Sodium-beta alumina is a solid-state electrolyte with outstanding chemical, electrochemical, and mechanical properties. Sodium polyaluminate is successfully employed in established Na–S and Na–NiCl₂ cell systems. It is a promising candidate for all-solid-state sodium batteries. However, humidity affects the performance of this solid electrolyte. In this work, the effect of humidity on disk-shaped samples of Li-stabilized sodium-beta alumina stored in three different environments is quantified. We used impedance analysis and additional characterizations to investigate the consequences of the occurring degradation, namely ion exchange and subsequent buildup of surface layers. Sodium-beta alumina’s ionic conductivity gradually deteriorates up to two orders of magnitude. This is due to layers developed superficially during storage, while its fracture strength of 240 MPa remains unaffected. Changes in microstructure, composition, and cycle life of Na|BASE|Na cells highlight the importance of proper storage conditions: In just one week of improper storage, the critical current density collapsed from the maximum of 9.1 mA cm⁻², one of the highest values reported for sodium-beta alumina, to 1.7 mA cm⁻² at 25 °C. The results validate former observations regarding sodium-beta alumina’s moisture sensitivity and suggest how to handle sodium-beta alumina used in electrochemical cell systems.

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 Na_xAlO_y 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.

Metal anodes offer substantially higher specific and volumetric capacities than conventional anode materials such as graphite in lithium-ion batteries or hard carbon in sodium-ion batteries. However, the integration of metal anodes into solid-state batteries poses significant challenges, particularly with respect to processing, interfacial stability, and cell assembly. Anode-free solid-state batteries (AFSSBs) address these challenges by eliminating the pre-installed metal anode, instead forming the metal in situ during the initial charging (formation) step. In anode-free solid-state batteries, the quality of the interfacial contact is particularly critical, as insufficient contact can lead to locally increased current densities. Consequently, the initial metal plating during the formation step plays a decisive role in determining the homogeneity and stability of the anode interface. Furthermore, conventional battery-grade copper foils (~10 µm) are considerably thicker than required for the targeted C-rates and are difficult to use as stand-alone anode-free current collectors, thereby hindering the industrial production of anode-free solid-state batteries. In this publication, we demonstrate the application of atmospheric plasma spraying (APS) to fabricate thin copper current collectors directly on the ceramic solid electrolytes LAGP (lithium aluminium germanium phosphate) and BASE (beta-alumina solid electrolyte) with superior interface contact. No mechanical damage or diffusion of copper into the solid electrolyte nor formation of secondary phases at the interfaces were observed in SEM or EDS despite the elevated process temperature. LAGP with a thickness as low as 300 µm was successfully coated and subsequently used for plating/stripping experiments. Finally, dense sodium metal was plated at the copper-substrate interface of a 1.4 mm thick BASE sample.