Mesoscale Morphological Control of Electrodeposited Manganese Dioxide Films

doi:10.1016/j.electacta.2015.04.036

Electrochimica Acta

Volume 170, 10 July 2015, Pages 343-352

https://doi.org/10.1016/j.electacta.2015.04.036 Get rights and content

Abstract

Multilayered films of hybrid manganese dioxide have been synthesised in an anodic pulse deposition study with the addition of phosphotungstic acid, H₃PW₁₂O₄₀ (PW) to an acidified MnSO₄ solution. These hybrid materials exhibit tuneable layered morphologies, which is not present in material synthesised in the absence of PW. Cyclic voltammetry analyses have been performed in situ on single pulse thin film depositions synthesised in the presence of varying concentrations of PW, where minor amounts of PW improves the cycle stability of the material, however larger concentrations lead to a degradation in material performance. In situ electrochemical analysis shows that the incorporated PW clusters do not affect material activity, however they do play a role in defining both meso- and micro-structure.

Section snippets

INTRODUCTION

The world in which we live is becoming increasingly reliant on energy storage devices for use in a wide range of applications including small scale consumer electronics and in larger devices such as electric or hybrid electric vehicles employing regenerative braking technology [1]. Many energy storage technologies exist, but those classified as electrochemical energy storage are receiving considerable attention at present in the scientific literature. These technologies include batteries,

Materials

The main materials used in this work were MnSO₄.2H₂O (≥99.99%), H₃PW₁₂O₄₀.xH₂O (PW; >97%), concentrated H₂SO₄ (98%), and Na₂SO₄ (≥99%), all of which were sourced from Sigma-Aldrich. Any solutions that were prepared were made using Milli-Q ultra-pure water (>18 MΩ.cm resistivity). The water content of the extremely hygroscopic H₃PW₁₂O₄₀.xH₂O was determined using a Perkin Elmer Diamond TGA-DTA by heating at 1 °C/min under nitrogen from ambient to 600 °C.

Electrochemical Cell

The electrochemical cell used for both

Linear Sweep Voltammetry (LSV)

Fig. 1 shows an example of a linear sweep voltammogram of the electrodeposition of manganese dioxide from an electrolyte of 0.01 M MnSO₄ + 0.1 M H₂SO₄. The voltammogram shows a peak for the oxidation of Mn²⁺ to MnO₂ at ∼1.15 V corresponding to the transition from kinetically limited oxidation to diffusion limited oxidation; i.e.,Mn²⁺ + 2H₂O → MnO₂ + 4H⁺ + 2e⁻

At higher potentials the current density increases exponentially, corresponding to the oxygen evolution reaction; i.e.,2H₂O → O₂ + 4H⁺ + 2e⁻

This was to be

CONCLUSIONS

The method for layer synthesis detailed here presents a straightforward route for increasing structural control in manganese dioxide thin films. From this study, it appears that a gradual change in the composition of a material during deposition, through use of an additive such as PW, can cause subsequent depositions in a pulsed series to nucleate additional layers rather than continuing a growth regime. The material deposited in subsequent pulses is forced into a new layer, rather than growing

ACKNOWLEDGEMENTS

The authors acknowledge the support of the University of Newcastle for the funding necessary to conduct this research. The authors also wish to acknowledge the Electron Microscope and X-Ray unit at the University of Newcastle, and Victor Wong for the provision of and assistance with the TEM.

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Mesoscale Morphological Control of Electrodeposited Manganese Dioxide Films

Abstract

Section snippets

INTRODUCTION

Materials

Electrochemical Cell

Linear Sweep Voltammetry (LSV)

CONCLUSIONS

ACKNOWLEDGEMENTS

Transportation Research Part D

Electrochimica Acta

Journal of Electroanalytical Chemistry

Journal of Solid State Chemistry

Electrochimica Acta

Journal of Power Sources

Journal of Electroanalytical Chemistry

Journal of Power Sources

Journal of Electroanalytical Chemistry and Interfacial Electrochemistry

Journal of Electroanalytical Chemistry

Electrochimica Acta