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<p>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<sup>+</sup> and O<sup>2−</sup> ions conduction in the Na<sub>0.96<i>x</i></sub>Ca<sub>0.04</sub>Nb<sub>0.96</sub>Zr<sub>0.04</sub>O<sub>3-<i>δ</i></sub> conductor is achieved by the non-stoichiometric ratio strategy. Crystal structure and electrical property analyses reveal that all samples feature a <i>Pbma</i> orthorhombic structure. With rising Na content, the defect characteristics shift from vacancies to interstitials, the NbO<sub>6</sub> 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<sup>+</sup> and O<sup>2−</sup> ions as well as electrons can be effectively regulated. The O<sup>2−</sup> ions are the main charge carriers for Na-deficient samples, stoichiometric samples feature the mixed O<sup>2−</sup> 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<sup>+</sup>/O<sup>2−</sup> ions migration pathways in solid-state ion conductors.</p>

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Tailoring sodium and oxygen mixed-ion conduction in the A-site non-stoichiometric NaNbO3-based ceramics

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月9日

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  • Zhiyong Liu,
  • Chenggong Xiang,
  • Pengrong Ren,
  • Kun Guo,
  • Bing Xie,
  • Pu Mao,
  • Haijun Sun,
  • Huiqing Fan

摘要

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 O2− ions conduction in the Na0.96xCa0.04Nb0.96Zr0.04O3-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 NbO6 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 O2− ions as well as electrons can be effectively regulated. The O2− ions are the main charge carriers for Na-deficient samples, stoichiometric samples feature the mixed O2− 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+/O2− ions migration pathways in solid-state ion conductors.