Interactive Multiscale Modeling to Bridge Atomic Properties and Electrochemical Performance in Li-CO$_2$ Battery Design

Mohammed Lemaalem; Selva Chandrasekaran Selvaraj; Ilias Papailias; Naveen K. Dandu; Arash Namaeighasemi; Larry A. Curtiss; Amin Salehi-Khojin; Anh T. Ngo

doi:10.1016/j.apenergy.2025.126693

paper

Interactive Multiscale Modeling to Bridge Atomic Properties and Electrochemical Performance in Li-CO $_{2}$ Battery Design

arXiv:2501.10954 · doi:10.1016/j.apenergy.2025.126693

Abstract

Li-CO $_{2}$ batteries are promising energy storage systems due to their high theoretical energy density and CO $_{2}$ fixation capability, relying on reversible Li $_{2}$ CO $_{3}$ /C formation during discharge/charge cycles. We present a multiscale modeling framework integrating Density Functional Theory (DFT), Ab-Initio Molecular Dynamics (AIMD), classical Molecular Dynamics (MD), and Finite Element Analysis (FEA) to investigate atomic and cell-level properties. The considered Li-CO $_{2}$ battery consists of a lithium metal anode, an ionic liquid electrolyte, and a carbon cloth cathode with Sb $_{0.67}$ Bi $_{1.33}$ Te $_{3}$ catalyst. DFT and AIMD determined the electrical conductivities of Sb $_{0.67}$ Bi $_{1.33}$ Te $_{3}$ and Li $_{2}$ CO $_{3}$ using the Kubo-Greenwood formalism and studied the CO $_{2}$ reduction mechanism on the cathode catalyst. MD simulations calculated the CO $_{2}$ diffusion coefficient, Li $^{+}$ transference number, ionic conductivity, and Li $^{+}$ solvation structure. The FEA model, parameterized with atomistic simulations data, reproduced the available experimental voltage-capacity profile at 1 mA/cm $^{2}$ and revealed spatio-temporal variations in Li $_{2}$ CO $_{3}$ /C deposition, porosity, and CO $_{2}$ concentration dependence on discharge rates in the cathode. Accordingly, Li $_{2}$ CO $_{3}$ can form large and thin film deposits, leading to dispersed and local porosity changes at 0.1 mA/cm $^{2}$ and 1 mA/cm $^{2}$ , respectively. The capacity decreases exponentially from 81,570 mAh/g at 0.1 mA/cm $^{2}$ to 6,200 mAh/g at 1 mA/cm $^{2}$ , due to pore clogging from excessive discharge product deposition that limits CO $_{2}$ transport to the cathode interior. Therefore, the performance of Li-CO $_{2}$ batteries can be improved by enhancing CO $_{2}$ transport, regulating Li $_{2}$ CO $_{3}$ deposition, and optimizing cathode architecture.

40 pages (main paper), 5 figures, graphical abstract, and supporting information file

Interactive Multiscale Modeling to Bridge Atomic Properties and Electrochemical Performance in Li-CO2​ Battery Design

Abstract

Interactive Multiscale Modeling to Bridge Atomic Properties and Electrochemical Performance in Li-CO $_{2}$ Battery Design