Rare earth tri‐doped precursor glasses (PGs) were prepared by traditional high‐temperature melting method, and NaSr2Nb5O15 transparent glass–ceramic (GC) was obtained by subsequent heat treatment. Results exhibit that the up‐conversion emission intensity of GC is greatly enhanced compared to PG. Benefiting from the multiple emission bands from Ho3+ and Tm3+ and their different temperature dependence, multi‐ratio optical temperature measurement is realized. The ultimate relative sensitivity (Sr‐max) can reach 2.00% K−1 between 298 and 598 K. It provides a possibility for self‐reference temperature measurement. Furthermore, under the actual charging and discharge conditions, the GC heated at 750°C has great energy density (Wd = 1.15 J/cm3@600 kV/cm) and high‐power density (Pd = 290.4 MW/cm3@600 kV/cm) with ultrafast discharge time (<15.8 ns). The previous results indicate that the obtained GC with good multifunctional properties is expected to be applied in the field of photoelectric conversion.
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