Chemical composition of a manganese nodule from the Blake Plateau, Atlantic Ocean

The area surveyed during project AMC-11-67 was the portion of the Blake Plateau between latitude 30°00'N and 33°00'N and between the 100 to 1000 fathom curves. The survey was conducted from 3 October until 18 October 1967. Survey operations included dredgings, camera and multi-sensor lowerings. A collection of manganese and phosphate concretions as well as coral and sediment samples were examined by the ESSA(NOAA) Atlantic Oceanographic Laboratories. Chemical analyses were conducted at the NASA Manned Spacecraft Center, Houston by Richard A. Laidley for X-Ray Fluorescence Analysis and H. Costello for Atomic Absorption Analysis. Later the whole collection of samples was transferred to the Smithsonian National Museum of Natural History were it is available for study (see, http://mineralsciences.si.edu/collections.htm).

(Page 290) Composition of a manganese deposit sample from the Todoroki Mine, Japan

The Todoroki Mine is situated about 25 kilometers to the south-east of Ginzan railway station in Siribesi Province, Hokkaido. The author analysed an interesting specimen of black manganese-ore which had a fractured surface which looked like that of a broken piece of wood. This new manganese mineral was studied in its form, physical properties and chemical composition. The author later named this mineral form as "todorokite".

(Table, page 95) Chemistry of bog manganese concretions and wad from the Columbia County, New York

Bog manganese was long ago reported from various places in Columbia county (1:54) and it seemed well to reexamine these occurrences. According to W. W. Mather in his report of the First District Survey, 1836-42, " in the counties of Columbia and Dutchess 50,000 tons of manganese could be procured without any great expense, if carefully prepared." He also stated that some of the bog manganese showed on analysis as high as 68.5 per cent manganese oxide and less than 5 per cent silica. At the direction of the State Geologist the writer has devoted most of the summer of 191 7 to this work. The results of this investigation, though not in any way confirming the quantitative results of Mr Mather, are herewith published as a matter of record and as an account of the manner of the occurrence and the genesis of postglacial bog manganese.

Description of manganese deposits from the Oriente province in Cuba

Deposits of manganese ore have been found in five of the six provinces of Cuba and have been reported from the sixth. Only Oriente and Pinar del Rio provinces have more than a few known deposits and only the deposits of Oriente have yielded any appreciable amount of ore. In this area the Cobre formation, of late Cretaceous(?) to middle Eocene age, overlies the Vinent formation but their stratigraphie relations are unknown. The Cobre overlies unconformably the Habana(?) formation. The Cobre formation consists of andesitic, basaltic, and dacitic tuff, agglomerate, and lavas with minor amounts of marine clastic and limestone deposits, and a prominent limestone bed, the Charco Redondo limestone member, at the top of the formation. All productive manganese deposits of Oriente are in the Cobre formation, usually within a few tens of meters above or below the base of the Charco Redondo limestone member.

(Table 1, page 1169) Chemical composition of land (fossil) manganese deposits rich in todorokite

Chemical, x-ray and other data are given for todorokite, (Mn, Mg, Ca, Ba, Na, K)2.Mn5O12.3H2O, from Charco Redondo, Cuba, Farragudo, Portugal, and Hüttenberg, Austria. Additional localities at Romanèche, France, Saipan Island, Bahia, Brazil and Sterling Hill, New Jersey, are noted. Delatorreite of Simon and Straczek (1958) is identical with todorokite.

(Table 2, page 1376) Chemical analyses of manganese nodules and crusts from the South-western Pacific

Phosphate deposits which apparently formed during the Miocene climatic optimum are widespread on the Chatham Rise and Camp bell Plateau, and on seamounts in the north Tasman Sea. They formed under oxidising conditions by the phosphatisation of older or contemporaneous foraminiferal oozes (Campbell Plateau and Chatham Rise) and coral limestones (Tasman Sea). The phosphorites of the rise and plateau were formed where current activity was sufficiently strong to prevent normal sedimentation, and now form lag deposits. After the Miocene, phosphorite formation ceased and was followed by manganese oxide deposition where conditions were highly oxidising on the eastern Campbell Plateau and north Tasman seamounts, and by glauconite formation in the much less oxidising environments of the western Campbell Plateau and the Chat ham Rise. The manganese deposits are not volcanogenic, as was formerly thought, but formed by slow precipitation from well oxygenated sea water.

