All ToF-SIMS data was acquired on an M6 Hybrid SIMS (IONTOF GmbH, Münster, Germany).

Measurements were conducted with the Analyzer setting "All Purpose" and LMIG setting "Spectrometry" with 700 µm aperture and Bi3+ as primary ion species in an area of 100x100 µm and 128x128 pixel. Dose density limit per measurement was set to 5E11 ions/cm^-2.

Folder structure:
Operando_LiI_S_C_LPSCl_txt_Export: Containing the positive and negative polarity spectra before connecting the potentiostat and after full discharge of the operando experiment in .txt format.
Operando_LiI_S_C_LPSCl_txt_Export/Oxidation: Containing the first 24 positive and negative polarity spectra of the operando experiment (Charge and OCV) in .txt format.
Operando_LiI_S_C_LPSCl_txt_Export/Reduction: Containing the following 12 positive and negative polarity spectra of the operando experiment (Discharge) in .txt format.

Operando_LPSCl_Carbon_txt_Export: Containing the 26 positive and negative polarity spectra of the operando experiment (charge & discharge) using only LPSCl with carbon as cathode composite in .txt format.

Reference LiI_S_C_LPSCl_without Electrochemistry_txt_Export: Containing the 36 positive and negative polarity spectra of the reference cathode without electrochemical influence in .txt format.

Reference LPSCl_Carbon_without Electrochemistry_txt_Export: Containing the 26 positive and negative polarity spectra of the reference cathode using only LPSCl with carbon as cathode composite without electrochemical influence in .txt format.

Reference_Cathode_Materials_containing_sulfur: Containing the positive and negative polarity spectra (3 per sample) of the pristine sulfur-containing materials LPSCl, Li2S and elemental sulfur (S) in .txt format.


The timestamps of the spectra acquisition for correlation with the electrochemical data are given in the .txt files "Timestamps_LiS_LiI_Operando_Oxidation.txt", "Timestamps_LiS_LiI_Operando_Reduction.txt" and "Timestamps_LPSCl_C_Operando".

Mass interval lists for lower and upper limit of the respective signal assignments in negative and positive polarity were exported from the first ToF-SIMS measurements of the LiI_S_LPSCl_C_cathode experiment.

Extracted intensities of the operando measurements are listed in "Operando_LiI_S_C_LPSCl_Negative_Intensities.txt", "Operando_LiI_S_C_LPSCl_Positive_Intensities.txt", "Operando_LPSCl_C_Negative_Intensities.txt", "Operando_LPSCl_C_Positive_Intensities.txt".