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Lithium metal as an anode has been widely accepted due to its higher negative electrochemical potential and theoretical capacity. Nevertheless, the existing safety and cyclability issues limit lithium metal anodes from practical use in high-energy density batteries. Repeated Li deposition and dissolution processes upon cycling lead to the formation of dendrites at the interface which results in reduced Li availability for electrochemical reactions, disruption in Li transport through the interface and increased safety concerns due to short circuiting. Here, we demonstrate a novel strategy using Ionic Liquid Crystals (ILCs) as the electrolyte cum pseudo-separator to suppress dendrite growth with their anisotropic properties controlling Li-ion mass transport. A thermotropic ILC with two-dimensional Li-ion conducting pathways was synthesized and characterized. Microscopic and spectroscopic analyses elucidate that the ILC formed with a smectic A phase, which can be utilized for wide temperature window operation. The results of electrochemical studies corroborate the efficacy of ILC electrolytes in mitigating dendrite formation even after 850 hours and it is further substantiated by numerical simulation and the mechanism involved in dendritic suppression was deduced.

Biobased fuels resulting from the pyrolysis of lignocellulosic materials suffer from several key issues. Only a portion of the biomass feedstock is converted to pyrolysis oil, and only a portion of compounds in that oil represent desired end products. Bio-oil contains myriad oxygenated and aromatic compounds, many of which form tars and impart high acidity, viscosity, and instability. This necessitates substantial upgrading to generate a stable, valuable product. The inclusion of in situ catalysts during pyrolysis can improve the pyrolysis oil by promoting the cracking of tarry compounds and formation of smaller furans and phenols. This study examines the impact of in situ transition metal catalysts on cellulose pyrolysis, quantifying changes in bio-oil composition and non-condensable gas generation. Cellulose was wet impregnated with six different metal acetates at a concentration of 0.05 M and pyrolyzed at 600 °C, and some samples additionally pyrolyzed at 350 °C. The metals enhanced devolatilization, increasing hydrogen gas production at high and low temperatures and improved bio-oil yields while decreasing the average molecular weight of the oil compounds. Nickel proved to be the most effective at generating hydrogen gas and producing a wider array of light-weight bio-oil compounds. Copper aided dehydrogenation at lower temperatures and began the initial stages of primary pyrolysis by generating levoglucosenone and glucopyranose. These findings shed light on metal-biomass interactions and contribute to the growing body of knowledge of in situ bio-oil upgrading. By understanding how catalysts improve bio-oils we can generate high-density and cleaner-burning liquid fuels to displace the use of fossil fuels.

Dendrite formation on the anode surface of a battery is closely related to the safety and capacity of high energy density batteries, thus suppressing dendrite growth will significantly improve the performance of batteries. Many experimental reports reveal that convection near the dendrite nucleation site can change the local mass transport, and ultimately affect dendrite growth. Investigation of the convection effect in batteries will guide the development of strategies to suppress dendrite growth in a convective electrolyte. Most of the existing electro-convection computational models for dendrite growth studies are based on Eulerian frameworks. These methods have difficulty modeling the moving boundaries associated with dendrite growth and are less computationally efficient in simulating convective fluid motion. In this paper we adopt a mesh-free particle based Lagrangian method to address the challenges of previous grid based Eulerian electro-convection models. The developed model is verified by comparison to analytical solutions, including verification of ion migration and the electric potential. Simulation results show that the predicted dendrite growth and electro-convective flow patterns compare well with experimental results during early dendrite growth stages. Parametric studies reveal that low viscosity electrolytes suppress the dendrite growth by increasing the mass transport of ions near the anode/electrolyte interface.

Studies have shown that the lifetime and performance of lithium batteries are greatly influenced by the charge/discharge cycles of the battery. The number of cycles over which a battery operates depends on the rate and depth of charge/discharge. Degradation in battery performance over multiple cycles is directly related to dendrite growth at the electrode-electrolyte interface in the battery. Understanding how cycling effects dendrite growth rates and morphology requires resolution of the chemical-physical processes at the electrode-electrolyte interface. In this study, a numerical model of dendrite growth at this electrode-electrolyte interface over multiple charge/discharge cycles is presented. In this work, dendrite growth over multiple charge/discharge cycles is simulated at the interfacial level where the effects on dendrite growth rate and morphology can be resolved. The simulations are able to predict qualitative dendrite morphologies presented in experimental studies, and the effects of fast charging scenarios on dendrite growth rate and morphology are discussed.

