Fingerprinting Mean Composition of Lithium Polysulfide Standard Solutions by Applying High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy.

In a lithium/sulfur (Li/S) battery, the reduction of sulfur during discharge involves a particular mechanism, where the active material successively dissolves into the electrolyte to form lithium polysulfide intermediate species (Li2Sx), with x being a function of the state of charge. In this work, sulfur K-edge resonant inelastic X-ray scattering measurements were performed for the characterization of different Li2Sx polysulfide standard solutions. High-energy resolution fluorescence detected X-ray absorption spectroscopy allowed clear separation the pre-edge absorption peak corresponding to terminal sulfur atoms from the main absorption peak due to internal atoms and allowed quantitative evaluation of the evolution of the peak area ratio as a function of the polysulfide chain length. Results of this experimental work demonstrate that the normalized area of the pre-edge is a reliable fingerprint of the Li2Sx mean chain length in agreement with recent theoretical predictions. As a perspective, this work confirms that operando HERFD XAS can be used to differentiate mean polysulfide composition, which is key issue in the characterization of Li/S cells.

Degradation of Li/S Battery Electrodes On 3D Current Collectors Studied Using X-ray Phase Contrast Tomography.

Lithium/sulphur batteries are promising candidates for future energy storage systems, mainly due to their high potential capacity. However low sulphur utilization and capacity fading hinder practical realizations. In order to improve understanding of the system, we investigate Li/S electrode morphology changes for different ageing steps, using X-ray phase contrast tomography. Thereby we find a strong decrease of sulphur loading after the first cycle, and a constant loading of about 15% of the initial loading afterwards. While cycling, the mean sulphur particle diameters decrease in a qualitatively similar fashion as the discharge capacity fades. The particles spread, migrate into the current collector and accumulate in the upper part again. Simultaneously sulphur particles lose contact area with the conducting network but regain it after ten cycles because their decreasing size results in higher surface areas. Since the capacity still decreases, this regain could be associated with effects such as surface area passivation and increasing charge transfer resistance.

NMR study of cation, anion, and solvent mobilities in macroporous poly(vinylidene fluoride).

The mobilities of lithium, PF6- and solvents in the electrolyte LiPF6-(ethylene carbonate-dimethyl carbonate-diethyl carbonate) were measured using the pulsed gradient spin-echo NMR. They were compared to those of the same electrolyte filling a macroporous poly(vinylidene fluoride) membrane. The conductivity decrease resulting in the incorporation of this macroporous membrane and the cationic transport number were analyzed in terms of (i) solvent/polymer and solvent/salt interactions, (ii) ionic dissociation, and (iii) tortuosity.