ergun, S.; Elliott, C.F.; Kaur, A.P.; Parkin, S.R.; Odom, S.A.* Journal of Physical Chemistry C, 2014, 118, 14824–14832. DOI: 10.1021/jp503767h
“Overcharge Performance of 3,7-Disubstituted N-Ethylphenothiazine Derivatives in Lithium-Ion Batteries.” Ergun, S.; Elliott, C.F.; Kaur, A.P.; Parkin, S.R.; Odom, S.A.* Chemical Communications, 2014, 50, 5339–5341. (invited for 2014 Emerging Investigators Issue) DOI: 10.1039/C3CC47503D
“A Fast, Inexpensive Method for Predicting Overcharge Performance in Lithium-Ion Batteries,” Odom, S.A.;* Ergun, S.; Poudel, P.P.; Parkin, S.R. Energy and Environmental Sciences, 2014, 7, 760–767. DOI: 10.1039/C3EE42305K

Presentations

2014

Presentations:

“On the Stability, Reactivity, and Performance of Electrolyte Additives for Overcharge Protection in Lithium-Ion Batteries.” Oak Ridge National Laboratory, July 7, 2014.
“Electrolyte Additives for Overcharge Protection in Lithium-Ion Batteries.” Kentucky Organic Electronic Materials Symposium, Lexington, KY, June 22, 2014.
“Stability and Reactivity of Aromatic Electrolyte Additives for Lithium-Ion Batteries.” George Washington University, Department of Chemistry, April 25, 2014.
“The Relationship of Radical Cation Stability and Overcharge Protection in Redox Shuttles for Lithium-Ion Batteries.” Odom, S.A.; Kaur, A.P.; Ergun, S.E.; Elliott, C.F., International Battery Association 2014 Meeting, Brisbane, Australia, March 3, 2014.

Grants

Odom, Susan PRF51860-DNI10 Robust Redox Shuttles for Overcharge Protection of Lithium Ion Batteries $100,000 American Chemical Society 1/1/2012 8/31/2015
Odom, Susan CHE-1300653 Understanding the Stability and Reactivity of Radical Cations for Improved Overcharge Protection in Lithium-Ion Batteries $413,000 National Science Foundation 7/1/2013 - 6/30/2016