Calcium-Ion Batteries: Identifying Ideal Electrolytes for Next Generation Energy Storage Using Computational Analysis
Standing
Undergraduate
Type of Proposal
Oral Presentation
Faculty
Faculty of Science
Proposal
In this computational study, we have analyzed the possibility of replacing lithium-ion batteries with calcium ion batteries in the near future. We utilized molecular dynamics simulations, and quantum mechanical calculations to investigate the solvation behaviour of calcium tetrafluoroborate in neat carbonates and carbonate mixtures. The results of our investigation indicate that both neat ethyl methyl carbonate (EMC) and a mixture of ethyl carbonate and diethyl carbonate (EC: DEC) show the highest free-energy of solvation for the Ca2+. Through studying the electronic characteristics and molecular interactions responsible for solvation using natural bond order analysis, quantum theory of atoms-in-molecules and noncovalent interaction analysis, our conclusions support the argument that the cation’s interaction with the carbonyls, of the coordinating solvents, rather than with the tetrafluoroborate counter ions, play a primary role in delocalizing the charge on Ca2+. As a result of the carbonyl groups stabilizing carbonate-calcium complexes and activating the carbonate solvent molecules, thorough calculations show that the HOMO-LUMO energy gap (Eg), electronic chemical potential (μ) and chemical hardness (η) of the complexes are directly proportional to the free energy of solvation of the complex. Trends with our previous results from Li+, Na+ and Mg+ ions show that this correlation is also observed in solvated magnesium ions, but not in lithium or sodium salts. This study will assist in the design of future battery materials in the rational selection of additives, counter ions or electrolyte solvents.
Grand Challenges
Sustainable Industry
Calcium-Ion Batteries: Identifying Ideal Electrolytes for Next Generation Energy Storage Using Computational Analysis
In this computational study, we have analyzed the possibility of replacing lithium-ion batteries with calcium ion batteries in the near future. We utilized molecular dynamics simulations, and quantum mechanical calculations to investigate the solvation behaviour of calcium tetrafluoroborate in neat carbonates and carbonate mixtures. The results of our investigation indicate that both neat ethyl methyl carbonate (EMC) and a mixture of ethyl carbonate and diethyl carbonate (EC: DEC) show the highest free-energy of solvation for the Ca2+. Through studying the electronic characteristics and molecular interactions responsible for solvation using natural bond order analysis, quantum theory of atoms-in-molecules and noncovalent interaction analysis, our conclusions support the argument that the cation’s interaction with the carbonyls, of the coordinating solvents, rather than with the tetrafluoroborate counter ions, play a primary role in delocalizing the charge on Ca2+. As a result of the carbonyl groups stabilizing carbonate-calcium complexes and activating the carbonate solvent molecules, thorough calculations show that the HOMO-LUMO energy gap (Eg), electronic chemical potential (μ) and chemical hardness (η) of the complexes are directly proportional to the free energy of solvation of the complex. Trends with our previous results from Li+, Na+ and Mg+ ions show that this correlation is also observed in solvated magnesium ions, but not in lithium or sodium salts. This study will assist in the design of future battery materials in the rational selection of additives, counter ions or electrolyte solvents.