Preparation and properties of electrolyc manganese dioxide

Rethinaraj, J. Prabhakar; Visvanathan, Susan

doi:10.1016/0378-7753(93)90001-h

Cited by 22 publications

(6 citation statements)

References 8 publications

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“…Although its use in alkaline batteries dates back about 40 years, there remains a technology drive to improve its rechargeability. [11][12][13][14][15][16] Low production cost, low environmental impact, high redox potential, high rate capability, better relative performance over a wide temperature range, and long storage life 15,[17][18][19] are distinct features of pure EMD. In improving the quality of EMD, surfactants play a role by modifying the microstructure, which in turn affects the electrochemical activity of the EMD.…”

mentioning

confidence: 99%

Dual Effect of Anionic Surfactants in the Electrodeposited MnO₂Trafficking Redox Ions for Energy Storage

Biswal

Tripathy

Subbaiah

et al. 2014

J. Electrochem. Soc.

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The dual effect of in-situ addition of anionic surfactants, sodium octyl sulfate (SOS), sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfate (STS) on the microstructure and electrochemical properties of electrolytic manganese dioxide (EMD) produced from waste low grade manganese residue is discussed. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), BET-surface area studies, thermogravimetry-differential thermal analysis (TG-DTA) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structure and chemistry of the EMD. All EMD samples were found to contain predominantly γ-phase MnO 2 , which is electrochemically active for energy storage applications. FESEM images showed that needle, rod and flower shaped nano-particles with a porous surface and platy nano-particles were obtained in the case of EMD deposited with and without surfactant respectively. Thermal studies showed loss of structural water and formation of lower manganese oxides indicating high stability of the EMD samples. The cyclic voltammetry and charge -discharge characteristics implied the presence of surfactants enhances the energy storage within the MnO 2 structure. Addition of the surfactant at its optimum concentration greatly increased the EMD surface area, which in turn improved the cycle life of the EMD cathode. EMD obtained in the presence of 25, 50, 25 ppm of SOS, SDS, and STS respectively showed an improved cycle life relative to the EMD obtained in the absence of surfactant. EMD obtained without surfactant showed a capacity fade of 20 mAh g −1 within 15 discharge-charge cycles, while surfactant modified samples showed stable cyclic behavior of capacity 95 mAh g −1 even after 15 cycles. Global demand for new energy materials and energy storage devices is increasing rapidly and in parallel with the quest for alternative energy resources. Substantial research and development effort continues to be invested in the synthesis of an economically viable, ecofriendly storage device from a natural source. Among the various energy storage devices, alkaline rechargeable batteries have become the ultimate choice for energy storage systems in the portable electronics market as well as electric transport systems.1-3 Worldwide research and development programs in this area have been underway for more than a century, 2 with most attention focused on Zn-Mn, Ni-Cd, Ni-Fe, Ni-Zn, Ni-MH, and Li-ion rechargeable systems.4 Among these, ZnMn alkaline batteries have held a strong position in the battery market for many decades.Manganese dioxide, used as the active material in Zn-MnO 2 batteries, can be prepared both by chemical synthesis (chemical manganese dioxide, CMD) or electrochemical deposition (electrodeposited manganese dioxide, EMD) methods. Adequate primary Mn resources are available from which manganese dioxide can be produced, but the rapidly growing demand for manganese/manganese oxide has made it increasingly important to develop processes for economic recovery of manganese from low-grade mang...

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confidence: 99%

Dual Effect of Anionic Surfactants in the Electrodeposited MnO₂Trafficking Redox Ions for Energy Storage

Biswal

Tripathy

Subbaiah

et al. 2014

J. Electrochem. Soc.

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“…56.0 and 66.7° are observed. Previous work reported that γ-MnO 2 could be preferentially electrodeposited in H 2 SO 4 containing Mn ions. − We hypothesize that MnN 0.84 will be dissolved to obtain Mn ions in the electrolyte during the anodic scan and the dissolved Mn ions can be redeposited as MnO x on the surface of MnN 0.84 . To test this hypothesis, we prepared electrolytic manganese dioxide (EMD) by electrodeposition from manganese sulfate/sulfuric acid electrolytes.…”

Section: Results and Discussionmentioning

confidence: 90%

Sandwich-like MnO_x/MnN_0.84/Mn Electrode toward Improved Electrocatalytic Oxygen Evolution in Acidic Media

Xu,

Ma,

Long

et al. 2024

ACS Appl. Eng. Mater.

