Doctoral Dissertations

Date of Award


Degree Type


Degree Name

Doctor of Philosophy


Mechanical Engineering

Major Professor

Doug Aaron

Committee Members

Doug Aaron, Kenneth Kihn, Seungha Shin, David Keffer


With the increased utilization of renewable energy sources, demand for long-duration energy storage systems has increased to moderate the intermittent power generation problem of these sources. Among the various energy storage technologies, those based on electrochemical conversion have received tremendous attention in recent decades. Organic redox flow batteries (ORFBs) are promising candidates for large-scale energy storage. The advantages of ORFBs are flexibility, wide voltage window, high energy density, and low cost. Although recent developments in ORFBs are promising, their future implementation requires further development, especially to understand their electrochemical performance and alleviate system inefficiencies. Most of ORFBs' performance loss comes from low power density caused by the low ionic conductivity of organic solvents and high kinetic loss due to sluggish reactions.

The first step to improve ORFBs' electrochemical performance is to quantitatively investigate the sources of voltage loss. Biphenyl (Bp)|sodium polysulfide (Na2Sx) is the system to be studied in this work since it is an emerging chemistry of organic batteries with encouraging potential. Various in-situ and ex-situ electrochemical diagnostic tools were used, such as polarization curves, electrochemical impedance spectroscopy, and cyclic voltammetry. These tools were combined with the following experimental setups: 3-electrode cell, symmetric cell, and a flow cell with an in-situ sodium/sodium ion reference electrode. The results from the experimental methods mentioned above showed that in Bp|Na2Sx ORFBs, Bp contributes more to the cell's voltage loss compared to Na2Sx. Deeper investigation for both Bp and Na2Sx followed, revealing kinetic overpotential as the dominant source of voltage loss. The methods demonstrated in this investigation are non-destructive and applicable to various electrochemical systems.

Next, graphene aerogel (GA) was used to synthesize a carbon electrode. The hydrothermal synthesis process was studied to control the electrode's physical and electrochemical properties. Results demonstrate that a GA-based carbon electrode can be synthesized with tunable microstructure, density, electrical conductivity, and catalytic activity. Directional freezing integrated with the hydrothermal synthesis process can be used to effectively tune pore size and directionality. Catalysts, such as copper nanoparticles, can be added to GA-based electrodes, aiding in reducing Na2Sx redox reaction kinetics.


This is the final submission of this dissertation. Please note that the abstract was revised.

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