13 research outputs found
Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Non-Aqueous Electrolytes
Multi-valent (MV) battery architectures based on pairing a Mg metal anode
with a high-voltage ( 3 V) intercalation cathode offer a realistic design
pathway toward significantly surpassing the energy storage performance of
traditional Li-ion based batteries, but there are currently only few
electrolyte systems that support reversible Mg deposition. Using both static
first-principles calculations and molecular dynamics, we perform
a comprehensive adsorption study of several salt and solvent species at the
interface of Mg metal with an electrolyte of Mg and Cl dissolved in
liquid tetrahydrofuran (THF). Our findings not only provide a picture of the
stable species at the interface, but also explain how this system can support
reversible Mg deposition and as such we provide insights in how to design other
electrolytes for Mg plating and stripping. The active depositing species are
identified to be (MgCl) monomers coordinated by THF, which exhibit
preferential adsorption on Mg compared to possible passivating species (such as
THF solvent or neutral MgCl complexes). Upon deposition, the energy to
desolvate these adsorbed complexes and facilitate charge-transfer is shown to
be small ( 61 46.2 kJ mol to remove 3 THF from the strongest
adsorbing complex), and the stable orientations of the adsorbed but desolvated
(MgCl) complexes appear favorable for charge-transfer. Finally,
observations of Mg-Cl dissociation at the Mg surface at very low THF
coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode
may occur upon plating. In the stripping process, this is beneficial by further
facilitating the Mg removal reaction
Elucidating the Structure of the Magnesium Aluminum Chloride Complex electrolyte for Magnesium-ion batteries
We present a rigorous analysis of the Magnesium Aluminum Chloro Complex
(MACC) in tetrahydrofuran (THF), one of the few electrolytes that can
reversibly plate and strip Mg. We use \emph{ab initio} calculations and
classical molecular dynamics simulations to interrogate the MACC electrolyte
composition with the goal of addressing two urgent questions that have puzzled
battery researchers: \emph{i}) the functional species of the electrolyte, and
\emph{ii}) the complex equilibria regulating the MACC speciation after
prolonged electrochemical cycling, a process termed as conditioning, and after
prolonged inactivity, a process called aging. A general computational strategy
to untangle the complex structure of electrolytes, ionic liquids and other
liquid media is presented. The analysis of formation energies and
grand-potential phase diagrams of Mg-Al-Cl-THF suggests that the MACC
electrolyte bears a simple chemical structure with few simple constituents,
namely the electro-active species MgCl and AlCl in equilibrium with
MgCl and AlCl. Knowledge of the stable species of the MACC electrolyte
allows us to determine the most important equilibria occurring during
electrochemical cycling. We observe that Al deposition is always preferred to
Mg deposition, explaining why freshly synthesized MACC cannot operate and needs
to undergo preparatory conditioning. Similarly, we suggest that aluminum
displacement and depletion from the solution upon electrolyte resting (along
with continuous MgCl regeneration) represents one of the causes of
electrolyte aging. Finally, we compute the NMR shifts from shielding tensors of
selected molecules and ions providing fingerprints to guide future experimental
investigations
Molten salt eutectics from atomistic simulations
Despite their importance for solar thermal power applications, phase-diagrams of molten salt mixture heat transfer fluids (HTFs) are not readily accessible from first principles. We present a molecular dynamics scheme general enough to identify eutectics of any HTF candidate mixture. The eutectic mixture and temperature are located using the liquid mixture free energy and the pure component solid-liquid free energy differences. The liquid mixture free energy is obtained using thermodynamic integration over particle identity transmutations sampled with molecular dynamics at a single temperature. Drawbacks of conventional phase diagram mapping methodologies are avoided by not considering solid mixtures, thereby evading expensive computations of solid phase free energies. Numerical results for binary and ternary mixtures of alkali nitrates agree well with experimental measurements
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Nucleation of metastable aragonite CaCO3 in seawater.
Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution
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Nucleation of metastable aragonite CaCO3 in seawater.
Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution
Nucleation of metastable aragonite CaCO[subscript 3] in seawater
Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.United States. Dept. of Energy. Office of Basic Energy Sciences (Contract DE-FG02-96ER45571)National Science Foundation (U.S.). Graduate Research Fellowshi
Molecular Simulation of the Thermal and Transport Properties of Three Alkali Nitrate Salts
Thermodynamic and transport properties for nitrate salts containing lithium, sodium, and potassium cations were Computed from molecular simulations. Densities for the liquid and crystal phases calculated from simulations were within 4% of the experimental values. A nonequilibrium molecular dynamics method was used to compute viscosities and thermal conductivities. The results for the three salts were comparable to the experimental values for both viscosity and thermal conductivity. Computed heat capacities were also in reasonable agreement with experimental values. The computed melting point for NaNO(3) was within 15 K of its experimental value, while for LiNO(3) and KNO(3), computed melting points were within 100 K of the experimental values. The results show that very small free-energy differences between the crystal and liquid phases can result in large differences in computed melting point. To estimate melting points with an accuracy of around 10 K, simulation methods and force fields must yield free energies with an accuracy of around 0.25 kcal/mol. Tests conducted on a well-studied sodium chloride model indicated negligible dependence of file computed melting point on system size or choice of integration temperature