Electrode Materials for Enhancing the Performance and Cycling Stability of Zinc Iodide Flow Batteries at High Current Densities.

Aqueous redox flow battery systems that use a zinc negative electrode have a relatively high energy density. However, high current densities can lead to zinc dendrite growth and electrode polarization, which limit the battery's high power density and cyclability. In this study, a perforated copper foil with a high electrical conductivity was used on the negative side, combined with an electrocatalyst on the positive electrode in a zinc iodide flow battery. A significant improvement in the energy efficiency (ca. 10% vs using graphite felt on both sides) and cycling stability at a high current density of 40 mA cm-2 was observed. A long cycling stability with a high areal capacity of 222 mA h cm-2 is obtained in this study, which is the highest reported areal capacity for zinc-iodide aqueous flow batteries operating at high current density, in comparison to previous studies. Additionally, the use of a perforated copper foil anode in combination with a novel flow mode was discovered to achieve consistent cycling at exceedingly high current densities of >100 mA cm-2. In situ and ex situ characterization techniques, including in situ atomic force microscopy coupled with in situ optical microscopy and X-ray diffraction, are applied to clarify the relationship between zinc deposition morphology on the perforated copper foil and battery performance in two different flow field conditions. With a portion of the flow going through the perforations, a significantly more uniform and compact zinc deposition was observed compared to the case where all of the flow passed over the surface of the electrode. Results from modeling and simulation support the conclusion that the flow of a fraction of electrolyte through the electrode enhances mass transport, enabling a more compact deposit.

Bitumen and asphaltene derived nanoporous carbon and nickel oxide/carbon composites for supercapacitor electrodes.

Asphaltenes from bitumen are abundant resource to be transformed into carbon as promising supercapacitor electrodes, while there is a lack of understanding the impact from different fractions of bitumen and asphaltenes, as well as the presence of transition metals. Here, nanoporous carbon was synthesized from bitumen, hexane-insoluble asphaltenes and N,N-dimethylformamide (DMF)-fractionated asphaltenes by using Mg(OH)2 nanoplates as the template with in-situ KOH activation, and used as an supercapacitor electrode material. All of the carbon exhibited large surface area (1500-2200 m2 g-1) with a distribution of micro and mesopores except for that derived from the DMF-soluble asphaltenes. The pyrolysis of asphaltenes resulted in the formation of nickel oxide/carbon composite (NiO/C), which demonstrated high capacitance of 380 F g-1 at 1 A g-1 discharge current resulting from the pseudocapacitance of NiO and the electrochemical double layer capacitance of the carbon. The NiO/C composite obtained from the DMF-insoluble portion had low NiO content which led to lower capacitance. Meanwhile, the specific capacitance of NiO/C composite from the DMF-soluble part was lower than the unfractionated asphaltene due to the higher NiO content resulting in lower conductivity. Therefore asphaltenes derived from nickel-rich crude bitumen is suitable for the synthesis of nanoporous NiO/C composite material with high capacitance.

Effects of support and oxygen vacancies on the energetics of NiO reduction with H2 for the chemical looping combustion (CLC) reaction; a DFT study.

Chemical looping combustion (CLC) technology is an innovative energy conversion technology that employs oxygen carriers (OC), typically metal oxides, to burn fossil fuels with a minimal carbon footprint. The performance of OCs can be enhanced by the support on which they are deposited through two mechanisms acting at different scales, viz., microstructural and synergetic effects. In this work, the synergetic effect of NiO supported on TiO2 in reaction with hydrogen as a fuel is studied using density functional theory (DFT). Changes in the energetics of the NiO-hydrogen reaction are explained as a consequence of the interaction between the TiO2 support and NiO. The results indicate that the electronic interaction of the TiO2 support with NiO lowers the energy of intermediate states and the energy of the reaction. The effect of TiO2 increases with the creation of more O vacancies as the reaction proceeded. This enhanced reactivity of the NiO-hydrogen reaction is attributed to both an electronic effect of TiO2 and a geometric effect due to O vacancy creation. The synergetic effect of the support on the OC reactions at the atomic level reported here can pave the path to differentiate the electronic and geometric effects and establish the knowledge for the rational design of OC and support systems.

X-ray diffraction and TGA kinetic analyses for chemical looping combustion applications.

Synthesis and characterization of supported metal-based oxygen carriers were carried out to provide information related to the use of oxygen carriers for chemical looping combustion processes. The Cu, Co, Fe, Ni metals supported with Al2O3, CeO2, TiO2, ZrO2 were prepared using the wetness impregnation technique. Then, the X-ray Diffraction (XRD) characterization of oxidized and reduced samples was obtained and presented. The kinetic analysis using Thermogravimetric analyzer (TGA) of the synthesized samples was conducted. The kinetics of reduction reaction of all samples were estimated and explained.

Development of oil-spill sorbent from straw biomass waste: Experiments and modeling studies.

