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This paper proposes molecular and supramolecular concepts for potential application in perovskite solar cells. New air-stable symmetrical imine, with thiadiazole moieties PPL2: (5E,6E)-N2,N5-bis(4-(diphenylamino)benzylidene)-1,3,4-thiadiazole-2,5-diamine), as a hole-transporting material was synthesised in a single-step reaction, starting with commercially available and relatively inexpensive reagents, resulting in a reduction in the cost of the final product compared to Spiro-OMeTAD. Moreover, camphorsulfonic acid (CSA) in both enantiomeric forms was used to change the HOMO-LUMO levels and electric properties of the investigated imine-forming complexes. Electric, optical, thermal, and structural studies of the imine and its complexes with CSA were carried out to characterise the new material. Imine and imine/CSA complexes were also characterised in depth by the proton Nuclear Magnetic Resonance 1H NMR method. The position of nitrogen in the thidiazole ring influences the basicity of donor centres, which results in protonation in the imine bond. Simple devices of ITO/imine (with or without CSA(−) or CSA(+))/Ag/ITO architecture were constructed, and a thermographic camera was used to find the defects in the created devices. Electric behaviour was also studied to demonstrate conductivity properties under the forward current. Finally, the electrical properties of imine and its protonated form with CSA were compared with Spiro-OMeTAD. In general, the analysis of thermal images showed a very similar response of the samples to the applied potential in terms of the homogeneity of the formed organic layer. The TGA analysis showed that the investigated imine exhibits good thermal stability in air and argon atmospheres. [ABSTRACT FROM AUTHOR]

Hexagonal Y1−xRxMnO3+δ (R: other than Y rare earth elements) oxides have been recently introduced as promising oxygen storage materials that can be utilized in the temperature swing processes for the oxygen separation and air enrichment. In the present work, the average and local structures of Tb- and Ce-substituted Y0.7Tb0.15Ce0.15MnO3+δ and Y0.6Tb0.2Ce0.2MnO3+δ materials were studied, and their oxygen storage-related properties have been evaluated. The fully oxidized samples show the presence of a significant amount of the highly oxygen-loaded the so-called Hex3 phase, attaining an average oxygen content of δ ≈ 0.41 for both compositions. Extensive studies of the temperature swing process conducted in air and N2 over the temperature range of 180–360 °C revealed large and reversible oxygen content changes taking place with only a small temperature differences and the high dependence on the oxygen partial pressure. Significant for practical performance, the highest reported for this class of compounds, oxygen storage capacity of 1900 μmol O g−1 in air was obtained for the optimized materials and swing process. In the combined temperature–oxygen partial pressure swing process, the oxygen storage capacity of 1200 μmol O g−1 was achieved. [ABSTRACT FROM AUTHOR]

The oxygen storage capacity, structure and thermodynamic stability were studied for hexagonal Y0.7Tb0.3MnO3+δ in oxygen and air to assess its applicability for oxygen separation from air by a temperature-swing adsorption process. We show that large amounts of oxygen excess can be reversibly incorporated into and extracted from small particle-size samples of Y0.7Tb0.3MnO3+δ prepared by sol–gel synthesis for fixed oxygen partial pressures. The hyperstoichiometric material, with δ≥ 0.45 prepared in oxygen or high-pressure oxygen atmospheres, assumes a new hexagonal structure with interstitial oxygen defects near the nominally five coordinated Mn site as determined by neutron diffraction and supported by scanning and transmission electron microscopy. Thermogravimetric measurements demonstrate reversible intercalation of oxygen in a pure O2 atmosphere at around 300 °C, but more importantly, also in air over a remarkably narrow temperature range of ∼20 °C, albeit producing smaller oxygen amounts δ≤ 0.25. Comparison of samples' properties obtained by the sol–gel and solid-state synthesis methods confirms enhanced oxygen storage capacity and oxygen exchange kinetics for the small particle-size samples which exhibit larger specific surface areas. Sequential temperature-swing absorption and long-term annealing experiments demonstrate the high practical potential of Y0.7Tb0.3MnO3 compounds for the industrial production of oxygen enriched gases by utilization of waste heat at 250–350 °C. [ABSTRACT FROM AUTHOR]

It has been documented that the total electrical conductivity of the hexagonal rare-earth manganites Y0.95Pr0.05MnO3+δ and Y0.95Nd0.05MnO3+δ, as well as the undoped YMnO3+δ, is largely dependent on the oxygen excess δ, which increases considerably at temperatures below ca. 300 °C in air or O2. Improvement for samples maintaining the same P63cm crystal structure can exceed 3 orders of magnitude below 200 °C and is related to the amount of the intercalated oxygen. At the same time, doping with Nd3+ or Pr3+ affects the ability of the materials to incorporate O2, and therefore indirectly influences the conductivity as well. At high temperatures (700–1000 °C) and in different atmospheres of Ar, air, and O2, all materials are nearly oxygen-stoichiometric, showing very similar total conduction with the activation energy values of 0.8–0.9 eV. At low temperatures in Ar (δ ≈ 0), the mean ionic radius of Y1−xLnx appears to influence the electrical conductivity, with the highest values observed for the parent YMnO3. For Y0.95Pr0.05MnO3+δ oxide, showing the largest oxygen content changes, the recorded dependence of the Seebeck coefficient on the temperature in different atmospheres exhibits complex behavior, reflecting oxygen content variations, and change of the dominant charge carriers at elevated temperatures in Ar (from electronic holes to electrons). Supplementary cathodic polarization resistance studies of the Y0.95Pr0.05MnO3+δ electrode document different behavior at higher and lower temperatures in air, corresponding to the total conduction characteristics. [ABSTRACT FROM AUTHOR]

