In this work, a comprehensive investigation of amorphous and crystalline modification of identical electrode active material as a thin-film electrode for a future all-solid-state Li-ion battery application is presented and discussed. Using the proposed micro-battery system, we aim to unravel the effect of the crystallinity of the positive electrode material on the intrinsic durability of all-solid-state thin-film Li-ion batteries during prolonged electrochemical cycling. We demonstrate the preparation, structural-, nanomechanical and electrochemical characteristics of molybdenum (VI) oxide (MoO₃) thin-film cathodes based on their different crystallinity. The nanomechanical properties of the electrode layers were determined using nanoindentation along with acoustic emission studies. Based on the electrochemical test results, as-prepared thin films that did not go under any heat treatment showed the best performance and stability throughout cycling around 50 μAh initial capacity when cycled at C/2. This suits well their nanomechanical properties, which showed the highest hardness but also the highest flexibility in comparison with the heat-treated layers with lower hardness, high brittleness, and numerous cracks upon mechanical loads. According to our results, we state that amorphous-type electrode materials are more durable against electro-chemo-mechanical-aging related battery performance loss in all-solid-state Li-ion batteries compared to their crystalline counterparts.

TiO₂-based mixed oxide–carbon composite supports have been suggested to provide enhanced stability for platinum (Pt) electrocatalysts in polymer electrolyte membrane (PEM) fuel cells. The addition of molybdenum (Mo) to the mixed oxide is known to increase the CO tolerance of the electrocatalyst. In this work Pt catalysts, supported on Ti_1−xMo_xO₂–C composites with a 25/75 oxide/carbon mass ratio and prepared from different carbon materials (C: Vulcan XC-72, unmodified and functionalized Black Pearls 2000), were compared in the hydrogen oxidation reaction (HOR) and in the oxygen reduction reaction (ORR) with a commercial Pt/C reference catalyst in order to assess the influence of the support on the electrocatalytic behavior. Our aim was to perform electrochemical studies in preparation for fuel cell tests. The ORR kinetic parameters from the Koutecky–Levich plot suggested a four-electron transfer per oxygen molecule, resulting in H₂O. The similarity between the Tafel slopes suggested the same reaction mechanism for electrocatalysts supported by these composites. The HOR activity of the composite-supported electrocatalysts was independent of the type of carbonaceous material. A noticeable difference in the stability of the catalysts appeared only after 5000 polarization cycles; the Black Pearl-containing sample showed the highest stability.

Ti_(1-x)Mo_xO₂-carbon composites are promising new supports for Pt-based electrocatalysts in polymer electrolyte membrane fuel cells offering exciting catalytic properties and enhanced stability against electrocorrosion. Pt and the mixed oxide form a couple liable for strong metal-support interaction (SMSI) phenomenon, generally manifesting itself in decoration of the metal particles by ultrathin layers of the support material upon annealing under reductive conditions. The aim of this work is to evaluate the SMSI phenomenon as a potential strategy for tailoring the properties of the electrocatalyst. A 20 wt% Pt/50 wt% Ti_0.8Mo_0.2O₂-50 wt% C electrocatalyst prepared on Black Pearls 2000 carbon functionalized with HNO₃ and glucose was reduced at 250 °C in H₂ in order to induce SMSI. The electrocatalytic properties and the stability of the reduced and the original catalysts were analyzed by cyclic voltammetry and CO_ads stripping voltammetry. Structural investigations as well as X-ray photoelectron spectroscopy (XPS) measurements were performed in order to obtain information about the details of the interaction between the oxide and the Pt particles. The electrochemical experiments pointed out a small loss of the electrochemically active surface area of Pt in the reduced catalyst along with enhanced stability with respect to the original one, while structural studies suggested only a minimal decrease of the Pt dispersion. At the same time, hydrogen exposure experiments combined with XPS demonstrated the presence of Mo species directly adsorbed on the Pt surface. Thus, the properties of the reduced catalyst can be traced to decoration of the surface of Pt by Mo-containing species.

The composites of transition metal-doped titania and carbon have emerged as promising supports for Pt electrocatalysts in PEM fuel cells. In these multifunctional supports, the oxide component stabilizes the Pt particles, while the dopant provides a co-catalytic function. Among other elements, Sn is a valuable additive. Stong metal-support interaction (SMSI), i.e., the migration of a partially reduced oxide species from the support to the surface of Pt during reductive treatment is a general feature of TiO₂-supported Pt catalysts. In order to explore the influence of SMSI on the stability and performance of Pt/Ti_0.8Sn_0.2O₂-C catalysts, the structural and catalytic properties of the as prepared samples measured using XRD, TEM, XPS and electrochemical investigations were compared to those obtained from catalysts reduced in hydrogen at elevated temperatures. According to the observations, the uniform oxide coverage of the carbon backbone facilitated the formation of Pt–oxide–C triple junctions at a high density. The electrocatalytic behavior of the as prepared catalysts was determined by the atomic closeness of Sn to Pt, while even a low temperature reductive treatment resulted in Sn–Pt alloying. The segregation of tin oxide on the surface of the alloy particles, a characteristic material transport process in Sn–Pt alloys after oxygen exposure, contributed to a better stability of the reduced catalysts.

TiO₂-based mixed oxide–carbon composite support for Pt electrocatalysts provides higher stability and CO tolerance under the working conditions of polymer electrolyte membrane fuel cells compared to traditional carbon supports. Non-traditional carbon materials like graphene nanoplatelets and graphite oxide used as the carbonaceous component of the composite can contribute to its affordability and/or functionality. Ti_(1−x)Mo_xO₂-C composites involving these carbon materials were prepared through a sol–gel route; the effect of the extension of the procedure through a solvothermal treatment step was assessed. Both supports and supported Pt catalysts were characterized by physicochemical methods. Electrochemical behavior of the catalysts in terms of stability, activity, and CO tolerance was studied. Solvothermal treatment decreased the fracture of graphite oxide plates and enhanced the formation of a reduced graphene oxide-like structure, resulting in an electrically more conductive and more stable catalyst. In parallel, solvothermal treatment enhanced the growth of mixed oxide crystallites, decreasing the chance of formation of Pt–oxide–carbon triple junctions, resulting in somewhat less CO tolerance. The electrocatalyst containing graphene nanoplatelets, along with good stability, has the highest activity in oxygen reduction reaction compared to the other composite-supported catalysts.

The influence of the semiconductor microstructure on the photocatalytic behavior of Pt-PtO_x/TiO₂ catalysts was studied by comparing the methanol-reforming performance of systems based on commercial P25 or TiO₂ from sol–gel synthesis calcined at different temperatures. The Pt co-catalyst was deposited by incipient wetness and formed either by calcination or high-temperature H₂ treatment. Structural features of the photocatalysts were established by X-ray powder diffraction (XRD), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS), optical absorption, Raman spectroscopy and TEM measurements. In situ reduction of Pt during the photocatalytic reaction was generally observed. The P25-based samples showed the best H₂ production, while the activity of all sol–gel-based samples was similar in spite of the varying microstructures resulting from the different preparation conditions. Accordingly, the sol–gel-based TiO₂ has a fundamental structural feature interfering with its photocatalytic performance, which could not be improved by annealing in the 400–500 °C range even by scarifying specific surface area at higher temperatures.