Wet Spinning of Graphene Oxide Fibers with Different MnO₂ Additives

We present the fabrication of graphene oxide (GO) and manganese dioxide (MnO₂) composite fibers via wet spinning processes, which entails the effects of MnO₂ micromorphology and mass loading on the extrudability of GO/MnO₂ spinning dope and on the properties of resulted composite fibers. Various sizes of rod and sea-urchin shaped MnO₂ microparticles have been synthesized via hydrothermal reactions with different oxidants and hydrothermal conditions. Both the microparticle morphology and mass loading significantly affect the extrudability of the GO/MnO₂ mixture. In addition, the orientation of MnO₂ microparticles within the fibers is largely affected by their microscopic surface areas. The composite fibers have been made electrically conductive via chemical or thermal treatments and then applied as fiber cathodes in Zn-ion battery prototypes. Thermal annealing under an argon atmosphere turns out to be an appropriate method to avoid MnO₂ dissolution and leaching, which have been observed in the chemical treatments. These rGO/MnO₂ fiber cathodes have been assembled into prototype Zn-ion batteries with Zn wire as the anode and xanthan-gum gel containing ZnSO₄ and MnSO₄ salts as the electrolyte. The resulted electrochemical output depends on the annealing temperature and MnO₂ distribution within the fiber cathodes, while the best performer shows stable cycling stability at a maximum capacity of ca. 80 mA h/g.