Visualization of Solid-State Synthesis for Chalcogenide Na Superionic Conductors by in-situ Neutron Diffraction

Chalcogenide superionic sodium (Na) conductors have great potential as solid electrolytes (SEs) in all-solid-state Na batteries with advantages of high energy density, safety, and cost effectiveness. The crystal structures and ionically conductive properties of solid Na-ion conductors are strongly influenced by synthetic approaches and processing parameters. Thus, understanding the synthesis process is essential to control the structures and phases and to obtain Na-ion conductors with desirable properties. Thanks to the high-flux and deep-penetrating time-of-flight neutron diffraction (ND), in-situ experiments were able to track real-time structural changes of two chalcogenide SEs (Na3SbS4 and Na3SbS3.5Se0.5) during the solid-state synthesis. For these two conductors, the ND results revealed a fast one-step reaction for the synthesis and the molten process when heating up, and the recrystallization as well as the cubic-to-tetragonal phase transition up on cooling. Moreover, Se-doping was found to influence the reaction temperatures, lattice parameter, and structure stability based on neutron experimental observations and theoretical simulation. This work presents a detailed structural study using in-situ ND technology for the solid synthesis process of chalcogenide Na-ion conductors, beneficial for the design and synthesis of new solid-state conductors.

Automated summary

Chalcogenide superionic sodium conductors show potential as solid electrolytes in all-solid-state sodium batteries, with a detailed study using in-situ neutron diffraction technology revealing the influence of synthesis processes on their structures and properties. The research highlights the importance of understanding the synthesis process for obtaining solid-state conductors with desirable performance.