Calcium-Ion Batteries: Identifying Ideal Electrolytes for Next-Generation Energy Storage Using Computational Analysis

Calcium ion batteries show promise as a high-density, next generation replacement for current lithium ion batteries. The precise chemical structure of the carbonate electrolyte solvent has a large impact on calcium battery efficacy. In this computational study, we have investigated the solvation behavior of calcium tetrafluoroborate in both neat carbonates and carbonate mixtures using combined molecular dynamics simulations and quantum mechanical calculations. Our results indicate that both neat ethyl methyl carbonate and a mixture of ethylene carbonate and diethyl carbonate show the highest free-energy of solvation for the Ca2+ ion, making them likely candidates for further focus. The cation’s interaction with the carbonyls of the coordinating solvents, rather than those with the tetrafluoroborate counterions, play the primary role in delocalizing the charge on Ca2+. Detailed calculations indicate that the HOMO-LUMO energy gap (Eg), electronic chemical potential (μ) and chemical hardness (η) of the calcium-carbonate complexes are directly proportional to the free energy of solvation of the complex. Comparison of these observed trends with our previous results from Li+, Na+ and Mg2+ ions show that this correlation is also observed in solvated magnesium ions, but not in lithium or sodium salts. This observation should assist in the rational design of next generation battery materials in the rational selection of additives, counterions, or electrolyte solvent

The effect of ionic liquid adsorption on the electronic and optical properties of fluorographene nanosheets

In the present study, we investigate the adsorption characteristics of six different ionic liquids (ILs) on a fully-fluorinated graphene (fluorographene, FG) surface using electronic structure studies and associated analysis methods. A systematic comparison of differences in IL binding energies (ΔEb) with fluorographene, graphene and hexagonal boron nitride surfaces indicates that fluorination strongly decreases the binding energy compared to the other two surfaces, hence resulting in the binding energetics: ΔEb (Graphene…IL) \u3e ΔEb (Hexagonal boron-nitride…IL) \u3e ΔEb (Fluorographene…IL). To probe the reasons for this difference, quantum theory of atoms in molecules (QTAIM) analysis and non-covalent interactions (NCI) analyses were carried out. Results indicate that the stability of complexes of FG surface with ILs (FG…IL) arises only due to the presence of the expected weak non-covalent intermolecular interactions. The calculation of charge transfers by employing the ChelpG method shows that the interaction of ILs with FG surface generally induces a negative charge on the FG surface. Furthermore, these interactions lead to a decrease of the HOMO-LUMO energy gap (Eg) of the FG surface, enhancing its electrical conductivity. In addition, a detailed analysis of the global molecular descriptors including the Fermi energy level (EFL), work function (WF), electronic chemical potential (μ), chemical hardness (η), global softness (S) and electrophilicity index (ω) was carried out for both the FG surface alone and the adsorbed complexes showing that there are small, but meaningful, differences in the reactivity of the surface depending on the nature of the IL. Finally, time-dependent DFT (TD-DFT) calculations of the optical properties of FG surface and FG…IL complexes reveal that the absorption spectrum of the FG surface undergoes a red shift following IL adsorption. This study demonstrates that FG provides a useful complementary tool to graphene and boron nitride materials, allowing for the fine-tuning of the optoelectronic properties of these monolayer materials. These results will assist in the development of these types of ILs for applications in optoelectronics

A DFT study of the adsorption of deep eutectic solvents onto graphene and defective graphene nanoflakes

The interaction of four deep choline chloride-derived eutectic solvents (DESs) with both graphene nanoflakes (GNF) and its defective double-vacancy and Stone–Wales forms (DV-GNF and SW-GNF), was evaluated using density functional theory (DFT). The presence of defects increases the adsorption energy of DESs, following the order DES∩DV-GNF \u3e DES∩SW-GNF \u3e DES∩GNF. Non-covalent interaction and energy decomposition analyses show that the interactions are noncovalent and dominated by dispersive forces. Furthermore, we find that the presence of aromatic moieties in the DESs increases the van der Waals interactions with the surfaces. These interactions decrease the HOMO-LUMO (Eg) energy gap of the surfaces and thus increase reactivity. Reactivity parameter calculations indicate that the chemical potential (μ) and chemical hardness (η) of the complexes follow the order DES∩GNF \u3e DES∩SW-GNF \u3e DES∩DV-GNF. This order is reversed for the global softness (S) and electrophilicity index (ω). Time-dependent DFT (TD-DFT) calculations predict that the adsorption of DESs onto DV-GNF and SW-GNF should red shift absorption, while the absorption spectrum of GNF surface remains unchanged upon DES adsorption. The biggest changes in the absorption spectra are observed upon adsorption of DESs on the DV-GNF surface due to the stronger affinity of the DESs for this surface

Adsorption of choline benzoate ionic liquid on graphene, silicene, germanene and boron-nitride nanosheets: a DFT perspective