Hexagonal Y1−xRxMnO3+δ (R: other than Y rare earth elements) oxides have been recently introduced as promising oxygen storage materials that can be utilized in the temperature swing processes for the oxygen separation and air enrichment. In the present work, the average and local structures of Tb- and Ce-substituted Y0.7Tb0.15Ce0.15MnO3+δ and Y0.6Tb0.2Ce0.2MnO3+δ materials were studied, and their oxygen storage-related properties have been evaluated. The fully oxidized samples show the presence of a significant amount of the highly oxygen-loaded the so-called Hex3 phase, attaining an average oxygen content of δ ≈ 0.41 for both compositions. Extensive studies of the temperature swing process conducted in air and N2 over the temperature range of 180–360 °C revealed large and reversible oxygen content changes taking place with only a small temperature differences and the high dependence on the oxygen partial pressure. Significant for practical performance, the highest reported for this class of compounds, oxygen storage capacity of 1900 μmol O g−1 in air was obtained for the optimized materials and swing process. In the combined temperature–oxygen partial pressure swing process, the oxygen storage capacity of 1200 μmol O g−1 was achieved. [ABSTRACT FROM AUTHOR]

The A-site cation-ordered GdBa 0.5 Sr 0.5 Co 2- x Cu x O 5+δ (GBSCC) double perovskites are evaluated regarding the development of high-performance oxygen electrodes for reversible solid oxide cells (rSOCs). The aims are to maximally decrease the content of toxic and expensive cobalt by substitution with copper while at the same time improving or maintaining the required thermomechanical and electrocatalytic properties. Studies reveal that compositions with 1 ≤ x ≤ 1.15 are particularly interesting. Their thermal and chemical expansions are decreased, and sufficient transport properties are observed. Complementary density functional theory calculations give deeper insight into oxygen defect formation in the considered materials. Chemical compatibility with La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM) and Ce 0.9 Gd 0.1 O 2-δ (GDC) solid electrolytes is evaluated. It is documented that the GdBa 0.5 Sr 0.5 Co 0.9 Cu 1.1 O 5+δ oxygen electrode enables obtaining very low electrode polarization resistance ( R p ) values of 0.017 Ω cm 2 at 850 °C as well as 0.111 Ω cm 2 at 700 °C, which is lower in comparison to that of GdBa 0.5 Sr 0.5 CoCuO 5+δ (respectively, 0.026 and 0.204 Ω cm 2 ). Systematic distribution of relaxation times analyses allows studies of the electrocatalytic activity and distinguishing elementary steps of the electrochemical reaction at different temperatures. The rate-limiting process is found to be oxygen atom reduction, while the charge transfer at the electrode/electrolyte interface is significantly better with LSGM. The studies also allow elaborating on the catalytic role of the Ag current collector as compared with Pt. The electrodes manufactured using materials with x = 1 and 1.1 permit reaching high power outputs, exceeding 1240 mW cm -2 at 850 °C and 1060 mW cm -2 at 800 °C, for the LSGM-supported cells, which can also work in the electrolysis mode.

Planar perovskite solar cells were fabricated on F-doped SnO 2 (FTO) coated glass substrates, with 4,4'-((1E,1'E)-((1,2,4-thiadiazole-3,5-diyl)bis(azaneylylidene))bis(methaneylylidene))bis( N , N -di-p-tolylaniline) (bTAThDaz) as hole transport material. This imine was synthesized in one step reaction, starting from commercially available and relatively inexpensive reagents. Electrochemical, optical, electrical, thermal and structural studies including thermal images and current-voltage measurements of the full solar cell devices characterize the imine in details. HOMO-LUMO of bTAThDaz were investigated by cyclic voltammetry (CV) and energy-resolved electrochemical impedance spectroscopy (ER-EIS) and were found at -5.19 eV and -2.52 eV (CV) and at -5.5 eV and -2.3 eV (ER-EIS). The imine exhibited 5% weight loss at 156 °C. The electrical behavior and photovoltaic performance of the perovskite solar cell was examined for FTO/TiO 2 /perovskite/bTAThDaz/Ag device architecture. Constructed devices exhibited good time and air stability together with quite small effect of hysteresis. The observed solar conversion efficiency was 14.4%.