Abstract
Tailoring the electronic or ionic conduction properties of solid-state electrolytes with precision is essential to fulfilling the functional demands of electrochemical energy storage and conversion technologies. Here, the synergistic regulation of Na(+) and O(2-) ions conduction in the Na(0.96x)Ca(0.04)Nb(0.96)Zr(0.04)O(3-δ) conductor is achieved by the non-stoichiometric ratio strategy. Crystal structure and electrical property analyses reveal that all samples feature a Pbma orthorhombic structure. With rising Na content, the defect characteristics shift from vacancies to interstitials, the NbO(6) octahedra experience a change from being compressed to normal and then to being obliquely flattened, which leads to an expansion of the corresponding interstitials in the Na-O-Na and Na-O-Nb networks. By changing the structures of these three types of polyhedron and networks, the conduction channels of Na(+) and O(2-) ions as well as electrons can be effectively regulated. The O(2-) ions are the main charge carriers for Na-deficient samples, stoichiometric samples feature the mixed O(2-) ions and intrinsic electrons, while Na⁺ ions become the dominant carriers for Na-excess samples. This work highlights the important role of lattice defects and oxygen octahedral distortions/twisting on the conductivity, offering insights into the design of and Na(+)/O(2-) ions migration pathways in solid-state ion conductors.