Computational and Experimental Study of a Sustainable Lithium Acetate and Urea-Based Electrolyte for Lithium-Ion Batteries

Abstract

Lithium-ion batteries (LIBs) are the most widely used energy storage systems in portable devices, electric vehicles, large-scale energy storage power, and other applications. The optimal performance and safety of LIBs are mainly determined by the electrolyte, which facilitates the transport of Li+ ions and promotes the formation of the SEI layer. Since commercial LIBs are predominantly composed of organic-based electrolytes, these present elevated costs, safety risks, and environmental hazards due to their elevated flammability and fluorinated composition. To address these concerns, aqueous electrolytes have been explored as safer alternatives to organic solvents. However, the use of aqueous LIB electrolytes is restricted due to the narrow electrochemical stability window of water (ESWH2O ≈ 1.23 V). This problem is usually overcomed by using superconcentrated electrolytes, including "water-in-salt" and "water-in-bisalt," which extend the ESW. However, their practicality remains uncertain due to the high concentration of fluorinated salts, which leads to increased cost and toxicity.1 In this study, we employed computational and experimental methods to investigate the use of non-fluorinated aqueous electrolytes prepared by combining different ratios of LiCH3COOH and a water-urea mixture of fixed composition (LiCH3COO-H2O-CO(NH2)2) for their use as an electrolyte for LIBs. ESWs were determined by cyclic voltammetry using GCE, Pt, and Al as working electrodes. The electrolyte with the highest ESW (3.2 V) was probed to be compatible with commercial electrodes such as TiO2, LTO, LMO, and LFP, and was used to assemble a LIB cell with LTO and LMO as electrodes. This cell presented an average output voltage of 2.3 V and a specific capacity of 105 mAh/g over 200 cycles at a current density of 0.5 A/g. Furthermore, the thermodynamic and kinetic factors associated with the electrochemical stability of the electrolyte have been studied using DFT and molecular dynamics (MD), respectively. Adiabatic redox potentials of the electrolyte species obtained by DFT show calculated ESWs higher than 4.5 V. Transport properties of the species in the electrolyte were studied via molecular dynamics and these show that the diffusion of Li+ is comparable to the diffusion observed in organic electrolytes.2 Structurally, we also observed that urea disrupts the Li-water structure, leading to a decrease in the coordination number of water molecules to Li+ (CNLi-H2O = 1.4). This result has been experimentally confirmed using NIR and Raman spectroscopy. Overall, these results demonstrate the effectiveness of employing a lithium acetate-urea-based aqueous electrolyte as an alternative to organic electrolytes for the development of more secure, environmentally friendly, and sustainable LIBs.1. Brown, J.; Grimaud, A. With Only a Grain of Salt. Nat. Energy 2022, 7 (2), 126–127.2. Galvez-Aranda, D. E.; Seminario, J. M. Ion Pairing, Clustering and Transport in a LiFSI-TMP Electrolyte as Functions of Salt Concentration Using Molecular Dynamics Simulations. J. Electrochem. Soc. 2021, 168 (4), 040511.