Free-standing and binder-free highly N-doped carbon/sulfur cathodes with tailorable loading for high-areal-capacity lithium-sulfur batteries

A practical high-loading Li–S battery is realized by using free-standing and highly conductive N-doped carbon paper as sulfur host.</p

Transport properties of mixed ionic and electronic conductors - from bulk to nanostructure

Ceria-based materials exhibit mixed ionic and electronic conductivity due to the redox-activity of the cation (Ce4+/Ce3+) and the oxygen ion mobility in the fluorite-type lattice, which intrinsically tends to form a high concentration of Anti-Frenkel defects. Both electrons and ions migrate by an activated hopping mechanism with activation barriers of 0.4 eV for the hopping process of small polarons, 0.8 eV and up to 1.6 eV for the migration and the extrinsic formation and migration of oxygen vacancies, respectively. This leads to a p(O2)-sensitive electrical conductivity, which can be dominated by each process depending on temperature and oxygen activity. Moreover, the material is quite tolerant regarding the substitution of cations. By choosing the type and range of substitution, electrical properties can be adjusted in different ways. Therefore, ceria and its substituted analogues qualify for various applications as solid electrolytes in oxygen membranes, electrode material in solid oxide fuel cells (SOFCs) and in combination with the high oxygen storage capacity for support material in heterogeneous catalysis. The defect chemistry of ceria is already extensively investigated in literature. Thus the material is an ideal model system to study interface effects, in particular the concentration and type of electronic and ionic defects as well as their transport properties in the vicinity of interfaces, complementing the established defect chemical models for bulk material. Within this work we compare the solid solution of ceria and praseodymia (Ce1-xPrxO2-δ) with the solid solution of ceria and zirconia (Ce1-xZrxO2-δ). It is already known, that due to the redox-activity of Pr-ions the combination with praseodymia can lead to an additional transport of polarons, increasing the electronic contribution to electrical conductivity. In contrast, the combination with isovalent zirconia results in an increase of the so-called reducibility of ceria due to the size mismatch of the cations. To gain a deeper understanding of the role of these substitutions on electrochemical transport processes at interfaces, highly ordered mesoporous thin films of Ce1-xPrxO2-δ (CPO) and Ce1-xZrxO2-δ (CZO) have been investigated. The mesoporous samples have been synthesized by a sol-gel process using evaporation induced self-assembly, resulting in a regular pore structure surrounded by a closed packed, interconnected 3D architecture of nanocrystallites. The structural properties were analyzed by SEM, WAXD, XRD, XPS and Raman spectroscopy, confirming the successful synthesis of a mesoporous material of high structural quality, where the surface dominates over the bulk behaviour. The electrical properties were investigated as a function of temperature and oxygen partial pressure using electrochemical impedance spectroscopy. The comparison of the results with previous results of single crystalline samples elucidates the effect of the continuous pore structure on electrical transport properties. The CZO thin films show an unusual p(O2)-dependence at high oxygen partial pressures, which cannot be explained by standard defect chemical models. Furthermore, both mesoporous samples reveal a conductivity plateau under strongly reducing conditions, which is discussed in terms of hopping statistics and defect-defect interaction

Cleavable Biotin Probes for Labeling of Biomolecules via Azide−Alkyne Cycloaddition

The azide−alkyne cycloaddition provides a powerful tool for bio-orthogonal labeling of proteins, nucleic acids, glycans, and lipids. In some labeling experiments, e.g., in proteomic studies involving affinity purification and mass spectrometry, it is convenient to use cleavable probes that allow release of labeled biomolecules under mild conditions. Five cleavable biotin probes are described for use in labeling of proteins and other biomolecules via azide−alkyne cycloaddition. Subsequent to conjugation with metabolically labeled protein, these probes are subject to cleavage with either 50 mM Na_2S_2O_4, 2% HOCH_2CH_2SH, 10% HCO_2H, 95% CF_3CO_2H, or irradiation at 365 nm. Most strikingly, a probe constructed around a dialkoxydiphenylsilane (DADPS) linker was found to be cleaved efficiently when treated with 10% HCO_2H for 0.5 h. A model green fluorescent protein was used to demonstrate that the DADPS probe undergoes highly selective conjugation and leaves a small (143 Da) mass tag on the labeled protein after cleavage. These features make the DADPS probe especially attractive for use in biomolecular labeling and proteomic studies

DFT+U studies including spin-orbit coupling - a case study for f-electrons in praseodymium-doped ceria

