Operando Synchrotron X-ray Diffraction Studies on TiS2: The Effect of Propylene Carbonate on Reduction Mechanism

We present herein a systematic study of solvent co-intercalation during electrochemical reduction of titanium disulfide in lithium cells using state of the art in situ cells and synchrotron X-ray diffraction. To understand the role of the electrolyte components, four salts (LiBF4, LiBOB, LiPF6 and LiTFSI) and three solvents (ethylene carbonate, propylene carbonate and dimethyl carbonate) were investigated. Various types of in situ cells were assembled and X-ray diffraction patterns were collected in operando upon cycling. Co-intercalated phase formation was found to be triggered by the presence of propylene carbonate and to be electrochemically driven. This co-intercalated phase is formed in the early stages of reduction, with cell parameters a = 3.514 angstrom, c = 17.931 angstrom, corresponding approximately to a tripling of the pristine TiS2 cell along the c-axis. This phase does not seem to evolve upon further oxidation and hence induces an overall loss of capacity. Whereas the nature of the anion does not appear to influence the co-intercalated phase formation, the content of propylene carbonate in the electrolyte is clearly correlated to both its amount and the extent of capacity loss.

Automated summary

In this study, a systematic investigation was conducted on solvent co-intercalation during the electrochemical reduction of titanium disulfide in lithium cells. It was found that the formation of co-intercalated phase is mainly triggered by the presence of propylene carbonate, and the extent of capacity loss is correlated to the content of propylene carbonate in the electrolyte.