Primary alkaline battery cathodes a three-scale model

A mathematical model for the galvanostatic discharge and recovery of porous, electrolytic manganese dioxide cathodes, similar to those found within primary alkaline batteries is presented. The phenomena associated with discharge are modeled over three distinct size scales, a cathodic (or macroscopic) scale, a porous manganese oxide particle (or microscopic) scale, and a manganese oxide crystal (or submicroscopic) scale. The physical and chemical coupling between these size scales is included in the model. In addition, the model explicitly accounts for the graphite phase within the cathode. The effects that manganese oxide particle size and proton diffusion have on cathodic discharge and the effects of intraparticle voids and microporous electrode structure are predicted using the model.

Morphological differentiation observed in manganese oxidizing bacterial colonies

Bacteria play a vital role in bringing about Mn(II) oxidation in the natural environment. A study was conducted to identify the potential threat offered by these bacteria in bringing about biomineralisation of manganese dioxide on titanium surfaces exposed to seawater. During the study it was observed that the bacteria such as Pseudomonas and Bacillus formed brown colonies on agar plates amended with Mn2+ indicating their ability to oxidize Mn(II). These colonies showed distinct morphologies when grown on plates containing Mn(II) while they formed normal colonies in the absence of Mn.(II).Hence it is possible that these morphologically distinct structures produced by the bacterial colonies assist these bacteria to perform this function of Mn-oxidation.

Equivalent circuit parameters of the film-covered magnesium/electrolyte interface in Mg/MnO2 dry cells from transient and ac impedance measurements

The electrochemical properties of the film-covered anode/solution interface in the magnesium/ manganese dioxide dry cell have been evaluated. The most plausible electrical equivalent circuit description of the Mg/solution interface with the passive film intact, has been identified. These results are based on the analysis of ac impedance and voltage transient measurements made on the dry cell under conditions which cause no damage to the protective passive film on the anode. The study demonstrates the complementary character of impedance and transient measurements when widely different frequency ranges are sampled in each type of investigation. The values and temperature dependence of the anode-film resistance, film capacitance, double-layer capacitance and charge-transfer resistance of the film-covered magnesium/solution interface have been determined. The magnitude of these values and its implications in understanding the important performance aspects of the magnesium/manganese dioxide dry cell are discussed. The study may be extended, in principle, to Li, Al and Ca batteries.

Equivalent circuit parameters of the film-covered magnesium/electrolyte interface in Mg/MnO2 dry cells from transient and ac impedance measurements

The electrochemical properties of the film-covered anode/solution interface in the magnesium/ manganese dioxide dry cell have been evaluated. The most plausible electrical equivalent circuit description of the Mg/solution interface with the passive film intact, has been identified. These results are based on the analysis of ac impedance and voltage transient measurements made on the dry cell under conditions which cause no damage to the protective passive film on the anode. The study demonstrates the complementary character of impedance and transient measurements when widely different frequency ranges are sampled in each type of investigation. The values and temperature dependence of the anode-film resistance, film capacitance, double-layer capacitance and charge-transfer resistance of the film-covered magnesium/solution interface have been determined. The magnitude of these values and its implications in understanding the important performance aspects of the magnesium/manganese dioxide dry cell are discussed. The study may be extended, in principle, to Li, Al and Ca batteries.

Lithium and oxygen adsorption at the b-MnO2 (110) surface

The adsorption and co-adsorption of lithium and oxygen at the surface of rutile-like manganese dioxide(b-MnO2), which are important in the context of Li–air batteries, are investigated using density functional theory. In the absence of lithium, the most stable surface of b-MnO2, the (110), adsorbs oxygen in the form of peroxo groups bridging between two manganese cations. Conversely, in the absence of excess oxygen, lithium atoms adsorb on the (110) surface at two different sites, which are both tricoordinated to surface oxygen anions, and the adsorption always involves the transfer of one electron from the adatom to one of the five-coordinated manganese cations at the surface, creating (formally) Li+ and Mn3+ species. The co-adsorption of lithium and oxygen leads to the formation of a surface oxide, involving the dissociation of the O2 molecule, where the O adatoms saturate the coordination of surface Mn cations and also bind to the Li adatoms. This process is energetically more favourable than the formation of gas-phase lithium peroxide (Li2O2) monomers, but less favourable than the formation of Li2O2 bulk. These results suggest that the presence of b-MnO2 in the cathode of a nonaqueous Li–O2 battery lowers the energy for the initial reduction of oxygen during cell discharge.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Description and chemical composition of manganese deposits during the deep-sea expedition of the streamer Valdivia in 1898-1899

