Nido-Hydroborate-Based Electrolytes for All-Solid-State Lithium Batteries

Hydroborate-based solid electrolytes have recently been successfully employed in high voltage, room temperature all-solid-state sodium batteries. The transfer to analogous lithium systems has failed up to now due to the lower conductivity of the corresponding lithium compounds and their high cost. Here LiB₁₁H₁₄ nido-hydroborate as a cost-effective building block and its high-purity synthesis is introduced. The crystal structures of anhydrous LiB₁₁H₁₄ as well as of LiB₁₁H₁₄-based mixed-anion solid electrolytes are solved and high ionic conductivities of 1.1 × 10⁻⁴ S cm⁻¹ for Li₂(B₁₁H₁₄)(CB₁₁H₁₂) and 1.1 × 10⁻³ S cm⁻¹ for Li₃(B₁₁H₁₄)(CB₉H₁₀)₂ are obtained, respectively. LiB₁₁H₁₄ exhibits an oxidative stability limit of 2.6 V versus Li⁺/Li and the proposed decomposition products are discussed based on density functional theory calculations. Strategies are discussed to improve the stability of these compounds by modifying the chemical structure of the nido-hydroborate cage. Galvanostatic cycling in symmetric cells with two lithium metal electrodes shows a small overpotential increase from 22.5 to 30 mV after 620 h (up to 0.5 mAh cm⁻²), demonstrating that the electrolyte is compatible with metallic anodes. Finally, the Li₂(B₁₁H₁₄)(CB₁₁H₁₂)  electrolyte is employed in a proof-of-concept half cell with a TiS₂ cathode with a capacity retention of 82% after 150 cycles at C/5.     

Solidification of Be-free Ni-based dental alloy

A novel, Nb- and Si-rich and Be-free Ni-based alloy was cast by two methods of investment casting and continuous casting to study the microstructure evolution during solidification and its mechanical properties. The solidification of the alloy started with the primary crystallization of FCC-γ, followed by a binary eutectic reaction, with the formation of a heterogeneous constituent: FCC-γ+G-phase, which replaced the low-melting eutectic (FCC-γ+NiBe) in the Be-bearing alloys. AlNi₆Si₃ and γ′ formed during the terminal stages of solidification by investment casting, while the formation of AlNi₆Si₃ was suppressed by continuous casting. The Scheil solidification model agreed very well with the experimental results.     

Design of tailored biodegradable implants: The effect of voltage on electrodeposited calcium phosphate coatings on pure magnesium

Magnesium, as a biodegradable metal, offers great potential for use as a temporary implant material, which dissolves in the course of bone tissue healing. It can sufficiently support the bone and promote the bone healing process. However, the corrosion resistance of magnesium implants must be enhanced before its application in clinical practice. A promising approach of enhancing the corrosion resistance is deposition of bioactive coating, which can reduce the corrosion rate of the implants and promote bone healing. Therefore, a well-designed substrate-coating system allowing a good control of the degradation behavior is highly desirable for tailored implants for specific groups of patients with particular needs. In this contribution, the influence of coating formation conditions on the characteristics of potentiostatically electrodeposited CaP coatings on magnesium substrate was evaluated. Results showed that potential variation led to formation of coatings with the same chemical composition, but very different morphologies. Parameters that mostly influence the coating performance, such as the thickness, uniformity, deposits size, and orientation, varied from produced coating to coating. These characteristics of CaP coatings on magnesium were controlled by coating formation potential, and it was demonstrated that the electrodeposition could be a promising coating technique for production of tailored magnesium-CaP implants.     

Indium as a cathodic material: catalytic reduction of formaldehyde

The performance of indium as cathodic material for the electroreduction of small organic molecules is considered. The cathodic reduction of formaldehyde (FA) is an ideal model reaction for this purpose since indium has a very large overpotential for the hydrogen evolution reaction with and without FA. Kinetic sets of the reaction pathways, with respect to the Tafel slope and reaction order, are considered on the basis of quasi-potentiostatic measurements and cyclic voltammetry. The value of the Tafel slope bc60mVdec-1 indicates that the protonation of the adsorbed radical is the rate determining step in the proposed CECE mechanism. The reaction order with respect to FA is close to one in the limiting current regions but smaller in the Tafel region. The existence and kinetics of the radicals adsorbed during FA reduction are evidenced by very fast potentiodynamic experiments, with scan rates between 40 and 80Vs-1. Electrochemical measurements are carried out on freshly in situ prepared In-electrodes. During cathodic polarization, the surface oxide film is reduced to In-metal via a solid-state mechanism. The crystallization kinetics of indium in the oxide matrix is also discussed.     

Optical quantities of multi-layer systems with randomly rough boundaries calculated using the exact approach of the Rayleigh–Rice theory

In this paper, the exact approach of the Rayleigh–Rice theory enabling us to calculate optical quantities of multi-layer systems with boundaries exhibiting slight random roughness is presented. This approach is exact in the sense that it takes into account the propagation of perturbed electromagnetic fields (waves) among randomly rough boundaries including all cross-correlation and auto-correlation effects. The restriction to the second order of perturbation, which is the lowest order that gives nonzero corrections to coherent waves (obeying the Snell’s law), represents the only approximation used in our calculations. It is assumed that the layers and the substrates are formed by optically homogeneous and isotropic materials. The formulae obtained in the theoretical part are used to investigate the influence of layer thicknesses and roughness parameters on reflectances and associated ellipsometric parameters of the selected numerical examples of a three-layer system. The presented approach represents the generalization of the exact approach for single-layer systems and the improvement of the approximate approach for multi-layer systems published earlier. The exact approach of the RRT has a substantial importance for the optical characterization of multi-layer systems occurring in applied research and optics industry applications.     

