Browsing by Author "Robertson, Lily A."

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    A cooperative degradation pathway for organic phenoxazine catholytes in aqueous redox flow batteries
    (Elsevier, 2023-03) Fang, Xiaoting; Zeng, Lifan; Li, Zhiguang; Robertson, Lily A.; Shkrob, Ilya A.; Zhang , Lu; Wei, Xioaliang; Mechanical Engineering, School of Engineering and Technology
    Redox-active organic molecules that store positive charge in aqueous redox flow cells (catholyte redoxmers) frequently exhibit poor chemical stability for reasons that are not entirely understood. While for some catholyte molecules, deprotonation in their charged state is resposible for shortening the lifetime, for well designed molecules that avoid this common fate, it is seldom known what causes their eventual decomposition as it appears to be energetically prohibitive. Here, a highly soluble (1.6 M) phenoxazine molecule with a redox potential of 0.48 V vs. Ag/AgCl has been examined in flow cells. While this molecule has highly reversible redox chemistry, during cycling the capacity fades in a matter of hours. Our analyses suggest a cooperative decomposition pathway involving disproportionation of two charged molecules followed by anion substitution and deprotonation. This example suggests that cooperative reactions can be responsible for unexpectedly low chemical instability in the catholyte redoxmers and that researchers need to be keenly aware of such reactions and methods for their mitigation.
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    Fluorination Enables Simultaneous Improvements of a Dialkoxybenzene-Based Redoxmer for Nonaqueous Redox Flow Batteries
    (American Chemical Society, 2022) Bheemireddy, Sambasiva R.; Li, Zhiguang; Zhang, Jingjing; Agarwal, Garvit; Robertson, Lily A.; Shkrob, Ilya A.; Assary, Rajeev S.; Zhang, Zhengcheng; Wei, Xiaoliang; Cheng, Lei; Zhang, Lu; Mechanical and Energy Engineering, Purdue School of Engineering and Technology
    Redoxmers or redox-active organic materials, are one critical component for nonaqueous redox flow batteries (RFBs), which hold high promise in enabling the time domain of the grid. While tuning redox potentials of redoxmers is a very effective way to enhance energy densities of NRFBs, those improvements often accompany accelerated kinetics of the charged species, undermining stability and cycling performance. Herein, a strategy for designing redoxmers with simultaneous improvements in redox potential and stability is proposed. Specifically, the redoxmer 1,4-di-tert-butyl-2,5-bis(2,2,2-trifluoroethoxy)benzene (ANL-C46) is developed by incorporating fluorinated substitutions into the dialkoxybenzene-based platform. Compared to the non-fluorinated analogue, ANL-C46 demonstrates not only an increased (∼0.41 V) redox potential but also much enhanced stability (1.6 times) and cyclability (4 times) evidenced by electron paramagnetic resonance kinetic study, H-cell and flow cell cycling. In fact, the cycling performance of ANL-C46 is among the best of high potential (>1.0 V vs Ag/Ag+) redoxmers ever reported. Density functional theory calculations suggest that while the introduced fluorine substitutions elevate the redox potentials, they also help to depress the decomposition reactions of the charged redoxmers, affording excellent stability. The findings represent an interesting strategy for simultaneously improving energy density and stability, which could further prompt the development of high-performance redoxmers.