This monograph forms the fourth part of the tenth volume of the scientific results of the voyage of the German exploring ship Valdivia in the Atlantic and Indian Oceans, made during the years 1898-1899. These volumes are published under the editorship of Prof. Chun, the zoologist of Leipzig, who was leader of the expedition ; and Prof. E. Philippi with the cooperation of Sir John Murray. The nature of the materials brought up at various points during the voyage is well illustrated by a series of plates, similar to those accompanying the Challenger volumes. Among the concretions from the Agulhas Bank were found phosphatic nodules containing 33 per cent, of calcium carbonate, 28 of calcium phosphate, 14.6 of calcium sulphate, and 4.8 of magnesium carbonate, with some ferric oxide, alumina, and silica. These nodules were dredged at a depth of 155 metres. Off the coast of Namibia, a large quantity of manganese nodules were also dredged. Their chemical analysis performed at the Mineralogical Institute of the University Jena show similar composition as the nodules recovered by the "Challenger" at station 253 in the Pacific Ocean.

Major and minor elements in hydrothermal and pelagic sediments at DSDP Leg 70 Holes

Interaction between young basaltic crust and seawater near the oceanic speading centers is one of the important processes affecting the chemical composition of the oceanic layer. The formation of metalliferous hydrothermal sediments results from this interaction. The importance of the interaction between seawater and basalt in determining the chemical composition of pore waters from sediments is well known. The influence of mineral solutions derived from this interaction on ocean water composition and the significant flux of some elements (e.g., Mn) are reported by Lyle (1976), Bogdanov et al. (1979), and others. Metal-rich sediments found in active zones of the ocean basins illustrate the influence of seawater-basalt interaction and its effect on the sedimentary cover in such areas. The role of hydrothermal activity and seawater circulation in basalts with regard to global geochemistry cycles has recently been demonstrated by Edmond, Measures, McDuff, McDuff et al. (1979), and Edmond, Measures, Mangum (1979). In the area of the Galapagos Spreading Center the interaction of sediments and solutions derived from interaction of seawater and basalt has resulted in the formation of hydrothermal mounds. The mounds are composed of manganese crusts and green clay interbedded and mixed with pelagic nannofossil ooze. These mounds are observed only in areas characterized by high heat flow (Honnorez, et al., 1981) and high hydrothermal activity.

Geochemistry at DSDP Leg 70 Holes

A total of 32 holes at five sites near 1°N, 86°W drilled on Deep Sea Drilling Project (DSDP) Leg 70 (November- December 1979) provide unique data on the origin of the hydrothermal mounds on the southern flank of the Galapagos Spreading Center. Hydrothermal sediments, primarily Mn-oxide and nontronite, are restricted to the immediate vicinity of the mounds (< 100 m) and are probably formed by the interaction of upward-percolating hydrothermal solutions with seawater and pelagic sediments above locally permeable zones of ocean crust. Mounds as high as 25 meters form in less than a few hundred thousand years, and geothermal and geochemical gradients indicate that they are actively forming today. The lack of alteration of upper basement rocks directly below the mounds and throughout the Galapagos region indicates that the source of the hydrothermal solutions is deeper in the crust.

Composition of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus

Detailed data obtained on chemistry of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus that were dated at the Cenomanian/Turonian boundary and formed during Oceanic Anoxic Event 2 make it possible to calculate dissolved oxygen concentration in bottom waters of the sedimentation basin. Enrichment factors of trace elements in black shales are revised and an explanation is suggested for genesis of the rocks with regard for unusual climatic changes.

Documentation of manganese nodules form the northwest Indian Ocean

Microscopic and electron probe examination of some manganese nodules show that they consist of segregations of manganese-iron oxides in an interstitial material almost free of manganese but rich in iron and silicates. The segregations are widely spaced in the volcanic cores of the nodules but become more abundant towards their outer crusts where they form the centres of linked polygons of interstitial materials. Most of the minor elements are concentrated in the segregations compared to the interstitial materials. It is suggested that the structures observed result partly from solution and reprecipitation of elements in the original volcanic cores of the nodules and partly from the replacement and coating of these cores by manganese-iron oxides precipitated from sea water.