The Cathodic Reduction Mechanism of Electrolytic Manganese Dioxide in Alkaline Electrolyte

Kozawa, Akiya; Yeager, J. F.

doi:10.1149/1.2423350

Cited by 190 publications

(144 citation statements)

References 15 publications

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“…Most of the reported literature on EMD material in aqueous solutions is based on the wellknown protonation or lithiation mechanisms. [24][25][26][27][28] In this work, TEM imaging and Rutherford back scattering analyses gave intriguing insights suggesting that the potassium ion may be intercalated in the c-MnO 2 structure. The extent of intercalation depends on the type of surfactant used.…”

Section: The Intense Interest In Manganese Oxides For Energymentioning

confidence: 75%

“…The product obtained is in accordance with the well-known mechanism of c-MnO 2 as an insertion electrode in aqueous KOH electrolyte involves H + insertion forming the manganese oxy hydroxides (MnOOH) and manganese (III) oxide (Mn 3 O 4 ). [24][25][26] The TEM images of the discharged material, on the other hand, show a different but intriguing picture. The TEM images of the cathode (c-MnO 2 ) material prepared in the presence of surfactants before and after discharge are shown in Figure 9.…”

Section: G Electrochemical Activitymentioning

confidence: 99%

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Effect of Non-ionic Surfactants and Its Role in K Intercalation in Electrolytic Manganese Dioxide

Biswal

Tripathy

Subbaiah

et al. 2014

Metallurgical and Materials Transactions E

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The effect of non-ionic surface active agents (surfactants) Triton X-100 (TX-100) and and their role in potassium intercalation in electrolytic manganese dioxide (EMD) produced from manganese cake has been investigated. Electrosynthesis of MnO 2 in the absence or presence of surfactant was carried out from acidic MnSO 4 solution obtained from manganese cake under optimized conditions. A range of characterization techniques, including field emission scanning electron microscopy, transmission electron microscopy (TEM), Rutherford back scattering (RBS), and BET surface area/porosity studies, was carried out to determine the structural and chemical characteristics of the EMD. Galvanostatic (discharge) and potentiostatic (cyclic voltammetric) studies were employed to evaluate the suitability of EMD in combination with KOH electrolyte for alkaline battery applications. The presence of surfactant played an important role in modifying the physicochemical properties of the EMD by increasing the surface area of the material and hence, enhancing its electrochemical performance. The TEM and RBS analyses of the discharged EMD (c-MnO 2 ) material showed clear evidence of potassium intercalation or at least the formation of a film on the MnO 2 surface. The extent of intercalation was greater for EMD deposited in the presence of TX-100. Discharged MnO 2 showed products of Mn 2+ intermediates such as MnOOH and Mn 3 O 4 .

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Section: The Intense Interest In Manganese Oxides For Energymentioning

confidence: 75%

Section: G Electrochemical Activitymentioning

confidence: 99%

Effect of Non-ionic Surfactants and Its Role in K Intercalation in Electrolytic Manganese Dioxide

Biswal

Tripathy

Subbaiah

et al. 2014

Metallurgical and Materials Transactions E

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“…2a). These peaks, which are ascribed to Mn 3+ -Mn 4+ redox reactions in 1M KOH electrolyte, 26,30 differs from the nearly rectangular CV of the Mn oxide in Na 2 SO 4 electrolyte. 2,3 The CV of the Co sample shows one oxidation peak at ca.…”

Section: Resultsmentioning

confidence: 86%

Composite Electrodes Made from Carbon Cloth as Supercapacitor Material and Manganese and Cobalt Oxide as Battery One

Aldama

Barranco

Centeno

et al. 2016

J. Electrochem. Soc.

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Mn oxide and/or Co oxide are deposited on flexible carbon cloth by a cathodic potentiodynamic procedure from their respective sulfates. In KOH electrolyte, the charge stored from reversible redox reactions of the two oxides (battery response) overlaps with the charge stored from the double layer of the carbon cloth (supercapacitor response). These charges or capacities are compared. For the electrodes having one oxide only, either Mn or Co oxide, the highest capacity is obtained for 8 wt% oxide load. To overcome this limitation, both Mn and Co oxide are simultaneously or sequentially electrodeposited on carbon cloth over a broad compositional range. The electrode capacity can reach 71 mA · h · g −1 or 0.9 mA · h · cm −2 , which are higher than the values found for the bare carbon cloth. The electrode capacity depends on the relative content of the carbon cloth and the two deposited oxides according to the rule of mixtures. The decrease of the specific surface area of the carbon cloth is discussed in relation to the deposited oxide. The high capacity retention vs current is due to the contribution of the carbon cloth substrate. The electrode cycle life is discussed on the basis of the supercapacitor response and battery one.