(Table 2) Location, age of accompanied sediments, chemical and Sr isotopic compositions of manganese nodules in DSDP/ODP cores

Strontium isotopic compositions of acetic acid (HOAc) leachate fractions of eight manganese oxide deposits from the modern seafloor, and of twenty-one buried manganese nodules from Cretaceous to Recent sediments in DSDP/ODP cores were measured. ratios of HOAc leachates in all modern seafloor manganese oxides of various origins are identical with present seawater. The ratios of the HOAc leachates of buried nodules from DSDP/ODP cores are significantly lower than those of nodules from the modern seafloor and are mostly identical with coeval seawater values estimated from the age of associated sediments. It is suggested that the buried nodules in DSDP/ODP cores are not artifacts transported from the present seafloor during the drilling process, but are in situ fossil deposits from the past deep-sea floor during Cretaceous to Quaternary periods. The formation of deep-sea fossil nodules prior to the formation of Antarctic Bottom Water (AABW) indicates that the circulation of oxygenated deep seawaters have activately deposited manganese oxides since the Eocene Epoch, or earlier.

Chemical composition of manganese deposits (Birnessite) from Scotland

A manganese pan near Birness contains grains of an optically uniaxial negative mineral near (Na0.7Ca0.3)Mn7O14·2·8H2O, giving an X-ray powder pattern similar to that of synthetic materials described as 'manganous manganite' and delta-MnO2. Material giving a similar pattern has been described from a natural occurrence in Canada, but no mineral name was assigned; the name birnessite is now proposed. The mineral is probably formed by air-oxidation of manganous oxides under alkaline conditions.

INVESTIGATION OF MAGNESIUM ION CHARGE STORAGE MECHANISM IN MANGANESE DIOXIDE

Magnesium (Mg) battery is considered as a promising candidate for the next generation battery technology that could potentially replace the current lithium (Li)-ion batteries due to the following factors. Magnesium possesses a higher volumetric capacity than commercialized Li-ion battery anode materials. Additionally, the low cost and high abundance of Mg compared to Li makes Mg batteries even more attractive. Moreover, unlike metallic Li anodes which have a tendency to develop a dendritic structure on the surface upon the cycling of the battery, Mg metal is known to be free from such a hazardous phenomenon. Due to these merits of Mg as an anode, the topic of rechargea¬ble Mg batteries has attracted considerable attention among researchers in the last few decades. However, the aforementioned advantages of Mg batteries have not been fully utilized due to the serious kinetic limitation of Mg2+ diffusion process in many hosting compounds which is believed to be due to a strong electrostatic interaction between divalent Mg2+ ions and hosting matrix. This serious kinetic hindrance is directly related to the lack of cathode materials for Mg battery that provide comparable electrochemical performances to that of Li-based system. Manganese oxide (MnO2) is one of the most well studied electrode materials due to its excellent electrochemical properties, including high Li+ ion capacity and relatively high operating voltage (i.e., ~ 4 V vs. Li/Li+ for LiMn2O4 and ~ 3.2 V vs. Mg/Mg2+). However, unlike the good electrochemical properties of MnO2 realized in Li-based systems, rather poor electrochemical performances have been reported in Mg based systems, particularly with low capacity and poor cycling performances. While the origin of the observed poor performances is believed to be due to the aforementioned strong ionic interaction between the Mg2+ ions and MnO2 lattice resulting in a limited diffusion of Mg2+ ions in MnO2, very little has been explored regarding the charge storage mechanism of MnO2 with divalent Mg2+ ions. This dissertation investigates the charge storage mechanism of MnO2, focusing on the insertion behaviors of divalent Mg2+ ions and exploring the origins of the limited Mg2+ insertion behavior in MnO2. It is found that the limited Mg2+ capacity in MnO2 can be significantly improved by introducing water molecules in the Mg electrolyte system, where the water molecules effectively mitigated the kinetic hindrance of Mg2+ insertion process. The combination of nanostructured MnO2 electrode and water effect provides a synergic effect demonstrating further enhanced Mg2+ insertion capability. Furthermore, it is demonstrated in this study that pre-cycling MnO2 electrodes in water-containing electrolyte activates MnO2 electrode, after which improved Mg2+ capacity is maintained in dry Mg electrolyte. Based on a series of XPS analysis, a conversion mechanism is proposed where magnesiated MnO2 undergoes a conversion reaction to Mg(OH)2 and MnOx and Mn(OH)y species in the presence of water molecules. This conversion process is believed to be the driving force that generates the improved Mg2+ capacity in MnO2 along with the water molecule’s charge screening effect. Finally, it is discussed that upon a consecutive cycling of MnO2 in the water-containing Mg electrolyte, structural water is generated within the MnO2 lattice, which is thought to be the origin of the observed activation phenomenon. The results provided in this dissertation highlight that the divalency of Mg2+ ions result in very different electrochemical behaviors than those of the well-studied monovalent Li+ ions towards MnO2.

