Liquid‐Like Li‐Ion Conduction in Oxides Enabling Anomalously Stable Charge Transport across the Li/Electrolyte Interface in All‐Solid‐State Batteries

The softness of sulfur sublattice and rotational PS4 tetrahedra in thiophosphates result in liquid-like ionic conduction, leading to enhanced ionic conductivities and stable electrode/thiophosphate interfacial ionic transport. However, the existence of liquid-like ionic conduction in rigid oxides remains unclear, and modifications are deemed necessary to achieve stable Li/oxide solid electrolyte interfacial charge transport. In this study, by combining the neutron diffraction survey, geometrical analysis, bond valence site energy analysis, and ab initio molecular dynamics simulation, 1D liquid-like Li-ion conduction is discovered in LiTa2 PO8 and its derivatives, wherein Li-ion migration channels are connected by four- or five-fold oxygen-coordinated interstitial sites. This conduction features a low activation energy (0.2 eV) and short mean residence time (<1 ps) of Li ions on the interstitial sites, originating from the Li-O polyhedral distortion and Li-ion correlation, which are controlled by doping strategies. The liquid-like conduction enables a high ionic conductivity (1.2 mS cm-1 at 30 °C), and a 700 h anomalously stable cycling under 0.2 mA cm-2 for Li/LiTa2 PO8 /Li cells without interfacial modifications. These findings provide principles for the future discovery and design of improved solid electrolytes that do not require modifications to the Li/solid electrolyte interface to achieve stable ionic transport.