Nanofibrous solid polymer electrolytes were prepared using the electrospinning method. These nanofibres were constructed from poly(ethylene oxide), lithium perchlorate and ethylene carbonate, which were incorporated with multi‐walled carbon nanotube (MWCNT) and graphene oxide (GO). The morphological properties of the as‐prepared electrolytes and the interaction between the components of the composites were characterized using scanning electron microscopy and Fourier transform infrared spectroscopy, respectively. X‐ray spectra and differential scanning calorimetry indicated an increase in amorphous regions of the nanofibrous electrolytes on addition of the fillers. However, the crystalline regions were increased on incorporation of fillers into polymeric film electrolytes. The conductivity values of the nanofibrous electrolytes reached 0.048 and 0.057 mS cm−1 when 0.35 wt% MWCNT and 0.21 wt % GO were introduced into the nanofibrous structures, respectively. The capacity and cycling stability of the nanofibrous electrolytes were improved by incorporation of MWCNT filler. Furthermore, stress and elongation modulus were improved at low MWCNT and GO filler contents. Results revealed that the nanofibrous structures could be promising candidates as solvent‐free electrolytes applicable in lithium ion batteries. © 2019 Society of Chemical Industry

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