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material loading, etc.) may change the equilibria and the involved redox reactions. Working mechanism of Li/S batteries is, therefore, composed of many pieces of puzzle, which could not be directly compared. However, all together, they bring very fruitful information to the Li/S community and deeper understanding of the mechanisms and redox reactions hidden behind. Figure 1-20. Proposed detailed redox reactions together with disproportionation and dissociation reactions, during initial discharge studied by coupling three techniques: UV-Vis, HPLC and RPE194. The kinetics of the reactions, where longer chain polysulfides are involved (more soluble species), starting from S8 through Li2S4 formation (thus, along upper discharge plateau and the sloping step) are believed to be fast195,196. On the other hand, the reactions of shorter chain polysulfides (along the lower discharge plateau), together with solid product(s) formation, are known to present much slower kinetics (large overpotential)197. The specificity of the Li/S system, as previously mentioned, comes from the fact that the physical state of active material (solid, soluble, both) is strongly dependent from the state of discharge/charge of the battery. Therefore, depending on their particularity, some of the techniques can be applied with more success to analyze solid reaction products, like X-ray diffraction (XRD)23-25,198-200, transmission X-ray spectroscopy (TXM)199,201, K-edge X-ray absorption near edge structure (XANES), scanning electron microscopy (SEM). On the contrary, other techniques are more appropriate for soluble polysulfides investigation/identification, i.e. UV-Vis spectroscopy27,172,194, Raman spectroscopy196, X-Ray Absorption spectroscopy (XAS)29,202-204, HPLC194, or Rotating Ring Disk Electrode technique (RRDE)173. Chapter 1: Literature review 39PDF Image | Accumulateur Lithium Soufre
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