Solvation structure and dynamics of Li and LiO2 and their transformation in non-aqueous organic electrolyte solvents from first-principles simulations

doi:10.1016/S1872-2067(22)64098-1

Abstract

Abstract:

Density functional theory calculations together with ab initio molecular dynamics (AIMD) simulations have been used to study the solvation, diffusion and transformation of Li⁺ and LiO₂ upon O₂reduction in three organic electrolytes. These processes are critical for the performance of Li-air batteries. Apart from studying the structure of the solvation shells in detail, AIMD simulations have been used to derive the diffusivity and together with the Blue Moon ensemble approach to explore LiO₂ formation from Li⁺ and O₂^- and the subsequent disproportionation of 2LiO₂ into Li₂O₂ + O₂. By comparing the results of the simulations to gas phase calculations, the impact of electrolytes on these reactions is assessed which turns out to be more pronounced for the ionic species involved in these reactions.

Key words: Li-air batteries, Li oxide, Oxygen reduction, Density functional theory, Ab initio molecular dynamics, Solvation, Diffusivity, Disproportionation

Behnaz Rahmani Didar, Axel Groß. Solvation structure and dynamics of Li and LiO₂and their transformation in non-aqueous organic electrolyte solvents from first-principles simulations[J]. Chinese Journal of Catalysis, 2022, 43(11): 2850-2857.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64098-1

https://www.cjcatal.com/EN/Y2022/V43/I11/2850

Figures/Tables 7

Table 1 Interaction energies (in eV) of Li and LiO2 with electrolyte molecules obtained from DFT calculations using Eq. (1).

Electrolyte	PBE	PBE-D3	RPBE	RPBE-D3
Li
ACN (Li-N)	‒0.50	‒0.52	‒0.47	‒0.49
DMSO (Li-O)	‒0.76	‒0.79	‒0.67	‒0.72
DME (Li-O)	‒0.82	‒0.83	‒0.70	‒0.80
LiO₂
ACN (Li-N)	‒0.84	‒0.88	‒0.81	‒0.86
DMSO (Li-O)	‒0.98	‒1.01	‒0.94	‒1.00
DME (Li-O)	‒1.05	‒1.06	‒0.95	‒1.14

Table 2 Bond lengths in Å for the interactions of Li and LiO2 with electrolyte molecules obtained from DFT calculations. As far as the Li?O distances with respect to the complexes of LiO2 with DMSO and DME are concerned, the first line presents the Li distance to the oxygen atoms of the solvent molecules and the second line the Li?O distance within LiO2. The O?O distance always refers to the LiO2 compound.

Electrolyte	PBE	PBE-D3	RPBE	RPBE-D3
Li
ACN (Li-N)	1.94	1.94	1.99	2.00
DMSO (Li-O)	1.80	1.80	1.85	1.82
DME (Li-O)	1.98	1.99	2.00	2.04
LiO₂
ACN (Li-N)	2.07	2.04	2.16	2.05
Li-O	1.82	1.81	1.83	1.83
O-O	1.36	1.37	1.37	1.37
(DMSO) Li-O	1.88	1.90	1.92	1.91
Li-O	1.81	1.82	1.83	1.83
O-O	1.37	1.37	1.37	1.37
(DME) Li-O	2.06	2.16	2.12	2.09
Li-O	1.83	1.83	1.84	1.83
O-O	1.37	1.37	1.37	1.38

Fig. 1. Charge density difference ∆ρ upon the interaction of Li with ACN (a), DMSO (b) and DME (c) molecules, and LiO2 with ACN (d), DMSO (e) and DME (f) molecules, as obtained from DFT calculations using Eq. (2). Cyan and yellow regions correspond to electron accumulation and depletion, respectively. The isosurface levels are ±0.005 eV Å-3.

Fig. 2. Radial distribution functions of the Li?O and Li?N distances, respectively, obtained from AIMD simulations of Li (a) and LiO2 (b) in 1 mol/L ACN, DMSO and DME electrolytes. Insets show the first solvation shells for each case.

Fig. 3. Solvation energies obtained from AIMD simulations of Li (a) and LiO2 (b) in 1 mol/L of each of ACN, DMSO and DME electrolytes.

Fig. 4. Mean square displacement (MSD) obtained from AIMD simulations of Li (a) and LiO2 (b) in 1 mol/L of each of ACN, DMSO and DME electrolytes.

Fig. 5. Reaction energy barriers obtained from the Blue Moon method of AIMD simulations for (Association) Li + O2- → LiO2) (a) and (Disproportionation) 2(LiO2) → Li2O2 + O2 (b) in vacuum and 1 mol/L of each of ACN, DMSO and DME electrolytes.

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Solvation structure and dynamics of Li and LiO₂and their transformation in non-aqueous organic electrolyte solvents from first-principles simulations

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