Structure and Ionic Conductivity of the Li-disordered Bismuth ortho-Thiophosphate Li60– 3xBi16+x(PS4)36 with x = 4.2 to 6.7

28 March 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The structure of the first lithium containing bismuth ortho-thiophosphate was solved using a combination of powder X-ray, neutron, and electron diffraction. Li60–3xBi16+x(PS4)36 with x in the range of 4.2 to 6.7 possesses a complex monoclinic structure (space group C2/c, no. 15) and a large unit cell with lattice parameters a = 15.487Å, b = 10.323Å, c = 33.767Å, and = 85.394° for Li44.4Bi21.2(PS4)36. The disordered distribution of lithium ions within the interstices of the dense host-structure as well as the Li ion dynamics and diffusion pathways have been investigated by X-ray and neutron PDF analysis, solid-state NMR spectroscopy, PFG-NMR diffusion measurements, and BVS calculations. The total lithium ion conductivities range from 2.6 × 10−7 to 2.8 × 10−6 S cm−1 at 20 °C with activation energies between 0.29 and 0.32 eV, depending on the bismuth content. Despite the highly disordered nature of lithium ions in Li60–3xBi16+x(PS4)36, the underlying dense host-framework appears to limit the dimensionality of the lithium diffusion pathways and emphasizes once more the necessity of a close inspection of structure-property relationships in solid electrolytes.


solid electrolyte

Supplementary materials

Supporting Information
The Supporting Information contains additional data like electron diffraction images and their comparison with the simulation, crystallographic information obtained from the Rietveld refinements of the NPD and PXRD data, ss- NMR spectra of 6Li, 7Li and 31P, Raman spectra, results of the softBV calculations, details about the electrochemical characterization like fitting procedure, Nyquist, Bode and current vs. voltage plots, as well as the results obtained from PFG-NMR.
Crystallographic Information File
Crystallographic Information File obtained from Rietveld refinement of the NPD diffraction data


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