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(a) (b) (c) Figure 6-20. Resistance and capacitance values (a) obtained from fitting the MF semicircle (Li/electrolyte interphase), together with the fitting errors value (b) and electrolyte resistance evolution together with the voltage profile (c). It can be seen that the capacitance values drastically increase exactly at the moment of complete discharge. On the other hand, the fitting error is also very high (even 65 %). It brings us to the conclusion that, with the simple model we designed for fitting, we can probably not extract all the information due to the presence of large errors appearing for some state of discharge/charge. As concerning the LF semicircle evolution, previously attributed to the charge transfer reaction of the polysulfide species (RPS//CPEPS), appearance of a small loop just after the first discharge plateau (i.e. spectra # 3 on Figure 6-9) can be observed. This loop has the relaxation frequency of ~ 37 Hz, and its appearance corresponds to the moment where polysulfides are progressively formed in the electrolyte. During the region between two plateaus (2.3 V – 2.1 V; Nyquist plots # 4 and # 6), the concentration of polysulfides is progressively increasing (see Rel evolution, Figure 6-16), however, the charge transfer resistance is too small (fast kinetic) and the response is ‘hidden’ by a large response of the Li electrode. Starting from the beginning of lower discharge plateau (EIS spectra # 6), a semicircle related to charge transfer reaction contribution starts to be visible, with progressively increasing resistance by the end of Chapter 6: EIS and low temperature studies 216PDF Image | Accumulateur Lithium Soufre
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