Lead-free (1 − x)K0.5Na0.5NbO3–xSr(Yb0.5Nb0.5)O3 (KNN–xSYbN, x = 0.15, 0.175, 0.20, 0.225, 0.25, 0.30) ceramics have been fabricated using the traditional solid-phase sintering method. The effects of Sr(Yb0.5Nb0.5)O3 doping on the microstructure, phase transition, and optical and electrical properties were investigated in detail. X-ray diffraction analysis revealed that the ceramics had pseudocubic phase structure. At x = 0.175, the near-infrared light transmittance of the ceramic reached 43.5% and the optical bandgap Eg was 2.89 eV. After introduction of Sr(Yb0.5Nb0.5)O3, the crystal grains of the ceramic became fine dense small cubes. Excessive doping (x ≥ 0.20) reduced the density of the ceramic and melted the ceramic surface. The ceramic with x = 0.175 exhibited optimized energy storage properties with Wrec = 0.21 J/cm3 and η = 78.2%. The maximum dielectric constant of 1867.9 was obtained at x = 0.175, and its Tm peaks shifted toward lower temperature. The good insulation performance of the ceramics was confirmed by impedance spectroscopy.
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