Herein, the influence of nanosized amorphous intermediate domains such as Na3Bi and NaGe on the electrochemical characteristics of the new Na2O–Bi2O3 glass anode network mixed with “GeO2” nanocrystals is highlighted. High‐resolution transmission electron microscopy pictures are evident of Bi2O3 and GeO2 crystals in the amorphous plain bright Na–Bi glass phase which is also justified in the X‐ray diffraction studies. The initial (1st) and final (500th) charge and discharge capacities are recorded to be 1097/783 and 621/614, respectively. The columbic efficiency ranged between 71% and 98.8% as the current rate varies from 0.1 to 5 C. The ionic conductivity achieved is quite high even for the 500th cycle. This is due to the lowest value of R ct in the electro impedance spectroscopy spectra, which indicates a rise in electronic conductivity. The appreciable results obtained in this investigation create potential interest in designing and developing various glass and glass–ceramic anodes for large‐scale energy storage applications.

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