During the past decades, the development of alternative energy sources has become increasingly important as the growing consumption of non-regenerative fossil energy poses a threat to the environment. Hence, developing of next-generation batteries featuring high capacity, reduced costs and improved safety, such as in lithium-sulfur batteries, is of utmost importance. The benefits of lithium-sulfur batteries have led to widespread efforts to understand the fundamentals of the sulfur redox chemistry that drives their operation, as capacity fade has been observed in almost all Li-S batteries.[1] Therefore, the involved local structural changes that correlate with the (electro)chemical processes need to be unveiled during the operation of Li-S batteries, suitably by in situ and in operando methods. This presentation will demonstrate the development and application of one such (operando) technique: nuclear magnetic resonance (NMR) spectroscopy. NMR spectroscopic measurements allow the probing of the structural changes in a battery during electrochemical cycling. In particular, the application of a non-invasive experimental set-up, which can follow the reaction inside the battery in operando is highly desirable as it provides real-time structural information compared to ex situ analysis.[2] Lithium-sulfur batteries contain various NMR-active nuclear isotopes, like 7Li, 6Li and 33S, which allow the following of the chemical reactions during the charge-discharge process. This includes the transition between elemental sulfur and polysulfides on the cathode side, the formation of the solid-electrolyte interface (SEI) and the metal plating and stripping on the anode side. Herein, we use for the first time a combination of lithium and sulfur in operando NMR spectroscopy to reveal a fundamental understanding of the reaction pathway of lithium-sulfur batteries during the cycling process.Lithium NMR spectroscopy is a powerful technique to apply to batteries, as demonstrated by many previous investigations on different lithium battery systems, since it enables the detection of the chemical environments of lithium species during electrochemical cycling and parasitic reactions in the cell.[3] The great advantage of in operando 7Li NMR spectroscopy is that the 7Li signals of the lithium anode and the deposited metal differ due to the bulk magnetic susceptibility effects and the surface area, bringing the skin depth effect into play. Thus, this method enables a time-resolved and quantitative evaluation of the electrochemical metal deposition during electrochemical cycling. Therefore, it is possible to investigate a critical problem that reduces the cell performance – the formation of lithium dendrites. This lithium deposition is particularly problematic if it occurs uncontrolled and inhomogeneous and the exact mechanism of nucleation and propagation of dendrites is not yet fully understood.[4] The developed technique helps to understand this deposition to improve the safety during cycling. The interpretation of the electrolyte signal in the in operando 7Li spectra is much more difficult because of the overlapping signals. Therefore, in situ 33S and 6Li NMR spectroscopy supports the identification and quantification of (poly-)sulfides during the charge-discharge-process. 33S NMR experiments are rarely reported since 33S is a quadrupolar nucleus characterized by a low natural abundance and magnetogyric ratio, resulting in a very low receptivity. Nevertheless, the developed 33S NMR technique allows the detection of the formation Li2S under in operando conditions.[5] Additional in operando 6Li NMR experiments allow to follow the (poly-)sulfide formation as the spectra yield much sharper lines in asymmetric lithium environments in comparison to 7Li NMR experiments.[6] Thus, these techniques provide complementary results to the 7Li NMR spectroscopic studies and help to elucidate the sulfur redox mechanism in lithium-sulfur batteries.Our developed in situ NMR spectroscopic set-up is a powerful analytical method since real-time qualitative and quantitative detection of different sulfur and lithium species is crucial for understanding the electrochemical process in sulfur batteries. The first time, a combination of in operando lithium and sulfur NMR spectroscopy is presented, providing new insights at the molecular level that are essential for accelerating the development of lithium-sulfur battery technologies.[1] H. Wang, N. Sa, et al., The Journal of Physical Chemistry C 2017, 121, 6011–6017.[2] J. B. Richter, et al., Chemical Communications 2019, 55, 6042–6045.[3] R. Bhattacharyya, et al., Nat Mater 2010, 9, 504–510.[4] A. B. Gunnarsdóttir, et al., J Mater Chem A Mater 2020, 8, 14975–14992.[5] R. Musio, in Annu Rep NMR Spectrosc, 2006, pp. 1–88.[6] L. A. Huff, et al., Surf Sci 2015, 631, 295–300.
Read full abstract
Oct 14, 2024
Mohammed Mahmud + 2
Open Access