We report on a corroborative study of the structural, morphological and electrical property alterations of free-standing graphene oxide (GO) papers subject to thermal reduction. Structural analysis performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman techniques prove that the onset of major structural changes, characterized by removal of oxygen functionalities, occur in the 200–300 °C temperature range. The results are corroborated with related morphological changes observed using Scanning electron microscopy (SEM) and Atomic force microscopy (AFM) imaging. Elemental analysis shows the GO paper reduced at 600 °C to contain an 85 wt. % carbon content and a remnant oxygen level of 13.31 wt. %. At the highest reduction temperatures, we see evidence of vacancy-type defects impeding the overall effectiveness of the reduction process. Detailed electrical resistance measurements and current–voltage (I-V) profiling conducted using four-point probe method reveals a several orders of magnitude drop in the sample resistance once the reduction temperature exceeds 200 °C, in good agreement with the structural and morphological changes. The fundamental insights revealed through these studies will be important for future applications where the electrical and mechanical properties of free-standing GO and reduced graphene oxide (rGO) are exploited in practical devices. Graphical abstract

Free-standing reduced graphene oxide (rGO) has been gaining popularity for its use in supercapacitors and battery applications due its facile synthesis, multilayered structure, and high-current carrying capacity. Pertinent to successful implementation of such applications, however, is the need to develop a thorough understanding of the electrical properties of such materials when subject to high applied electric fields. In this work, we undertake a detailed study of high-field electrical properties of mm-scale, lightly-reduced, rGO papers. Our results reveal that the I-V curves exhibit substantial nonlinearity with associated hysteresis that depends strongly on the applied electric field. The nonlinear behaviour which was interpreted using conventional transport models of Fowler-Nordheim (FN) tunneling and space charge limited conduction (SCLC) revealed that while these models provided good qualitative fits to our data, they were quantitatively lacking, thus leaving the issue of high-field transport mechanisms in rGO open for debate. Careful I-V cycling experiments with measurement time-delay introduced between cycles revealed that the observed hysteresis contained recoverable and non-recoverable parts that we identified as arising from charge trapping and Joule heating effects, respectively. Time-dependent measurements showed that these effects were characterized by two distinct time scales. Importantly, the Joule heating was found to cause a permanent conductivity improvement in the rGO via the "current annealing" effect by effectively eliminating oxygenated groups from the rGO. The analysis of the electrical breakdown in our samples resembled a thermal runaway-like event that resulted in premature damage to the rGO. Finally, we investigated the low-field resistivity in the 80 – 300 K temperature range. The reduced activation energy analysis revealed a robust power law behaviour below 230 K, while deviating from this trend at higher temperatures. For samples that received current annealing treatment, a reduced value for the power law exponent was obtained, confirming the effective lowering of disordered regions.