Phosphorous - Containing Activated Carbon Derived From Natural Honeydew Peel Powers Aqueous Supercapacitors.

The introduction of phosphorous (P), and oxygen (O) heteroatoms in the natural honeydew chemical structure is one of the most effective, and practical approaches to synthesizing activated carbon for possible high-performance energy storage applications. The performance metrics of supercapacitors depend on surface functional groups and high-surface-area electrodes that can play a dominant role in areas that require high-power applications. Here, we report a phosphorous and oxygen co-doped honeydew peel-derived activated carbon (HDP-AC) electrode with low surface area for supercapacitor via H3PO4 activation. This activator form phosphorylation with cellulose fibers in the HDP. The formation of heteroatoms stabilizes the cellulose structure by preventing the formation of levoglucosan (C6H10O5), a cellulose combustion product, which would otherwise offer a pathway for a substantial degradation of cellulose into volatile products. Therefore, heteroatom doping has proved effective, in improving the electrochemical properties.  The improved performance is attributed to the high phosphorous doping with a hierarchical porous structure, which enables the transportation of ions at higher current rates. The high specific capacitance of 486, and 478 F/g at 0.6, and 1.3 A/g in 1M H2SO4 electrolyte with a prominent retention of 98% is observed for 2M H3PO4 having an impregnation ratio of 1:4.

Tuning the Nanoparticle Interfacial Properties and Stability of the Core-Shell Structure in Zn-Doped NiMoO4@AWO4.

The ability to tune the interfacial region in core-shell nanocomposites with a surface reconstruction as a source for surface energy (de)stabilization is presented. We consider Zn-doped nickel molybdate (NiMoO4) (ZNM) as a core crystal structure and AWO4 (A = Co or Mg) as a shell surface. Based on the density-functional theory method, the interfacial models of Zn-doped NiMoO4@AWO4 (ZNM@AW) core@shell structures are simulated and revealed to undergo surface reconstruction on the (-110) and (-202) surfaces of the AW shells, where the surface degradation of ZNM@MW(-110) is observed. The theoretical simulation is validated against the electrochemical performance of supercapacitor studies. To verify, we synthesize the hierarchical ZNM@AW core@shell semiconductor structured nanocomposites grown on a nickel foam conductive substrate using a facile and green two-step hydrothermal method. The morphology and chemical and electrochemical properties of the hierarchically structured nanocomposites are characterized in detail. The performance of the core@shell is significantly affected by the chosen intrinsic properties of metal oxides and exhibited high performance compared to a single-component system in supercapacitors. The proposed asymmetric device, Zn-doped NiMoO4@CoWO4 (ZNM@CW)||activated carbon, exhibits a superior pseudo-capacitance, delivering a high areal capacitance of 0.892 F cm-2 at a current density of 2 mA cm-2 and an excellent cycling stability of 96% retention of its initial capacitance after 1000 charge-discharge cycles. These fundamental theoretical and experimental insights with the extent of the surface reconstruction sufficiently explain the storage properties of the studied materials.

Zn Metal Atom Doping on the Surface Plane of One-Dimesional NiMoO4 Nanorods with Improved Redox Chemistry.

The effect of zinc (Zn) doping and defect formation on the surface of nickel molybdate (NiMoO4) structures with varying Zn content has been studied to produce one-dimensional electrodes and catalysts for electrochemical energy storage and ethanol oxidation, respectively. Zn-doped nickel molybdate (Ni1-xZnxMoO4, where x = 0.1, 0.2, 0.4, and 0.6) nanorods were synthesized by a simple wet chemical route. The optimal amount of Zn is found to be around 0.25 above which the NiMoO4 becomes unstable, resulting in poor electrochemical activity. This result agrees with our density functional theory calculations in which the thermodynamic stability reveals that Ni1-xZnxMoO4 crystallized in the ß-NiMoO4 phase and is found to be stable for x≤0.25. Analytical techniques show direct evidence of the presence of Zn in the NiMoO4 nanorods, which subtly alter the electrocatalytic activity. Compared with pristine NiMoO4, Zn-doped NiMoO4 with the optimized Zn content was tested as an electrode for an asymmetric supercapacitor and demonstrated an enhanced specific capacitance of 122 F g-1 with a high specific energy density of 43 W h kg-1 at a high power density of 384 W kg-1. Our calculations suggest that the good conductivity from Zn doping is attributed to the formation of excess oxygen vacancies and dopants play an important role in enhancing the charge transfer between the surface and OH- ions from the electrolyte. We report electrochemical testing, material characterization, and computational insights and demonstrate that the appropriate amount of Zn in NiMoO4 can improve the storage capacity (∼15%) due to oxygen vacancy interactions.

