Photocatalytic activity of oxide systems based on doped d-elements of titanium alloys

CO-, W-, MO- and Zn-containing hetero-oxide nanostructured coatings on titanium and its alloys formed by plasma-electrolyte oxidation in galvanostatic mode from alkaline electrolytes were investigated. The morphology of the surface of the formed coatings was studied by scanning microscopy on the Zeiss Evo 40XVP microscope. The phase composition of the obtained coatings was determined on the X-ray diffractometer Drone-2. Photocatalytic activity of ZnO-WO3/TiO2 films, ZnO-MOO3/TIO2, ZnO-Co3O4/TiO2, CoO-WO3/TiO2 tested in a model reaction of decomposition of an aqueous solution of azobye with a concentration of 12,2·10-5 mol/L (MО) at UV irradiation. It is shown that with plasma-electrolyte oxidation of titanium and its alloys in alkaline diphosphate electrolytes in the mode of «drop-down power» forming heterostructural composites with micro-globular surface morphology. The possibility of controlling the phase and elemental composition of oxide layers, as well as the topography of the surface by changing the composition of the electrolyte and the content of individual components, as well as the modes of formation is confirmed. Heteroxide coatings formed in PEO modes differ in composition and surface morphology, but all exhibit photocatalytic properties of varying degrees of activity. The study of the photocatalytic activity of the obtained coatings in the azo dye decomposition reaction by means of UV testing allowed to rank the heteroxide systems according to the specified parameter. Thus, the degree of decomposition of MF on ZnO-WO3/TiO2 films in 50 minutes was 23 %. Metal oxide systems ZnO-Co3O4/TiO2 had similar characteristics of the degree of decomposition – 21 %. The incorporation of CoO and WO3 oxides into the coating composition reduced the catalytic activity of the system to 19 %. The unstable mode of formation of ZnO-MoO3/TiO2 oxides and the low speed of the process have affected the quality of the catalytic coating activity, reduced the degree of decomposition of MO to values of titanium monoxide Ti/TiO2 without dopants. Comparison of quantitative characteristics of the properties of the obtained coatings allowed to determine the effects of dopants, incorporated into metal oxide systems, on their photocatalytic activity.

Electrolyte Oxidation Pathways in Lithium-Ion Batteries

<p>The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO₂/Li cells were cycled with a lithium-ion conducting glass-ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ~4.7 V vs Li/Li⁺ for LiCoO₂), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterised, and a detailed reaction scheme is constructed to rationalise the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have direct impact on understanding and mitigating degradation in high voltage/higher energy density LiCoO₂-based cells,and more generally for cells containing nickel-containing cathode materials (e.g. LiNi_xMn_yCo_zO₂; NMCs), as they lose oxygen at lower operating voltages.</p>

Electrolyte Oxidation Pathways in Lithium-Ion Batteries

<p>The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO₂/Li cells were cycled with a lithium-ion conducting glass-ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ~4.7 V vs Li/Li⁺ for LiCoO₂), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterised, and a detailed reaction scheme is constructed to rationalise the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have direct impact on understanding and mitigating degradation in high voltage/higher energy density LiCoO₂-based cells,and more generally for cells containing nickel-containing cathode materials (e.g. LiNi_xMn_yCo_zO₂; NMCs), as they lose oxygen at lower operating voltages.</p>