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Viscosity measurements of different ‘catholyte’ solutions (Li2Sx + 1M LiTFSI in TEGDME/DIOX 1/1 vol), having the same molar concentration (0.1 M) but different polysulfide composition, i.e. Li2S4, Li2S6 and Li2S8, were also performed (Figure 6-17). The results clearly show the dependence of viscosity vs. the polysulfides composition. The most comparable values are the one at the slower shear rate (1 s-1), since are the closest to the real battery operation (no shearing). Li2S4 solution leads to higher viscosity (210-2 Pa.s) than Li2S8 (810-3 Pa.s) and Li2S6 (610-3 Pa.s) ones, in good agreement with the evolution of the resistance values at the ‘maximum points’ (R’max and R”max) during discharge and charge. Moreover, the same resistance value as the one recorded at R”max point, i.e. 8.3 Ω was also recorded during discharge, just at the end of upper plateau (see the green dashed line on Figure 6-16). The end of upper discharge plateau is considered as the moment with the highest concentration of Li2S8 and Li2S6 species246. It clearly shows then, that the electrolyte resistance is strictly dependent on the polysulfides composition at given state of charge/discharge point. Figure 6-17. Viscosity measurement of ‘catholyte’ solution: 1 M LiTFSI in TEGDME/DIOX 1/1 vol having the same 0.1 M concentration of polysulfides species, of different compositions: Li2S4 (in blue), Li2S6 (in red), Li2S8 (in black). 6.5.4.b) High to medium frequency region (50 kHz - 1 Hz) We previously showed that there is a constant contribution of the bulk of positive electrode (RNwC//CPENwC) (attributed to the carbon based current collector). This semicircle (~ 1 – 2 Ω, at ~ 6 – 9 kHz) at the initial state of Li/S cell is totally covered by the significant response of Li negative electrode, while being more visible/‘uncovered’ where the lithium resistance is decreasing upon discharge (see Nyquist plot evolution at different DOD%; Figure 6-9). Chapter 6: EIS and low temperature studies 212PDF Image | Accumulateur Lithium Soufre
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