Role of Additives in Electrochemical Deposition of Ternary Metal Oxide Microspheres for Supercapacitor Applications.

A simple two-step approach has been employed to synthesize a cobalt-nickel-copper ternary metal oxide, involving electrochemical precipitation/deposition followed by calcination. The ternary metal hydroxide gets precipitated/deposited from a nitrate bath at the cathode in the catholyte chamber of a two-compartment diaphragm cell at room temperature having a pH ≈ 3. The microstructure of the ternary hydroxides was modified in situ by two different surfactants such as cetyltrimethylammonium bromide and dodecyltrimethylammonium bromide in the bath aiming for enhanced storage performance in the electrochemical devices. The effect of the surfactant produces a transition from microspheres to nanosheets, and the effect of micelle concentration produces nanospheres at a higher ion concentration. The ternary hydroxides were calcined at 300 °C to obtain the desired ternary mixed oxide materials as the electrode for hybrid supercapacitors. X-ray diffraction analysis confirmed the formation of the ternary metal oxide product. The scanning electron microscopy images associated with energy-dispersive analysis suggest the formation of a nanostructured porous composite. Ternary metal oxide in the absence and presence of a surfactant served as the cathode and activated carbon served as the anode for supercapacitor application. DTAB-added metal oxide showed 95.1% capacitance retention after 1000 cycles, achieving 188 F/g at a current density of 0.1 A/g, and thereafter stable until 5000 cycles, inferring that more transition metals in the oxide along with suitable surfactants at an appropriate micellar concentration may be better for redox reactions and achieving higher electrical conductivity and smaller charge transfer resistance. The role of various metal cations and surfactants as additives in the electrolytic bath has been discussed.

Effect of Transition Metal Cations on Stability Enhancement for Molybdate-Based Hybrid Supercapacitor.

The race for better electrochemical energy storage systems has prompted examination of the stability in the molybdate framework (MMoO4; M = Mn, Co, or Ni) based on a range of transition metal cations from both computational and experimental approaches. Molybdate materials synthesized with controlled nanoscale morphologies (such as nanorods, agglomerated nanostructures, and nanoneedles for Mn, Co, and Ni elements, respectively) have been used as a cathode in hybrid energy storage systems. The computational and experimental data confirms that the MnMoO4 crystallized in ß-form with α-MnMoO4 type whereas Co and Ni cations crystallized in α-form with α-CoMoO4 type structure. Among the various transition metal cations studied, hybrid device comprising NiMoO4 vs activated carbon exhibited excellent electrochemical performance having the specific capacitance 82 F g-1 at a current density of 0.1 A g-1 but the cycling stability needed to be significantly improved. The specific capacitance of the NiMoO4 electrode material is shown to be directly related to the surface area of the electrode/electrolyte interface, but the CoMoO4 and MnMoO4 favored a bulk formation that could be suitable for structural stability. The useful insights from the electronic structure analysis and effective mass have been provided to demonstrate the role of cations in the molybdate structure and its influence in electrochemical energy storage. With improved cycling stability, NiMoO4 can be suitable for renewable energy storage. Overall, this study will enable the development of next generation molybdate materials with multiple cation substitution resulting in better cycling stability and higher specific capacitance.

Correlation among physical and electrochemical behaviour of nanostructured electrolytic manganese dioxide from leach liquor and synthetic for aqueous asymmetric capacitor.

An attempt has been made to correlate the differences in structural parameters, surface areas, morphology etc. with the electrochemical capacitive behaviour of the EMDs. The nanostructured electrolytic manganese dioxides (EMD) have been synthesized through electrodepositing MnO2 from two different leach liquors and a synthetic analogue thereof. The structural and chemical state was determined using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) respectively. Multiplet structure determination led to estimates of the manganese valence states present in the EMD. The EMDs have been tested in an asymmetric capacitor which we have developed. This used activated carbon as the negative electrode and the various EMDs as the positive electrode. Aqueous 2 M NaOH solution was used as the electrolyte. The capacitor achieved 1.6 V corresponding to a capacitance of ∼50 F g(-1) of the EMDs from leach liquors. The EMD derived from the synthetic solution showed an inferior capacitance of 25 F g(-1). Extended cycling (2000 cycles), showed 100% capacity retention was achieved for one EMD produced from the leach liquor derived from low-grade manganese ore/residue. This outstanding capacitor performance was correlated with the presence of a nanofibrous morphology. These findings open up the possibility of extracting a high performance EMD product from a low cost, low-grade source of manganese.