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The state-of-the-art technology of raw silver refining in a silver nitrate-based electrorefining process (Moebius-electrolysis) is accompanied by several disadvantages, both from a technological and from an ecological point of view. In addition, increasing concentrations of critical impurities from secondary sources, like palladium, in raw silver are a further challenge for the future of silver refining. Thus, there is strong motivation for the development of an adequate, alternative process of raw silver refining to substitute the existing Moebius-electrolysis. Due to its less environmentally toxic character and the high aqueous solubility of its silver salt, methanesulfonic acid (MSA) is a possible base chemical for the design of an efficient refining method based on leaching of raw silver followed by electrowinning, with less ecological and technological complications. In this paper the results of some fundamental investigations on the leaching of raw silver granules, containing approx. 94% silver, with methanesulfonic acid and hydrogen peroxide as an oxidation agent are presented. Agitation leaching experiments were conducted on a laboratory scale and the effects of the solid concentration, the hydrogen peroxide dosage and the temperature as leaching parameters were studied. The obtained results indicate that silver leaching yields of more than 90% are achievable with leaching at elevated temperatures of 65 °C or 80 °C, solid concentrations of 500 g/L and at a stoichiometric H2O2:Ag-ratio of 3:1. Increased solid concentrations greater than 500 g/L and elevated temperatures of 65 °C or 80 °C additionally improved the selectivity of the process regarding the leaching of Pd.

Na-β″-alumina is the commercially most successful solid electrolyte due to its application in ZEBRA and NAS® batteries. In this work, Li-stabilized Na-β″-alumina electrolytes were doped with 3d transition metal oxides, namely TiO2, Mn3O4, and NiO, in order to improve their ionic conductivity and fracture strength. Due to XRD and EDX measurements, it was concluded that Mn- and Ni-ions are incorporated into the crystal lattice of Na-β″-alumina. In contrast, TiO2 doping results in the formation of secondary phases that enable liquid-assisted sintering at temperatures as low as 1500 °C. All dopants increased the characteristic fracture strength of the electrolytes; 1.5 wt% of NiO doping proved to be most efficient and led to a maximal characteristic fracture strength of 296 MPa. Regarding the ionic conductivity, TiO2 doping showed the uppermost value of up to 0.30 S cm−1 at 300 °C. In contrast to the other dopants, TiO2 doping lowered the sintering temperature needed to obtain a dense, stable, and highly conductive Na-β″-alumina electrolyte suitable for applications in Na based batteries.

A new preparation concept of a partially porous solid-state bilayer electrolyte (BE) for high-temperature sodium-ion batteries has been developed. The porous layer provides mechanical strength and is infiltrated with liquid and highly conductive NaAlCl4 salt, while the dense layer prevents short circuits. Both layers consist, at least partially, of Na-β-alumina. The BEs are synthesized by a three-step procedure, including a sol-gel synthesis, the preparation of porous, calcined bulk material, and spin coating to deposit a dense layer. A detailed study is carried out to investigate the effect of polyethylene oxide (PEO) concentration on pore size and crystallization of the bulk material. The microstructure and crystallographic composition are verified for all steps via mercury intrusion, X-ray diffraction, and scanning electron microscopy. The porous bulk material exhibits an unprecedented open porosity for a NaxAlOy bilayer-system of ≤57% with a pore size of ≈200–300 nm and pore volume of ≤0.3 cm3∙g−1. It contains high shares of crystalline α-Al2O3 and Na-β-alumina. The BEs are characterized by impedance spectroscopy, which proved an increase of ionic conductivity with increasing porosity and increasing Na-β-alumina phase content in the bulk material. Ion conductivity of up to 0.10 S∙cm−1 at 300 °C is achieved.

The wetting behavior was measured for Al2O3-C in contact with AlSi7Mg with a conventional sessile drop test (vacuum, 950 °C and 180 min) and a sessile drop test with a capillary purification unit (vacuum, 730 °C and 30 min). The conventional test yielded contact angles of around 92°, whereas the sessile drop measurement with capillary purification showed a strongly non-wetting behavior with a determined apparent contact angle of the rolling drop of 157°. Filtration tests, which were repeated twice, showed that the Al2O3-C filter possessed a better filtration behavior than the Al2O3 reference filter. For both filtration trials, the PoDFA (porous disc filtration analysis) index of the Al2O3-C filter sample was equal to half of the PoDFA index of the Al2O3 reference filter sample, indicating a significantly improved filtration performance when using Al2O3-C filter. Notable is the observation of a newly formed layer between the aluminum and the Al2O3-C coating. The layer possessed a thickness between 10 µm up to 50 µm and consisted of Al, C, and O, however, with different ratios than the original Al2O3-C coating. Thermodynamic calculations based on parameters of the wetting and filtration trials underline the possible formation of an Al4O4C-layer.