Realigning the Chemistry and Parameterization of Lithium‐Sulfur Battery Models to Accommodate Emerging Experimental Evidence and Cell Configurations

Abstract

Experimental insights into lithium-sulfur (LiS) battery chemistry have resulted in practical improvements in cell coulombic efficiency, sulfur utilization, and cycle life. However, optimization of this complex battery chemistry requires experimentally aligned modeling tools. A porous electrode theory-based model incorporating key electrolyte dissociation chemistry is developed for the LiS cell. The proposed chemistry produces a radical anion species that is widely observed spectroscopically in LiS electrolytes. We explore the implications of radical anion formation on the current-voltage behavior within the context of a state-of-art high energy density LiS cell with low electrolyte: sulfur (E/S) ratio and ideally-protected anode. Parameters describing the dissociation reaction equilibrium and kinetics are shown to alter the electrolyte speciation in ways that can be linked to observations from LiS electrolyte engineering experiments.

Working Mechanisms and Structure Engineering of Renewable Biomass‐Derived Materials for Advanced Lithium‐Sulfur Batteries: A Review

“…In addition, inherent doping helps natural enhance the chemical interaction between sulfur and carbon, so the pursuit of natural in‐situ heteroatom‐doped biomass materials has a long‐term future. (4) Researching and developing theoretical models of carbon and its composite materials derived from biomass to guide specific research work [132] . The research and development of the model is conducive to having a deeper understanding of the reaction process.…”

Toward Rigorous Validation of Li-S Battery Models

“…Simulating these operations out-of-sample should be considered a part of model validation. 15 ✓ Neidhardt et al 25 ✓ Fronczek et al 26 ✓ ✓ Hofmann et al 16 ✓ ✓ ✓ ✓ ✓ Zhang et al 19 ✓ ✓ ✓ Danner et al 9 ✓ ✓ ✓ Marinescu et al 27 ✓ ✓ Thangavel et al 28 ✓ ✓ Barai et al 17 ✓ ✓ ✓ Ren et al 18 ✓ ✓ Yoo et al 20 ✓ ✓ Zhang et al 10 ✓ ✓ Marinescu et al 21 ✓ ✓ Andrei et al 11 ✓ ✓ Hua et al 11 ✓ ✓ Danner & Latz 29 ✓ ✓ ✓ ✓ ✓ Xiong et al 23 ✓ Erisen et al 30 Emerce & Eroglu 31 Kamyab et al 32 ✓ ✓ ✓ Parke et al 33 ✓ ✓ Erisen & Eroglu 34 ✓ Parke et al 35 ✓ ✓ modifying an existing zero-dimensional model on the basis of the following analysis.…”

Towards Rigorous Validation of Li-S Battery Models

“…Within model validation, models which perform poorly under particular operational loads can be easily detected and the necessary modifications can be quickly proposed. Within model selection, the comparison of two [35] models is difficult when one model is published with discharge simulations only and the other with charge simulations only. As discussed in section 3 and illustrated in Table 2, this is not unusual.…”

“…These rate-dependent predictions are out-of-sample but no experimental data is provided to suggest these results align with a known Li-S cell. Park et al [35] improved upon their previous model by incorporating new parameterisations and electrochemical pathways but the distinction between in-sample and out-of-sample was not present. Further, only discharge was considered.…”