context: The electrochemical data were collected using assembled 2032-coin cells. The cathode electrode was prepared by mixing the as-prepared MVO microspheres or V2O5·nH2O, carbon black and polytetrafluoroethylene (PTFE) binder in a weight ratio of 6:3:1. The coin cells were assembled using the prepared cathode, zinc metal as the anode, and the prepared PAM–CNF film as the electrolyte and separator. Galvanostatic charge/discharge electrochemical tests were performed on an eight-channel LAND battery analyzer (CT3001A, LAND Electronics Corporation, Wuhan, China) in the voltage range of 0.2–1.6 V. Cyclic voltammetry (CV) measurements were carried out on an electrochemical workstation (CHI 760e) in the potential range of 0.2–1.6 V. Electrochemical impedance spectroscopy (EIS) was carried out by applying an AC potential of 5 mV amplitude in the frequency range of 0.01–100 kHz. A freeze-resistance test was carried out at −18 °C in a freezer. Heat-resistance properties were tested in an EQ-DHG-9015 oven (MTI Inc., Richmond, CA, USA).