Browsing by Subject "Electrochemical performance"

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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.
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    Studies of Rechargeable Lithium-Sulfur Batteries
    (2016-05) Cui, Yi; Fu, Yongzhu; Xie, Jian; Zhu, Likun; Anwar, Sohel
    The studies of rechargeable lithium-sulfur (Li-S) batteries are included in this thesis. In the first part of this thesis, a linear sweep voltammetry method to study polysulfide transport through separators is presented. Shuttle of polysulfide from the sulfur cathode to lithium metal anode in rechargeable Li-S batteries is a critical issue hindering cycling efficiency and life. Several approaches have been developed to minimize it including polysulfide-blocking separators; there is a need for measuring polysulfide transport through separators. We have developed a linear sweep voltammetry method to measure the anodic (oxidization) current of polysulfides crossed separators, which can be used as a quantitative measurement of the polysulfide transport through separators. The electrochemical oxidation of polysulfide is diffusion-controlled. The electrical charge in Coulombs produced by the oxidation of polysulfide is linearly related to the concentration of polysulfide within a certain range (≤ 0.5 M). Separators with a high porosity (large pore size) show high anodic currents, resulting in fast capacity degradation and low Coulombic efficiencies in Li-S cells. These results demonstrate this method can be used to correlate the polysulfide transport through separators with the separator structure and battery performance, therefore provide guidance for developing new separators for Li-S batteries. The second part includes a study on improving cycling performance of Li/polysulfide batteries by applying a functional polymer on carbon current collector. Significant capacity decay over cycling in Li-S batteries is a major impediment for their practical applications. Polysulfides Li2Sx (3 < x ≤ 8) formed in the cycling are soluble in liquid electrolyte, which is the main reason for capacity loss and cycling instability. Functional polymers can tune the structure and property of sulfur electrodes, hold polysulfides, and improve cycle life. We have examined a polyvinylpyrrolidone-modified carbon paper (CP-PVP) current collector in Li/polysulfide cells. PVP is soluble in the electrolyte solvent, but shows strong affinity with lithium polysulfides. The retention of polysulfides in the CP-PVP current collector is improved by ~50%, which is measured by a linear sweep voltammetry method. Without LiNO3 additive in the electrolyte, the CP-PVP current collector with 50 ug of PVP can significantly improve cycling stability with a capacity retention of > 90% over 50 cycles at C/10 rate. With LiNO3 additive in the electrolyte, the cell shows a reversible capacity of > 1000 mAh g ⁻¹ and a capacity retention of > 80% over 100 cycles at C/5 rate. The third part of this thesis is about a study on a binder-free sulfur/carbon composite electrode prepared by a sulfur sublimation method for Li-S batteries. Sulfur nanoparticles fill large pores in a carbon paper substrate and primarily has a monoclinic crystal structure. The composite electrode shows a long cycle life of over 200 cycles with a good rate performance in Li-S batteries.