Amalgamation of MnWO4 nanorods with amorphous carbon nanotubes for highly stabilized energy efficient supercapacitor electrodes.

Enhanced electrochemical performance of supercapacitors can be achieved through optimal hybridization of electroactive nanomaterials, as it effectively increases the overall surface area and ensures greater electrolyte-electrode interaction. This work reports the realization of a manganese tungstate and amorphous carbon nanotube (MnWO4-aCNT) hybrid and its utilization as the electrodes for a solid-state asymmetric supercapacitor. Large-scale synthesis of aCNTs was carried out via an economical solid-state reaction at low temperature and the walls of these nanotubes were decorated with MnWO4 nanorods via a surfactant-free in situ hydrothermal process. The as-fabricated electrode based on this hybrid over nickel foam delivered a high specific capacitance of 542.18 F g-1 at a scan rate of 2 mV s-1, which is much superior to the values of the structural units separately. This MnWO4-aCNT based electrode showed a high-rate capacity with ∼100% capacitance retention and a coulombic efficiency of ∼100% even after operation for 15 000 cycles. A solid-state asymmetric supercapacitor based on this hybrid attained an energy density of 5.6 W h kg-1 and a power density as high as 893.6 W kg-1. Significantly enhanced electrochemical behaviour registered from the hybrid sample is accounted for by its enhanced surface area and thereby greater number of redox reaction sites along with the positive synergetic effect of the building blocks. This study unlocks further exploration possibilities with other types of aCNT-based hybrid materials for the development of highly stable, non-toxic and cost-effective sustainable energy storage systems.

Negative capacitance switching in size-modulated Fe3O4 nanoparticles with spontaneous non-stoichiometry: confronting its generalized origin in non-ferroelectric materials.

Persistent low-frequency negative capacitance (NC) dispersion has been detected in half-metallic polycrystalline magnetite (Fe3O4) nanoparticles with varying sizes from 13 to 236 nm under the application of moderate dc bias. Using the Havriliak-Negami model, 3D Cole-Cole plots were employed to recapitulate the relaxation times (τ) of the associated oscillating dipoles, related shape parameters (α, ß) and resistivity for the nanoparticles with different sizes. The universal Debye relaxation (UDR) theory requires a modification to address the shifted quasi-static NC-dispersion plane in materials showing both +ve and -ve capacitances about a transition/switching frequency (f0). A consistent blue-shift in 'f0' is observed with increasing external dc field and decreasing particle size. Based on this experimental data, a generalized dispersion scheme is proposed to fit the entire positive and negative capacitance regime, including the diverging transition point. In addition, a comprehensive model is discussed using phasor diagrams to differentiate the underlying mechanisms of the continuous transition from -ve to +ve capacitance involving localized charge recombination or time-dependent injection/displacement currents, which has been adequately explored in the scientific literature, and the newly proposed 'capacitive switching' phenomenon. An inherent non-stoichiometry due to iron vacancies [Fe3(1-δ)O4], duly validated from first principles calculations, builds up p-type nature, which consequently promotes more covalent and heavier dipoles and slows the dipolar relaxations; this is incommensurate with Maxwell-Wagner interfacial polarization (MWIP) dynamics. This combinatorial effect is likely responsible for the sluggish response of the associated dipoles and the stabilization of NC.