The mixed ionic electronic conductor Ceria exhibits not only a high concentration of Anti-Frenkel defects with high mobility, resulting in ionic conductivity of oxygen ions, but also enables an additional electronic conduction mechanism in form of small polaron hopping between the f-states of the cations. This promotes the reversible exchange of oxygen with the surrounding atmosphere and thus the oxygen storage capacity of the binary oxide CeO2-δ. The material has been established as a model system to describe both ionic and electronic transport processes in bulk material to gain deeper insights into the characteristics of polaron hopping and defect-defect interactions in mixed conductors. By introducing the redox active lanthanide Praseodymium to the Ceria host lattice, both electronic and ionic conductivities are increased in temperature and oxygen partial pressure regions where pure Ceria lacks of good performance. The redox properties of Pr-ions, shifting the equilibrium from Pr4+ to Pr3+ and forming oxygen vacancies, is key to understand the additional contribution to the total electrical conductivity and the enhanced catalytic activity. So far in literature, only the effect of Pr3+-ions in the Ceria host lattice has been investigated by means of density functional theory. To complement these investigations with the impact of Pr-ions in both oxidation states, density functional theory was applied, including a Hubbard-U correction for electronic correlation in the f-states of both cations in Ce1-xPrxO2-δ. A systematic study of spin polarization, antiferromagnetic coupling and spin-orbit interaction of the unpaired 4f-electrons was performed to investigate the influence of magnetic interactions on the description of localized polarons. The preferred localization of the excess electrons on Pr- rather than Ce-ions as well as the defect formation and configuration is discussed by analyzing the resulting energy levels and densities of states of the investigated ideal and defective super cells

Comparing the electrical and protonic conductivity of mesoporous and nanocrystalline thin films of ceria-zirconia solid solutions

Due to the redox activity of the redox couple Ce3+/Ce4+, ceria-based solid solutions are typical mixed electronic and ionic conductors (MIECs) which are used e.g. as solid electrolytes in oxygen membranes or as electrode material in solid oxide fuel cells. CexZr1-xO2 (CZO) solid solutions not only show an increased thermal and mechanical stability compared to the corresponding binary oxides, but also exhibit an improved oxygen storage capacity making CZO a prominent material system for heterogeneous catalysis. Besides the control over composition, the defect chemistry of CZO may be optimized by nanostructuring. Here we present investigations of the electrical properties of mesoporous C0.8Z0.2O2 thin films prepared by solution phase coassembly of salt precursors with an amphiphilic diblock copolymer using an evaporation-induced self-assembly (EISA) process. The mesoporous thin films exhibit a regular pore network with a high surface to volume ratio making them an ideal model system to study the influence of surface effects on the transport properties. Structural characterization using SEM, WAXD, XRD, XPS and Raman spectroscopy reveal the high structural quality of the thin films with 24 nm diameter pores which are surrounded by a crystalline wall structure consisting of 3 to 15 nm grains. Nanocrystalline thin films were prepared using pulsed laser deposition and characterized by SEM and XRD. Using electrochemical impedance spectroscopy, the electrical properties of the mesoporous and nanocrystalline thin films were investigated in a temperature range from room temperature to 500 °C and under different oxygen partial pressures between 1 and 10-4 bar. Measurements under varying humidity show large differences between the mesoporous and nanocrystalline thin films. While a significant increase in the conductivity is observed for the nanocrystalline thin films at temperatures below 250 °C and high humidity conditions, the mesoporous samples show no contribution of protonic conductivity. As will be discussed, these results indicate that the high surface area of the mesoporous samples has either no or very little effect on the protonic transport properties in CZO. Please click Additional Files below to see the full abstract

Measurement of the deuteron beam polarization at internal target at Nuclotron for DSS experiment

The current deuteron beam polarimetry at Nuclotron is provided by the Internal Target polarimeter based on the use of the asymmetry in dp- elastic scattering at large angles in the cms at 270 MeV. The upgraded deuteron beam polarimeter has been used obtain the vector and tensor polarization during 2016/2017 runs for the DSS experimental program. The polarimeter has been used also for tuning of the polarized ion source parameters for 6 different spin mode

Analyzing powers Ayy, Axx, Axz and Ay in the dd->3Hen reaction at 270 MeV

The data on the tensor Ayy, Axx, Axz and vector Ay analyzing powers in the dd->3Hen obtained at Td= 270 MeV in the angular range 0 - 110 degrees in the c.m. are presented. The observed negative sign of the tensor analyzing powers Ayy, Axx and Axz at small angles clearly demonstrate the sensitivity to the ratio of the D and S wave component of the 3He wave function. However, the one-nucleon exchange calculations by using the standard 3He wave functions have failed to reproduce the strong variation of the tensor analyzing powers as a function of the angle in the c.m.Comment: 8 pages, 7 figures, 4 tables. Submitted to EPJ