The recovery of oil spilled on land or water has become an important issue due to environmental regulations. Canadian biomasses as fibrous materials are naturally renewable and have the potential to absorb oil-spills at different ranges. In this work, four Canadian biomasses were examined in order to evaluate their oil affinities and study parameters that could affect oil affinity when used as sorbent, such as average particle size, surface coating and reusability. Moreover, one oil sorption model was adopted and coupled with another developed model to approximate and verify the experimental findings of the oil sorbent biomasses. At an average particle size of 150-1000 µm, results showed that barley straw biomass had the highest absorbency value at 6.07 g/g, while flax straw had the lowest value at 3.69 g/g. Wheat and oat straws had oil absorbency values of 5.49 and 5.00 g/g, respectively. An average particle size of 425-600 µm indicated better absorbency values for oat and wheat straws. Furthermore, the thermal stability study revealed major weight recovery for two flame retardant coatings at hemicellulose and lignocellulose degradation temperature ranges. It was also found that oat straw biomass could be regenerated and used for many sorption/desorption cycles, as the reusability experiment showed only a 18.45% reduction in the oil absorbency value after six consecutive cycles. The developed penetration absorbency (PA) model showed oat straw adsorbed oil at the inter-particle level; and, the results of the sorption capacity model coupled with the PA model excellently predicted the oil sorption of raw and coated oat straws.

Characterization, thermochemical conversion studies, and heating value modeling of municipal solid waste.

A study was carried out to examine the characteristics of municipal solid waste (MSW) from the City of Red Deer, Alberta, Canada. Experiments were performed for determining the moisture content, proximate and ultimate compositions, heating value of fourteen wastes in different categories. Their thermal weight loss behaviors under pyrolysis/torrefaction conditions were also investigated in a thermogravimetric analyzer (TGA). An empirical model was developed for the high heating value (HHV) estimation of MSW. A total of 193 experimental data were collected from this study and those in the literature, of which 161 data were used for model derivation; and, 32 additional data were used for model validation. The model was developed using multiple regression analysis and a stepwise regression method: HHV (MJ/kg)=0.350C+1.01H-0.0826O, which is expressed in terms of weight percentages on a dry basis of carbon (C), hydrogen (H) and oxygen (O). The validation results suggest that this model was effective in producing accurate outputs that were close to the experimental values. In addition, it had the lowest error level in comparison with seven other models from the literature.

Nutrient media optimization for simultaneous enhancement of the laccase and peroxidases production by coculture of Dichomitus squalens and Ceriporiopsis subvermispora.

Coculturing of two white-rot fungi, Dichomitus squalens and Ceriporiopsis subvermispora, was explored for the optimization of cultivation media for simultaneous augmentation of laccase and peroxidase activities by response surface methodology (RSM). Nutrient parameters chosen from our previous studies with the monocultures of D. squalens and C. subvermispora were used to design the experiments for the cocultivation study. Glucose, arabinose, sodium nitrate, casein, copper sulfate (CuSO4 ), and manganese sulfate (MnSO4 ) were combined according to central composite design and used as the incubation medium for the cocultivation. The interaction of glucose and sodium nitrate resulted in laccase and peroxidase activities of approximately 800 U/g protein. The addition of either glucose or sodium nitrate to the medium also modifies the impact of other nutrients on the ligninolytic activity. Both enzyme activities were cross-regulated by arabinose, casein, CuSO4 , and MnSO4 as a function of concentrations. Based on RSM, the optimum nutrient levels are 1% glucose, 0.1% arabinose, 20 mM sodium nitrate, 0.27% casein, 0.31 mM CuSO4 , and 0.07 mM MnSO4 . Cocultivation resulted in the production of laccase of 1,378 U/g protein and peroxidase of 1,372 U/g protein. Lignin (16.9%) in wheat straw was degraded by the optimized enzyme mixture.

Experimental study on local mass transfer in a simplified bifurcation model: potential role in atherosclerosis.

Local mass transfer coefficients and flow patterns were examined in an idealized human aortic bifurcation model. The objectives of this study are to gain further insights on the convective mass transfer process and its possible role in the localization of atherosclerotic lesions. The laser photochromic tracer method provided velocity and wall shear stress estimates in the plane of symmetry of a UV-transparent Plexiglas bifurcation model. Steady flow data were acquired at Reynolds numbers of 500, 600, and 750. A novel copper electrodeposition technique was used to obtain time-averaged convective local mass transfer coefficients in a model identical to that used in the flow experiments. The laminar flow mass transfer data for the trunk of the bifurcation are in good agreement with the analytical Levesque solution. At the bifurcation, higher mass transfer coefficients along the inner wall and lower ones along the outer wall were observed. Further, mass transfer and wall shear stress follow similar patterns both on the inner and outer walls in that StSc 2/3 and C(f)/2 demonstrate analogous behavior. Lower transfer rates of momentum and mass occurred along the outer wall of the branches where lesions tend to develop.