Twinned Growth of Metal‐Free,Triazine‐Based Photocatalyst Films as Mixed‐Dimensional (2D/3D) van der Waals Heterostructures

Design and synthesis of ordered, metal‐free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed‐dimensional (2D/3D) metal‐free van der Waals (vdW) heterostructures based on triazine (C₃N₃) linkers grow as large area, transparent yellow‐orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E _g,opt = 1.91 eV, E _g,elec = 1.84 eV) and are moderately porous (124 m² g^?1). The material consists of a crystalline 2D phase that is fully sp² hybridized and provides structural stability, and an amorphous, porous phase with mixed sp²–sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one‐pot reaction mixture: unprecedented for metal‐free frameworks and a direct consequence of on‐catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal‐free, light‐induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h^?1 g^?1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of “wet” chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.     

High‐Performance Supercapacitors Based on a Zwitterionic Network of Covalently Functionalized Graphene with Iron Tetraaminophthalocyanine

Graphene derivatives are promising candidates as electrode materials in supercapacitor cells, therefore, functionalization strategies are pursued to improve their performance. A scalable approach is reported for preparing a covalently and homogenously functionalized graphene with iron tetraaminophthalocyanine (FePc‐NH₂) with a high degree of functionalization. This is achieved by exploiting fluorographene's reactivity with the diethyl bromomalonate, producing graphene‐dicarboxylic acid after hydrolysis, which is conjugated with FePc‐NH₂. The material exhibits an ultrahigh gravimetric specific capacitance of 960 F g^?1 at 1 A g^?1 and zero losses upon charging–discharging cycling. The energy density of 59 Wh kg^?1 is eminent among supercapacitors operating in aqueous electrolytes with graphene‐based electrode materials. This is attributed to the structural and functional synergy of the covalently bound components, giving rise to a zwitterionic surface with extensive π–π stacking, but not graphene restacking, all being very beneficial for charge and ionic transport. The safety of the proposed system, owing to the benign Na₂SO₄ aqueous electrolyte, the high capacitance, energy density, and potential of preparing the electrode material on a large‐scale and at low cost make the reported strategy very attractive for development of supercapacitors based on the covalent attachment of suitable molecules onto graphene toward high‐synergy hybrids.     

Determination of transient two-dimensional heat transfer in ventilated lightweight low sloped roof using Fourier series

In this paper, the analysis of transient two-dimensional (2D) heat transfer in low sloped roof with forced ventilated cavity made from lightweight building elements (LBE) is presented. For the heat transfer analysis the 2D numerical model, which was verified with experiments, was used. Forced ventilated cavity was configured in two different ways. In the first case the cavity was configured with coloured thin metal sheet and in the second case with thin metal sheet with added layer of thermal insulation and radiation barrier. Beside the influence of the ventilated cavity configuration on the transient 2D heat transfer in the LBE and on the cavity outlet air temperature also the influence of the LBE thickness, specific air flow rate through the cavity, inner air temperature and wind velocity was analysed. Multi-parametric equations for determination of Fourier series coefficients were formed. These coefficients were used for evaluation of transient 2D heat transfer on the inner side of the roof and cavity outlet air temperature for a clear day.     

Cultivar differences of total anthocyanins and anthocyanidins in red and purple-fleshed potatoes and their relation to antioxidant activity

Total anthocyanins (TAC) and individual anthocyanidins (AN) after hydrolysis were measured in 15 red and purple-fleshed potato cultivars produced in five different locations in the Czech Republic and a new cultivar Blaue St. Galler from Switzerland. It was found that TAC, expressed as cyanidin content, varied between 0.7 mg 100 g⁻¹ FW (cv. Blue Congo) and 74.3 mg 100 g⁻¹ FW (cv. Blaue Ludiano). Major differences in cultivars were found for AN relative abundance. For cv. Highland Burgundy Red a high proportion of pelargonidin (98.7%) was characteristic, whereas cv. British Columbia Blue contained almost exclusively cyanidin. Cultivars Violette and Vitelotte showed a relatively high content of malvidin. Cultivar Shetland Black differed from others with its higher content of peonidin (on average 36.7%). High petunidin abundance in the cultivars Valfi, Blue Congo, Salad Blue, Blaue St. Galler, Blaue Hindel Bank, Blaue Ludiano, Blaue Schweden, Farbe Kartoffel and Salad Red was found. TAC and AN contents highly corresponded with antioxidant activity (AA) determined with the ABTS, FRAP and DPPH assays in vitro. High AA was shown by the cultivars Vitelotte, Violette, Blaue Ludiano, Hafija, and Highland Burgundy Red. Increased height above sea level, higher annual sum of precipitation, and lower annual average temperatures caused higher AA and TAC. A high degree of hydroxylation and/or methoxylation of individual anthocyanidins could contribute in conjunction with other phenolics to high AA (peonidin, delphinidin and malvidin in the cultivars Blue Congo, Highland Burgundy Red and Shetland Black). Consequently, new red and purple-fleshed cultivars with high TAC and highly methoxylated and/or hydroxylated AN could be a promising source of favourable antioxidants in human nutrition.