Using a combination of crystal structure search methods, first-principles calculations, and machine learning potential based simulations, we explored the lithium-lead system and predicted five phases: $I_4$/mcm ${\mathrm{LiPb}}_2$, Pnma LiPb, $I_4$/mmm ${\mathrm{Li}}_4\mathrm{Pb}, C2/m {\mathrm{Li}}_5\mathrm{Pb}$, and Cmcm ${\mathrm{Li}}_6\mathrm{Pb}$. Among them, $I_4$/mmm ${\mathrm{Li}}_4\mathrm{Pb}$ displayed remarkable properties, including superconductivity, plasticity, and superionic behavior at varying temperature ranges. At lower temperatures, $I_4$/mmm ${\mathrm{Li}}_4\mathrm{Pb}$ manifests superconductivity with a critical transition temperature of 4–5 K. Its superconducting behavior is attributed to the interplay between the $B_2$ _g vibration mode, which signifies the rotational motion of four-membered lithium rings within the stacking layer, and the participation of $p$-orbital electrons. As temperature rises, $I_4$/mmm ${\mathrm{Li}}_4\mathrm{Pb}$ first transitions into a plastic phase, marked by continuous collective rotation of intralayer four-membered lithium rings, and then shows superionic behavior characterized by the emergence of interlayer lithium atom diffusion. These unique behaviors stem from stronger Li-Li bonds within four-membered lithium rings and a lower energy barrier for collective motion, distinct from interstitial localized electrons in electrides found in other lithium-based systems. This work provides an intriguing platform for exploring distinct states and establishes a correlation between various physical phenomena and the system's structure and bonding.

Close

PrevNext

View figure in article

• Crystal structure
• Liquid-solid phase transition
• Pressure effects
• Structural phase transition
• Superconductivity
• Ab initio molecular dynamics
• First-principles calculations
• Machine learning