Ab Initio Molecular Dynamics Investigations of the Speciation and Reactivity of Deep Eutectic Electrolytes in Aluminum Batteries

Deep eutectic solvents (DES) have emerged as an alternative for conventional ionic liquids in aluminum batteries. Elucidating DES composition is fundamental to understand aluminum electrodeposition in the battery anode. Despite numerous experiemental efforts, the speciation of these DES remains elusive. This work shows how \textit{Ab initio} molecular dynamics (AIMD) simulations can shed light on the molecular composition of DES. For the particular example of AlCl$_{3}$:urea, one of the most popular DES, we carried out a systematic AIMD study, showing how an excess of AlCl$_{3}$ in the AlCl$_{3}$:urea mixture promotes the stability of ionic species vs neutral ones and also favors the reactivity in the system. These two facts explain the experimentally observed enhanced electrochemical activity in salt-rich DES. We also observe the transfer of simple $[$AlCl$_{x}$(urea)$_{y}]$ clusters between different species in the liquid, giving rise to free $[$AlCl$_{4}]^{-}$ units. The small size of these $[$AlCl$_{4}]^{-}$ units favors the transport of ionic species towards the anode, facilitating the electrodeposition of aluminum.

Download Full-text

Ab Initio Molecular Dynamics Investigations of the Speciation and Reactivity of Deep Eutectic Electrolytes in Aluminum Batteries

10.26434/chemrxiv.13720888.v1 ◽

2021 ◽

Author(s):

David Carrasco-Busturia ◽

Steen Lysgaard ◽

Piotr Jankowski ◽

Tejs Vegge ◽

Arghya Bhowmik ◽

...

Keyword(s):

Molecular Dynamics ◽

Ab Initio ◽

Deep Eutectic Solvents ◽

Ionic Species ◽

Electrochemical Activity ◽

Molecular Composition ◽

Ab Initio Molecular Dynamics ◽

The Stability ◽

Shed Light ◽

Battery Anode

Deep eutectic solvents (DES) have emerged as an alternative for conventional ionic liquids in aluminum batteries. Elucidating DES composition is fundamental to understand aluminum electrodeposition in the battery anode. Despite numerous experiemental efforts, the speciation of these DES remains elusive. This work shows how \textit{Ab initio} molecular dynamics (AIMD) simulations can shed light on the molecular composition of DES. For the particular example of AlCl$_{3}$:urea, one of the most popular DES, we carried out a systematic AIMD study, showing how an excess of AlCl$_{3}$ in the AlCl$_{3}$:urea mixture promotes the stability of ionic species vs neutral ones and also favors the reactivity in the system. These two facts explain the experimentally observed enhanced electrochemical activity in salt-rich DES. We also observe the transfer of simple $[$AlCl$_{x}$(urea)$_{y}]$ clusters between different species in the liquid, giving rise to free $[$AlCl$_{4}]^{-}$ units. The small size of these $[$AlCl$_{4}]^{-}$ units favors the transport of ionic species towards the anode, facilitating the electrodeposition of aluminum.

Download Full-text

Are There Magic Compositions in Deep Eutectic Solvents? Effects of Composition and Water Content in Choline Chloride/Ethylene Glycol from Ab Initio Molecular Dynamics

The Journal of Physical Chemistry B ◽

10.1021/acs.jpcb.0c04844 ◽

2020 ◽

Vol 124 (34) ◽

pp. 7433-7443 ◽

Cited By ~ 7

Author(s):

Vahideh Alizadeh ◽

Friedrich Malberg ◽

Agílio A. H. Pádua ◽

Barbara Kirchner

Keyword(s):

Molecular Dynamics ◽

Ethylene Glycol ◽

Ab Initio ◽

Water Content ◽

Choline Chloride ◽

Deep Eutectic Solvents ◽

Ab Initio Molecular Dynamics

Download Full-text

Ab-initio molecular dynamics study of the stability and reactivity of C60

Materials Science and Engineering A ◽

10.1016/s0921-5093(96)10312-9 ◽

1996 ◽

Vol 217-218 ◽

pp. 19-22 ◽

Cited By ~ 4

Author(s):

Kaora Ohno ◽

Yutaka Maruyama ◽

Yoshiyuki Kawazoe

Keyword(s):

