Elucidating the Nuanced Effects of Thermal Pretreatment on Carbon Paper Electrodes for Vanadium Redox Flow Batteries.

Sluggish vanadium reaction rates on the porous carbon electrodes typically used in redox flow batteries have prompted research into pretreatment strategies, most notably thermal oxidation, to improve performance. While effective, these approaches have nuanced and complex effects on electrode characteristics hampering the development of explicit structure-function relations that enable quantitative correlation between specific properties and overall electrochemical performance. Here, we seek to resolve these relationships through rigorous analysis of thermally pretreated SGL 29AA carbon paper electrodes using a suite of electrochemical, microscopic, and spectroscopic techniques and culminating in full cell testing. We systematically vary pretreatment temperature, from 400 to 500 °C, while holding pretreatment time constant at 30 h, and evaluate changes in the physical, chemical, and electrochemical properties of the electrodes. We find that several different parameters contribute to observed performance, including hydrophilicity, microstructure, electrochemical surface area, and surface chemistry, and it is important to note that not all of these properties improve with increasing pretreatment temperature. Consequently, while the best overall performance is achieved with a 475 °C pretreatment, this enhancement is achieved from a balance, rather than a maximization, of critical properties. A deeper understanding of the role each property plays in battery performance is the first step toward developing targeted pretreatment strategies that may enable transformative performance improvements.

Molecular Simulations of Hydrogen Bond Cluster Size and Reorientation Dynamics in Liquid and Glassy Azole Systems.

We simulated the dynamics of azole groups (pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, and tetrazole) as neat liquids and tethered via linkers to aliphatic backbones to determine how tethering and varying functional groups affect hydrogen bond networks and reorientation dynamics, both factors which are thought to influence proton conduction. We used the DL_Poly_2 molecular dynamics code with the GAFF force field to simulate tethered systems over the temperature range 200-900 K and the corresponding neat liquids under liquid state temperatures at standard pressure. We computed hydrogen bond cluster sizes; orientational order parameters; orientational correlation functions associated with functional groups, linkers, and backbones; time scales; and activation energies associated with orientational randomization. All tethered systems exhibit a liquid to glassy-solid transition upon cooling from 600 to 500 K, as evidenced by orientational order parameters and correlation functions. Tethering the azoles was generally found to produce hydrogen bond cluster sizes similar to those in untethered liquids and hydrogen bond lifetimes longer than those in liquids. The simulated rates of functional group reorientation decreased dramatically upon tethering. The activation energies associated with orientational randomization agree well with NMR data for tethered imidazole systems at lower temperatures and for tethered 1,2,3-triazole systems at both low- and high-temperature ranges. Overall, our simulations corroborate the notion that tethering functional groups dramatically slows the process of reorientation. We found a linear correlation between gas-phase hydrogen bond energies and tethered functional group reorientation barriers for all azoles except for imidazole, which acts as an outlier because of both atomic charges and molecular structure.

Reactive Liftoff of Crystalline Cellulose Particles.

The condition of heat transfer to lignocellulosic biomass particles during thermal processing at high temperature (>400 °C) dramatically alters the yield and quality of renewable energy and fuels. In this work, crystalline cellulose particles were discovered to lift off heated surfaces by high speed photography similar to the Leidenfrost effect in hot, volatile liquids. Order of magnitude variation in heat transfer rates and cellulose particle lifetimes was observed as intermediate liquid cellulose droplets transitioned from low temperature wetting (500-600 °C) to fully de-wetted, skittering droplets on polished surfaces (>700 °C). Introduction of macroporosity to the heated surface was shown to completely inhibit the cellulose Leidenfrost effect, providing a tunable design parameter to control particle heat transfer rates in industrial biomass reactors.