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6.5.3. Equivalent circuit In the literature, several propositions of equivalent circuit used for fitting the EIS data of Li/S cells were given, and some of them were presented in Table 6-1. Sometimes the model was modified (for the same cell) as a function of the discharge/charge state of the cell. Our (simple) circuit is preserved all along the cycling, even if very small contributions appear depending on the state of discharge/charge. The model is composed of following components connected in series: • Rel - attributed mainly to the electrolyte resistance; • RNwC//CPENwC - corresponds to the positive electrode bulk contribution and more precisely, to the non-woven carbon collector; • RLi//CPELi - attributed to the lithium/electrolyte interphase (SEI); • RPS//CPEPS - corresponds to the charge transfer of polysulfides species on positive electrode (i.e. polysulfides/carbon interface). When dominating species are soluble polysulfides (high-to-medium order ones), with fast kinetics of the reaction, a small semicircle is observed (~ 37 Hz). Formation of low-order ones (including solid Li2S) results in highly increased semicircle, and the characteristic frequency is shifted to lower values (~ 5 – 2 Hz); • CPEdiff - corresponds to the diffusion processes (ions and soluble polysulfides) through the electrolyte, inside the porous positive electrode and the passivation layer on lithium surface. Figure 6-14 shows the proposed model, together with the selected fitting example (at 80% DOD). Based on this proposed equivalent model, evolution at each region, i.e. HF, MF and LF is discussed in further section. 207 Chapter 6: EIS and low temperature studiesPDF Image | Accumulateur Lithium Soufre
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