Over their designed lifetime, high-temperature electrochemical devices, such as solid oxide fuel cells (SOFCs), can experience degradation in their electrochemical performance due to environmental conditions, operating conditions, contaminants, and other factors. Understanding the different degradation mechanisms in SOFCs and other electrochemical devices is essential to reducing performance degradation and increasing the lifetimes of these devices. In this paper, SOFC degradation mechanisms are evaluated, and a damage model is presented that describes performance degradation in SOFCs due to damage or degradation in the SOFC electrodes. A degradation classification scheme is presented, dividing the various SOFC electrode degradation mechanisms into categories based on their physical effects on the SOFC. The damage model and classification method are applied both to sulfur poisoning and antimony poisoning, which occur in the SOFC anode. For sulfur poisoning, the model can calculate degradation in SOFC performance based on the operating temperature of the fuel cell and the concentration of gaseous sulfur species in the anode. For antimony poisoning, the effects of nickel consumption from the anode matrix are investigated.

We present a pore-scale model of a solid oxide fuel cell (SOFC) cathode. Volatile chromium species are known to migrate from the current collector of the SOFC into the cathode where over time they decrease the voltage output of the fuel cell. A pore-scale model is used to investigate the reactive transport of chromium species in the cathode and to study the driving forces of chromium poisoning. A multi-scale modeling approach is proposed which uses a cell level model of the cathode, air channel and current collector to determine the boundary conditions for a pore-scale model of a section of the cathode. The pore-scale model uses a discrete representation of the cathode to explicitly model the surface reactions of oxygen and chromium with the cathode material. The pore-scale model is used to study the reaction mechanisms of chromium by considering the effects of reaction rates, diffusion coefficients, chromium vaporization, and oxygen consumption on chromium's deposition in the cathode. The study shows that chromium poisoning is most significantly affected by the chromium reaction rates in the cathode and that the reaction rates are a function of the local current density in the cathode.

The volatility of crude oil prices incentivizes the use of domestic alternative fossil fuel sources such as oil shale. For ex situ oil shale retorting to be economically and environmentally viable, we must convert the copious amounts of semi-coke waste to an environmentally benign, useable by-product. Using acid and acid + base treatments, we increased the surface area of the semi-coke samples from 15 m2/g (pyrolyzed semi-coke) to upwards of 150 m2/g for hydrochloric acid washed semi-coke. This enhancement in porosity and surface area is accomplished without high temperature treatment, which lowers the overall energy required for such a conversion. XRD analysis confirms that chemical treatments removed the majority of dolomite while retaining other carbonate minerals and maintaining carbon contents of approximately 10%, which is greater than many fly ashes that are commonly used as sorbent materials. SO2 gas adsorption isotherm analysis determined that a double HCl treatment of semi-coke produces sorbents for flue gas treatment with higher SO2 capacities than commonly used fly ash adsorbents. Computational fluid dynamics modeling indicates that the sorbent material could be used in a fixed bed reactor to efficiently remove SO2 from the gas stream.

This paper examines the electrochemical and direct internal steam–methane reforming performance of the solid oxide fuel cell when subjected to pressurization. Pressurized operation boosts the Nernst potential and decreases the activation polarization, both of which serve to increase cell voltage and power while lowering the heat load and operating temperature. A model considering the activation polarization in both the fuel and the air electrodes was adopted to address this effect on the electrochemical performance. The pressurized methane conversion kinetics and the increase in equilibrium methane concentration are considered in a new rate expression. The models were then applied in simulations to predict how the distributions of direct internal reforming rate, temperature, and current density are effected within stacks operating at elevated pressure. A generic 10 cm counter-flow stack model was created and used for the simulations of pressurized operation. The predictions showed improved thermal and electrical performance with increased operating pressure. The average and maximum cell temperatures decreased by 3% (20 °C) while the cell voltage increased by 9% as the operating pressure was increased from 1 to 10 atm.