Molecular Dynamics ◽

Ab Initio ◽

Ab Initio Molecular Dynamics ◽

The Stability

Download Full-text

Ab Initio Molecular Dynamics Study of the Structure and Properties of Nb-Doped Zr-Cu-Al Amorphous Alloys

Metals ◽

10.3390/met11111821 ◽

2021 ◽

Vol 11 (11) ◽

pp. 1821

Author(s):

Hongqing Wei ◽

Ping Zhang ◽

Yi Tang

Keyword(s):

Molecular Dynamics ◽

Ab Initio ◽

Amorphous Alloys ◽

Dynamics Simulation ◽

Ab Initio Molecular Dynamics ◽

Structure And Properties ◽

Stable Clusters ◽

Macroscopic Plasticity ◽

The Stability ◽

Stable Structures

In this paper, experiments were carried out on (Zr0.5Cu0.4Al0.1)100-xNbx (x = 0, 3, 6 at.%) amorphous alloys, and the corresponding ab initio molecular dynamics simulation was performed. The results showed that stable structures of Nb-centered and Al-centered icosahedral (-like) atomic clusters were formed after a small amount of (3 at.%) Nb was added. Stable and close-packed backbone structures were formed by the means of interconnection and matching of the two kinds of stable clusters in the alloys, which also enhanced the overall heterogeneity of the structures, thereby improving the strength and macroscopic plasticity. In addition, when more (6 at.%) Nb was added, the stable Al-centered clusters were replaced by some stable Nb-centered clusters in the alloys, and the stability and heterogeneity of the structures were partly reduced, which reduced the strength and macroscopic plasticity.

Download Full-text

Dissolution of NaCl nanocrystals: an ab initio molecular dynamics study

Physical Chemistry Chemical Physics ◽

10.1039/c4cp00635f ◽

2014 ◽

Vol 16 (33) ◽

pp. 17437-17446 ◽

Cited By ~ 17

Author(s):

Nico Holmberg ◽

Jian-Cheng Chen ◽

Adam S. Foster ◽

Kari Laasonen

Keyword(s):

Molecular Dynamics ◽

Ab Initio ◽

Ionic Species ◽

Ab Initio Molecular Dynamics

NaCl nanocrystal dissolution was investigated in atomistic detail revealing a difference in the solvation of two different ionic species.

Download Full-text

Structure of phosphorus-selenium glasses: results from ab initio molecular dynamics simulations

Molecular Physics ◽

10.1080/002689700162045 ◽

2000 ◽

Vol 98 (11) ◽

pp. 701-707

Author(s):

Alessandro Sergi, Mauro Ferrario, Francesco Bu

Keyword(s):

Molecular Dynamics ◽

Ab Initio ◽

Molecular Dynamics Simulations ◽

Ab Initio Molecular Dynamics ◽

Dynamics Simulations

Download Full-text

Combustion Driven by Fragment-based Ab Initio Molecular Dynamics Simulation

10.26434/chemrxiv.11462160.v1 ◽

2019 ◽

Author(s):

Liqun Cao ◽

Jinzhe Zeng ◽

Mingyuan Xu ◽

Chih-Hao Chin ◽

Tong Zhu ◽

...

Keyword(s):

Molecular Dynamics ◽

Ab Initio ◽

Large Scale ◽

Methane Combustion ◽

Combustion Method ◽

Dynamics Simulation ◽

Ab Initio Molecular Dynamics ◽

Computational Time ◽

Combustion Mechanism ◽

Daily Lives

Combustion is a kind of important reaction that affects people's daily lives and the development of aerospace. Exploring the reaction mechanism contributes to the understanding of combustion and the more efficient use of fuels. Ab initio quantum mechanical (QM) calculation is precise but limited by its computational time for large-scale systems. In order to carry out reactive molecular dynamics (MD) simulation for combustion accurately and quickly, we develop the MFCC-combustion method in this study, which calculates the interaction between atoms using QM method at the level of MN15/6-31G(d). Each molecule in systems is treated as a fragment, and when the distance between any two atoms in different molecules is greater than 3.5 Å, a new fragment involved two molecules is produced in order to consider the two-body interaction. The deviations of MFCC-combustion from full system calculations are within a few kcal/mol, and the result clearly shows that the calculated energies of the different systems using MFCC-combustion are close to converging after the distance thresholds are larger than 3.5 Å for the two-body QM interactions. The methane combustion was studied with the MFCC-combustion method to explore the combustion mechanism of the methane-oxygen system.

Download Full-text