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Developing efficient and robust noble-metal-free electrocatalysts capable of catalyzing water oxidation in acidic media is highly desirable for producing H 2 while it remains a great challenge. Herein, a selfsupported MnO x /MnN 0.84 /Mn electrode with a sandwich-like configuration was prepared by consecutive steps involving a nitridation treatment and an in situ electrochemical activation process. The electrode requires overpotentials of ca. 475 and 571 mV at current densities of 10 and 100 mA cm −2 , respectively, for the oxygen evolution reaction (OER) in 1.0 M H 2 SO 4 . More impressively, the electrode remains stable for over 300 h of continuous operation at a current density of 100 mA cm −2 , which is, as far as we know, among the best values reported for Mn-based materials in the field of acidic water electrolysis. It is found that the metallic MnN 0.84 layer is not only the precursor for the formation of MnO x nanosheet electrocatalysts as the actual catalyst for the OER but also enables efficient charge transfer between the active sites at the surface and the substrate. Moreover, the anticorrosive MnN 0.84 interlayer that acts as the binder between the Mn substrate and the MnO x catalyst can protect the Mn substrate from corrosion in acidic electrolytes, highlighting the importance of interlayer modification in stabilizing electrocatalysts in harsh reaction conditions.

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“…At 50 °C, there was a mixture of ɛ-MnO 2 and 𝛾-MnO 2 , while at 90 °C 𝛾-MnO 2 was the only morph deposited. Though in the industry and research field, preparation of electrolytic manganese dioxide (mainly 𝛾-MnO 2 ) at high temperature has been reported for the application in alkaline batteries, lithium manganese primary batteries, and supercapacitors, [51][52][53] this temperature-dependent polymorphism tuning is seldom reported for cycling Mn-based aqueous batteries under a two-electron transfer mechanism. In the corresponding XRD spectra (Figure 3b), the increasing peak intensities at 2𝜃 = 10.0 o (Mo sources) and the decreasing peak intensities at 2𝜃 = 29.4 o (Mo sources) were in accord with such a crystallographic transition.…”

Section: Polymorph Tuning Of the Electrochemically Deposited Mno 2 Vi...mentioning

confidence: 99%

Ultrahigh‐Loading Manganese‐Based Electrodes for Aqueous Batteries via Polymorph Tuning

Xiao

Zhang

et al. 2023

Advanced Materials

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Manganese‐based aqueous batteries utilizing Mn2+/MnO2 redox reactions are promising choices for grid‐scale energy storage due to their high theoretical specific capacity, high power capability, low‐cost, and intrinsic safety with water‐based electrolytes. However, the application of such systems is hindered by the insulating nature of deposited MnO2, resulting in low normalized areal loading (0.005–0.05 mAh cm−2) during the charge/discharge cycle. In this work, the electrochemical performance of various MnO2 polymorphs in Mn2+/MnO2 redox reactions is investigated, and ɛ‐MnO2 with low conductivity is determined to be the primary electrochemically deposited phase in normal acidic aqueous electrolyte. It is found that increasing the temperature can change the deposited phase from ɛ‐MnO2 with low conductivity to γ‐MnO2 with two order of magnitude increase in conductivity. It is demonstrated that the highly conductive γ‐MnO2 can be effectively exploited for ultrahigh areal loading electrode, and a normalized areal loading of 33 mAh cm−2 is achieved. At a mild temperature of 50 °C, cells are cycled with an ultrahigh areal loading of 20 mAh cm−2 (1–2 orders of magnitude higher than previous studies) for over 200 cycles with only 13% capacity loss.

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Preparation and properties of electrolyc manganese dioxide

Cited by 22 publications

References 8 publications

Dual Effect of Anionic Surfactants in the Electrodeposited MnO₂Trafficking Redox Ions for Energy Storage

Dual Effect of Anionic Surfactants in the Electrodeposited MnO₂Trafficking Redox Ions for Energy Storage

Sandwich-like MnO_x/MnN_0.84/Mn Electrode toward Improved Electrocatalytic Oxygen Evolution in Acidic Media

Ultrahigh‐Loading Manganese‐Based Electrodes for Aqueous Batteries via Polymorph Tuning

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Preparation and properties of electrolyc manganese dioxide

Cited by 22 publications

References 8 publications

Dual Effect of Anionic Surfactants in the Electrodeposited MnO2Trafficking Redox Ions for Energy Storage

Dual Effect of Anionic Surfactants in the Electrodeposited MnO2Trafficking Redox Ions for Energy Storage

Sandwich-like MnOx/MnN0.84/Mn Electrode toward Improved Electrocatalytic Oxygen Evolution in Acidic Media

Ultrahigh‐Loading Manganese‐Based Electrodes for Aqueous Batteries via Polymorph Tuning

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Dual Effect of Anionic Surfactants in the Electrodeposited MnO₂Trafficking Redox Ions for Energy Storage

Dual Effect of Anionic Surfactants in the Electrodeposited MnO₂Trafficking Redox Ions for Energy Storage

Sandwich-like MnO_x/MnN_0.84/Mn Electrode toward Improved Electrocatalytic Oxygen Evolution in Acidic Media