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.

Low-temperature synthesis of high-entropy amorphous metal oxides (HEOs) for enhanced oxygen evolution performance.

The rational design of multiple metal ions into high-entropy oxide electrode material via a single-step hydrothermal process is applicable to the evolution of oxygen molecules (O2) through simple water electrolysis. Their cost-effectiveness, high performance, and durable nature are the key factors of non-precious high-entropy multiple metal-based electrocatalysts, which can be used as replaceable catalysts instead of precious ones. This article reports a low-temperature synthesis of the cauliflower-type morphology of high-entropy amorphous metal oxides, and their electrochemical performances towards the oxygen evolution reaction (OER) are investigated. The multiple metal ion (Mn2+, Fe3+, Co2+, Ni2+, Cu2+) oxide electrode material shows an acceptable oxygen evolution reaction (OER) with an overpotential of 290 mV at a current density of 10 mA cm-2 and a lower Tafel slope value of 85 mV dec-1, respectively. Moreover, the 20 h durability test with negligible change in overpotential shows the efficacy of the modified electrode material in harsh alkaline media. The observed electrochemical results towards the OER correspond to the amorphous nature of the active material that displayed a cauliflower-type morphology, having a large specific surface area (240 m2 g-1) and providing higher electrochemical active sites as well. Consequently, post-stability characterization studies (such as PXRD, FESEM, TEM, and XPS) provide more information for understanding the post-structural and morphological results of the high-entropy amorphous metal oxide.

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.

Facile synthesis of a nanoporous sea sponge architecture in a binary metal oxide.

A novel galvanostatic electrochemical technique has been employed to synthesize a cobalt-nickel mixed oxide, a binary metal oxide, via a two-step route involving electrodeposition followed by calcination. A diaphragm cell was used for the electro-deposition of the binary hydroxide at room temperature in which the electrolyte comprises a nitrate and/or sulphate bath of the corresponding metal ions at pH 4. The electrodeposited product was calcined at 300 °C to obtain the desired oxide material. The formation of the binary metal oxide has been confirmed by X-ray diffraction analysis. The scanning electron microscopy images associated with energy dispersive analysis (EDS) suggest the formation of a nanoporous sea sponge architecture consisting of an interconnected array of nanosheets aligned perpendicular to each other. The elemental mapping analysis of the binary oxide illustrated the uniformity in the distribution of Co and Ni in the composite material. The TEM image shows that binary oxides are nanocrystalline materials. A nitrogen adsorption-desorption study supports the pore size distribution behaviour of the synthesized material. The hybrid capacitor based on the binary metal oxide cathode and activated carbon anode displayed a capacitive behaviour with a capacitance of 76 F g-1 at a current rate of 2 mA with 98% efficiency after 1000 cycles. Due to the unique interconnected porous network and the role of binary cations, Co-Ni oxide exhibits superior electrochemical behaviour. The synthesis of binary oxides forming various morphologies, such as hexagonal, flower-shape, and sea sponge has been discussed.

Probing the electrochemical properties of biopolymer modified EMD nanoflakes through electrodeposition for high performance alkaline batteries.

In the present work, a novel biopolymer approach has been made to electrodeposit manganese dioxide from manganese sulphate in a sulphuric acid bath containing chitosan in the absence and presence of glutaraldehyde as a cross-linking agent. Galvanostatically synthesised electrolytic manganese dioxide (EMD) nanoflakes were used as electrode materials and their electrochemical properties with the influence of biopolymer chitosan were systematically characterized. The structural determination, surface morphology and porosity of nanostructured EMD were evaluated using X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy and nitrogen adsorption-desorption techniques. The results obtained were compared with that of blank EMD (polymer free). The results indicated that the EMD having chitosan cross-linked with glutaraldehyde possesses a reduced particle size and more porous structure than the blank and EMDs synthesized in the presence of chitosan but without glutaraldehyde. The results revealed that chitosan was unable to play any significant role on its own but chitosan in the presence of glutaraldehyde forms a cross-linking structure, which in turn influences the nucleation and growth of the EMDs during electrodeposition. EMDs obtained in the presence of chitosan (1 g dm(-3)) and glutaraldehyde (1% glutaraldehyde) exhibited a reversible and better discharge capacity upon cycling than the blank which showed its typical capacity fading behaviour with cycling. In addition, EMD synthesized in the presence of 1 g dm(-3) chitosan and 2% glutaraldehyde exhibited a superior electrochemical performance than the blank and lower amounts (1%; 1.5%) of glutaraldehyde, showing a stable discharge capacity of 60 mA h g(-1) recorded up to 40 cycles in alkaline KOH electrolyte for a Zn-MnO2 system. Our results demonstrate the potential of using polymer modified EMDs as a new generation of alkaline battery materials. The XPS data show that a surface functional moiety arising from the cross-linked chitosan enhances the electrochemical properties of the Zn-MnO2 system.

Electrodeposition of Pluronic F127 assisted rod-like EMD/carbon arrays for efficient energy storage.

In the traditional Duracell battery, the results obtained to date remain marginal in terms of cyclability. The development of the existing Zn-MnO2 with superior electrochemical performance for use in alkaline rechargeable batteries is reported. Electrolytic manganese dioxide (EMD) was synthesized from a conventional manganese sulphate bath but having a unique non-ionic surfactant (Pluronic F127), and activated carbon, in an electrolytic cell. The surface areas and morphologies of the as-prepared EMDs were influenced by the presence of these novel additives in the solution while the X-ray data revealed that there was no noticeable change in the crystal orientations thus all the EMDs were structurally similar. The synergistic effect of the optimal ratio of surfactant to carbon powder produced rod-like arrays exhibiting a larger surface area, which facilitates ion transport for better energy storage. It is interesting to note that EMD deposited in the presence of F127 showed better cyclability whereas in the presence of carbon, although it showed better storage capability, it was endowed with poor efficiency when compared with the surfactant added sample, nevertheless the results are better than the existing Zn-MnO2 technology (additive free EMD). Therefore, both the surfactant (50 mg dm(-3)) and the activated carbon (5 g dm(-3)) have been added together in the bath and the resultant EMD exhibits a high specific capacity and an excellent cycling stability. Moreover, the presence of surfactant and activated carbon improved the discharge capacity and its retention thus making this alkaline technology feasible for storing renewable energy for future use. The synergistic effect and the mechanism involved have been discussed.