No abstract

The challenge for conformal modification of the ultra-high internal surface of nanoporous silicon was tackled by electrochemical polymerisation of 2,6-dihydroxynaphthalene using cyclic voltammetry or potentiometry and, notably, after the thermal treatment (800 °C, N2, 4 h) an assembly of interconnected networks of graphene strongly adhering to nanoporous silicon matrix resulted. Herein we demonstrate the achievement of an easy scalable technology for solid state supercapacitors on silicon, with excellent electrochemical properties. Accordingly, our symmetric supercapacitors (SSC) showed remarkable performance characteristics, comparable to many of the best high-power and/or high-energy carbon-based supercapacitors, their figures of merit matching under battery-like supercapacitor behaviour. Furthermore, the devices displayed high specific capacity values along with enhanced capacity retention even at ultra-high rates for voltage sweep, 5 V/s, or discharge current density, 100 A/g, respectively. The cycling stability tests performed at relatively high discharge current density of 10 A/g indicated good capacity retention, with a superior performance demonstrated for the electrodes obtained under cyclic voltammetry approach, which may be ascribed on the one hand to a better coverage of the porous silicon substrate and, on the other hand, to an improved resilience of the hybrid electrode to pore clogging.

Investigations performed on silicon nanowires of different lengths by scanning electron microscopy revealed coalescence processes in longer nanowires. Using X‐ray diffraction (XRD), it was found that the shape of the pole figure in reciprocal space is ellipsoidal. This is the signature of lattice defects generated by the relaxation of the strain concentrated in the coalescence regions. This observation is strengthened by the deviation of the XRD peaks from Gaussianity and the appearance of the acoustic phonon mode in the Raman spectrum. It implies that bending, torsion and structural defects coexist in the longer nanowires. To separate these effects, a grazing‐incidence XRD technique was conceived which allows the nanowire to be scanned along its entire length. Both ω and ϕ rocking curves were recorded, and their shapes were used to extract the bending and torsion profiles, respectively, along the nanowire length. Dips were found in both profiles of longer nanowires, while they are absent from shorter ones, and these dips correspond to the regions where both bending and torsion relax. The energy dissipated in the nanowires, which tracks the bending and torsion profiles, has been used to estimate the emergent dislocation density in nanowire arrays.