Surface Activity and Bulk Defect Chemistry of Solid Oxide Fuel Cell Cathodes

In the first half of this thesis, a new robotic instrument called a scanning impedance probe is presented that can acquire electrochemical impedance spectra in automated fashion from hundreds of thin film microelectrodes with systematically varied properties. Results from this instrument are presented for three catalyst compositions that are commonly considered for use in state-of-the-art solid oxide fuel cell cathodes. For (La_0.8Sr_0.2)_0.95Mn_O3+δ (LSM), the impedance spectra are well fit by a through-the-film reaction pathway. Transport rates are extracted, and the surface activity towards oxygen reduction is found to be correlated with the number of exposed grain boundary sites, suggesting that grain boundaries are more surface-active than grains. For La_0.5Sr_0.5Co_O3-δ (LSC), the surface activity degrades ~50x initially and then stabilizes at a comparable activity to that of previously measured Ba_0.5Sr_0.5Co_0.8Fe_0.2O3-δ films. For Sr_0.06Nb_0.06Bi_1.87O₃ (SNB), an example of a doped bismuth oxide, the activity of the metal-SNB boundary is measured.

In the second half of this thesis, SrCo_0.9Nb_0.1O_3-δ is selected as a case study of perovskites containing Sr and Co, which are the most active oxygen reduction catalysts known. Several bulk properties are measured, and synchrotron data are presented that provide strong evidence of substantial cobalt-oxygen covalency at high temperatures. This covalent bonding may be the underlying source of the high surface activity.

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.

The anodized crystalline WO3 nanoporous network with enhanced electrochromic properties

We demonstrate that a three dimensional (3D) crystalline tungsten trioxide (WO3) nanoporous network, directly grown on a transparent conductive oxide (TCO) substrate, is a suitable working electrode material for high performance electrochromic devices. This nanostructure, with achievable thicknesses of up to 2 μm, is prepared at room temperature by the electrochemical anodization of a RF-sputtered tungsten film deposited on a fluoride doped tin oxide (FTO) conductive glass, under low applied anodic voltages and mild chemical dissolution conditions. For the crystalline nanoporous network with thicknesses ranging from 0.6 to 1 μm, impressive coloration efficiencies of up to 141.5 cm2 C−1 are achieved by applying a low coloration voltage of −0.25 V. It is also observed that there is no significant degradation of the electrochromic properties of the porous film after 2000 continuous coloration–bleaching cycles. The remarkable electrochromic characteristics of this crystalline and nanoporous WO3 are mainly ascribed to the combination of a large surface area, facilitating increased intercalation of protons, as well as excellent continuous and directional paths for charge transfer and proton migration in the highly crystalline material.

Electrodeposited α- and β-phase MoO3 films and investigation of their gasochromic properties

α- and β-Phase MoO3 are synthesized using an electrodeposition method on fluorine-doped tin oxide (FTO) glass substrates from sodium-molybdate (Na2MoO4) solutions. We show that it is possible to obtain both α- and β-MoO3 by manipulating the cyclic voltammetry (CV) parameters during electrodeposition. Raman spectroscopy, X-ray diffraction, and scanning electron microscopy indicate that the applied potential range and sweep rate are strongly influential on the phase obtained and the surface morphology of the electrodeposited thin films. Gasochromic measurements were carried out on the annealed samples by exposing them to H2 gas. It was revealed that α-MoO3 thin films provided better response to H2 interaction than β-MoO3 films did. Additionally, porous films provided significantly larger responses than smooth films.

Ultrathin hematite films deposited layer-by-layer on TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe2O3) film deposited on a TiO2 underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO2 underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm−2 at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm−2) illumination. The TiO2 underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe2O3. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.