Stability-superconductivity map for compressed Na-intercalated graphite

Abstract

A recent ab initio investigation of Na-C binary compounds under moderate pressures has uncovered a possible stable NaC$_4$ superconductor with an estimated critical temperature up to 41K. We revisit this promising binary system by performing a more focused exploration of Na-intercalated graphite configurations, assessing the sensitivity of their thermodynamic stability to density functional approximations at different (T,P) conditions, and examining their superconducting properties with the anisotropic Migdal-Eliashberg formalism. The combinatorial screening of possible Na arrangements reveals additional stable stoichiometries, i.e., Na$_3$C$_{10}$, NaC$_8$, NaC$_{10}$, and NaC$_{12}$, that redefine the previously proposed convex hulls for pressures up to 10 GPa. The evaluation of formation enthalpies with different van der Waals functionals indicates that the proposed compounds might not be thermodynamically stable at zero temperature but some of them could stabilize due to the vibrational entropy or form via cold compression if graphite is used as a starting material. Our more rigorous modeling of the electron-phonon coupling in NaC$_4$ confirms the material's potential for high-temperature superconductivity, with a critical temperature reaching 48 K at 10 GPa, and reveals a well-defined two-gap structure unusual for an electron-doped compound. By tracking the position of the intercalant nearly free electron states with respect to the Fermi level in viable Na-C compounds, we map out the range of pressures and compositions needed for strong electron-phonon coupling and identify Na$_3$C$_{10}$ as an equally promising superconductor.