The adsorption of choline benzoate ([CH][BE]) ionic liquid (IL) on the surface of different hexagonal nanosheets has been studied using Density Functional Theory (DFT) methods. For this, the interaction mechanism, binding energies and electronic structure of [CH][BE] ionic liquid on four types of nanosheets, i.e., graphene, silicene, germanene and boron-nitride, were estimated and compared. The adsorption of [CH][BE] ionic liquid on different nanosheets is mainly featured by van der Waals forces, leading to strong benzoate ion–surface π-stacking. Likewise, there is also an important charge transfer from the anion to the sheet. The electronic structure analysis shows that Si- and Ge-based sheets lead to the largest changes in the HOMO and LUMO levels of choline benzoate. This paper provides new insights into the capability of DFT methods to provide useful information about the adsorption of ionic liquids on nanosheets and how ionic liquid features could be tuned through the adsorption on the suitable nanosheet.Ministerio de Economı´a y Competitividad (Spain, project CTQ2013-40476-R) and Junta de Castilla y León (Spain, project BU324U14)

Enhanced De-inking and Recyclability of Laser Printed Paper by Plasma-Assisted Fiber Coating

Office waste paper is one of the fastest growing segments of the recycled fiber industry. Toner particles are rigid, insoluble and difficult to disperse and detach from fibers. Therefore papers made from recycled office waste having high toner content will contain noticeable ink particles. This work will consider an alternative way of efficient de-inking using plasma polymers which will not affect the fibers chemically or mechanically. The focus is development and characterization of plasma-deposited films to serve as a barrier film for the adhesion of ink toner to the paper fibers and thereby enhance ink lift off from the fibers. The plasma treated paper is coated with fluorocarbon (PFE) and polyethylene glycol (PFE) films, with constant thickness of PFE and varying the thickness of PEG by 1500, from 1500 to 4500, for the three cases studied (PFE greater than PEG, PFE=PEG, PFE less than PEG). Handsheets were made using virgin fibers to eliminate effects of fillers. Once the sheets were coated and printing performed, they were re-pulped and both the slurry and the de-inking surfactant were placed in a flotation cell. Handsheets were made from the collected foam and stock and were scanned for particle count. The results indicated higher ink loss for the cases with increased thickness of polymer films. A handsheet with a 7500 film (PFE = 3000 and PEG = 4500) showed 61% ink removal compared to 38% for handsheets with no film deposited. There was also less material loss for the cases with higher polymer film thickness.M.S.Committee Co-Chair: Dr. Dennis Hess; Committee Co-Chair: Dr. Timothy Patterson; Committee Member: Jeff Empi

Ionic Liquid Based on α-Amino Acid Anion and N7,N9-Dimethylguaninium Cation ([dMG][AA]): Theoretical Study on the Structure and Electronic Properties

The interactions between five amino acid based anions ([AA]⁻ (AA = Gly, Phe, His, Try, and Tyr)) and N7,N9-dimethylguaninium cation ([dMG]⁺) have been investigated by the hybrid density functional theory method B3LYP together with the basis set 6-311++G­(d,p). The calculated interaction energy was found to decrease in magnitude with increasing side-chain length in the amino acid anion. The interaction between the [dMG]⁺ cation and [AA]⁻ anion in the most stable configurations of ion pairs is a hydrogen bonding interaction. These hydrogen bonds (H bonds) were analyzed by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. Finally, several correlations between electron densities in bond critical points of hydrogen bonds and interaction energy as well as vibrational frequencies in the most stable configurations of ion pairs have been checked

Orientation and Scientific Trend of Occupational Safety Studies published in Persian Scientific Journals of Iran from 2011 to 2022

Introduction: One of the questions that always arises in the minds of researchers, especially young researchers, is what pattern the progress of science follows in their field of expertise and what is the direction of the studies. The purpose of this study is to analyze the content of the studies published from 2011 to 2022 in Persian scientific journals in the field of workplace safety and determine the direction and scientific process of studies in this field. Material and Methods: All the studies published from the years 2011 to 2022 in the Persian scientific research journals ”Iran Occupational Health”, “Occupational Health and Safety”, “Occupational Health Engineering”, ”Iranian Journal of Ergonomics”, “Occupational Medicine” and “Occupational Health and Health Promotion” were gathered using census method from the websites of the journals. In total, 595 published articles were categorized according to the thematic codes determined by the opinion of experts, the theme of “risk analysis, assessment, and risk management” had the highest percentage of frequency (18.66 percent), while the theme of “safety application in other industries or specific workplaces” had the lowest frequency of percentage (0.34 percent). Approximately 50 percent of the variance of the published studies explained the themes of “risk analysis, risk assessment, and management”, “inspection, analysis and modeling of accidents”, “human error and safety”, “social, organizational factors, culture, safety climate, and behavior-based safety”. Conclusion: The existing trends emphasize the importance of learning lessons from accidents as a reactive approach and risk management, human factors, and behavioral aspects in safety interventions as a preventive approach. The research development of the country’s safety at the workplace should be further improved with new policies in different fields while taking advantage of international scientific advances on the specific functions and challenges of the country and with a problem-oriented approach