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“…5,6 Amorphous hydrous manganese oxides anodically deposited from MnSO 4 solutions of different pH show an acceptable capacity, high reversibility, and high pulse-power properties for electrochemical supercapacitors. 7,8 For battery-active manganese dioxides used in primary cells ͑␥-and -MnO 2 ), 9 the electroreduction process during the first cycle in alkaline electrolytes has been extensively studied. Kozawa and coworkers observed that the reduction process depends on KOH concentration.…”

mentioning

confidence: 99%

“…Kozawa and coworkers observed that the reduction process depends on KOH concentration. 9,10 Amarilla et al 11 have studied the influence of KOH concentration on the MnO 2 redox mechanism using step potential electrochemical spectroscopy ͑SPECS͒ and X-ray diffraction ͑XRDS͒. In 1 M KOH the voltamperometric and XRD data show that the redox mechanism can be described as a H ϩ /e Ϫ insertion/ desinsertion process with good reversibility.…”

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confidence: 99%

An Ellipsometric Study of Manganese Oxide Films

Ubeda

Pérez

Mishima

et al. 2005

J. Electrochem. Soc.

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The electrodeposition of manganese oxide films onto a platinum substrate was investigated by means of in situ ellipsometry. In the thickness range from 0 to 150 nm, the anodic oxide behaves as an isotropic single layer with optical constants that are independent of thickness. Deviations at higher thickness are explained in terms of anisotropic properties of the film. The electroreduction of thin films ͑up to ca. 150 nm͒ in an alkaline electrolyte leads to a decrease in both the refractive index and the extinction coefficient and is accompanied by a thickness increase of ca. 10%. The Mn͑IV͒ to Mn͑III͒ conversion takes place from the oxide/electrolyte interface inwards. © 2004 The Electrochemical Society. ͓DOI: 10.1149/1.1825951͔ All rights reserved. The wide spread use of MnO 2 for battery electrodes has continued over the years and has been extended today to nonaqueous lithium cells. [1][2][3][4] Manganese dioxide can exist as various polytypes denoted ␣-, ␤-, ␥-, ramsdellite, ␦-and -forms, with the ␥-form, referred to as nsutite, being the most active electrochemically. Among the samples referred to as ␥-MnO 2 and depending on their origin, natural MnO 2 , chemical MnO 2 ͑CMD͒, and electrolytic MnO 2 ͑EMD͒ can be distinguished. The differences are associated to subtle structural changes. Electrolytic MnO 2 films have been prepared using galvanostatic and potentiostatic methods. 5,6 Amorphous hydrous manganese oxides anodically deposited from MnSO 4 solutions of different pH show an acceptable capacity, high reversibility, and high pulse-power properties for electrochemical supercapacitors. 7,8 For battery-active manganese dioxides used in primary cells ͑␥-and -MnO 2 ), 9 the electroreduction process during the first cycle in alkaline electrolytes has been extensively studied. Kozawa and coworkers observed that the reduction process depends on KOH concentration. 9,10 Amarilla et al. 11 have studied the influence of KOH concentration on the MnO 2 redox mechanism using step potential electrochemical spectroscopy ͑SPECS͒ and X-ray diffraction ͑XRDS͒. In 1 M KOH the voltamperometric and XRD data show that the redox mechanism can be described as a H ϩ /e Ϫ insertion/ desinsertion process with good reversibility. For strongly alkaline KOH solutions, a different redox mechanism is observed after the first cycle and a loss of electrochemical activity is also noticed.In general, the reduction of ␥-MnO 2 occurs in two potential regions. The first step corresponds to a homogeneous reduction while the second step is a heterogeneous reduction process. investigated the reduction of electrodeposited manganese dioxide ͑EMD͒, birnessite, and Bi-birnessite electrodes and found that each type of manganese dioxide underwent a homogeneous reduction followed by a heterogeneous reduction stage.The electrochemical process of insertion/desinsertion of H ϩ was investigated by studying its influence on the evolution of the crystallographic structure of ␥-MnO 2 in EMD samples during the discharge and recharge processes of an alkaline batt...

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The Cathodic Reduction Mechanism of Electrolytic Manganese Dioxide in Alkaline Electrolyte

Cited by 190 publications

References 15 publications

Effect of Non-ionic Surfactants and Its Role in K Intercalation in Electrolytic Manganese Dioxide

Effect of Non-ionic Surfactants and Its Role in K Intercalation in Electrolytic Manganese Dioxide

Composite Electrodes Made from Carbon Cloth as Supercapacitor Material and Manganese and Cobalt Oxide as Battery One

An Ellipsometric Study of Manganese Oxide Films

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