Electrodeposited metal-organic framework films as self-assembled hierarchically superstructured supports for stable omniphobic surface coatings

Superhierarchically rough films are rapidly synthesised on metal substrates via electrochemically triggered self-assembly of meso/macroporous-structured metal-organic framework (MOF) crystals. These coatings are applied to immobilise a functional oil with low surface energy to provide stable coatings repellent to a wide range of hydrophobic as well as hydrophilic fluids. Such omniphobic surfaces are highly interesting for several applications such as anti-fouling, anti-icing, and dropwise condensation, and become easily scalable with the presented bottom-up fabrication approach. As investigated by environmental scanning electron microscopy (ESEM), the presented perfluorinated oil-infused Cu-BTC coating constitutes of a flat liquid-covered surface with protruding edges of octahedral superstructured MOF crystals. Water and non-polar diiodomethane droplets form considerably high contact angles and even low-surface-tension fluids, e.g. acetone, form droplets on the infused coating. The repellent properties towards the test fluids do not change upon extended water spraying in contrast to oil-infused porous copper oxide or native copper surfaces. It is discussed in detail, how the presented electrodeposited MOF films grow and provide a proficient surface morphology to stabilise the functional oil film due to hemiwicking

In situ Raman spectroscopy on silicon nanowire anodes integrated in lithium ion batteries

Rapid decay of silicon anodes during lithiation poses a significant challenge in application of silicon as an anode material in lithium ion batteries. In situ Raman spectroscopy is a powerful method to study the relationship between structural and electrochemical data during electrode cycling and to allow the observation of amorphous as well as liquid and transient species in a battery cell. Herein, we present in situ Raman spectroscopy on high capacity electrode using uncoated and carbon-coated silicon nanowires during first lithiation and delithiation cycle in an optimized lithium ion battery setup and complement the results with operando X-ray reflection diffraction measurements. During lithiation, we were able to detect a new Raman signal at 1859 cm−1 especially on uncoated silicon nanowires. The detailed in situ Raman measurement of the first lithiation/delithiation cycle allowed to differentiate between morphology changes of the electrode as well as interphase formation from electrolyte components

The troubadour Marcabru and his public

Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV$_{3}$O$_{8}$, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV$_{3}$O$_{8}$ can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg$^{−1}$ after 10 cycles in the potential window of 0.8–3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li$^+$ and Na$^+$ cations into LiV$_{3}$O$_{8}$, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li$_{0.7}$Na$_{0.7}$V$_{3}$O$_{8}$ in Na-rich electrolytes, or to LiV$_{3}$O$_{8}$ in Li-rich electrolytes. The chemical diffusion coefficients of Na+ and Li+ in crystalline LiV$_{3}$O$_{8}$ are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li$_{0.7}$Na$_{0.7}$V$_{3}$O$_{8}$-type structure favors intercalation of Na$^+$, whereas the LiV$_{3}$O$_{8}$-type prefers to accommodate Li$^+$ cations

Binding energy referencing for XPS in Alkali metal-based battery materials research (II): Application to complex composite electrodes

X-ray photoelectron spectroscopy (XPS) is a key method for studying (electro-)chemical changes in metal-ion battery electrode materials. In a recent publication, we pointed out a conflict in binding energy (BE) scale referencing at alkali metal samples, which is manifested in systematic deviations of the BEs up to several eV due to a specific interaction between the highly reactive alkali metal in contact with non-conducting surrounding species. The consequences of this phenomenon for XPS data interpretation are discussed in the present manuscript. Investigations of phenomena at surface-electrolyte interphase regions for a wide range of materials for both lithium and sodium-based applications are explained, ranging from oxide-based cathode materials via alloys and carbon-based anodes including appropriate reference chemicals. Depending on material class and alkaline content, specific solutions are proposed for choosing the correct reference BE to accurately define the BE scale. In conclusion, the different approaches for the use of reference elements, such as aliphatic carbon, implanted noble gas or surface metals, partially lack practicability and can lead to misinterpretation for application in battery materials. Thus, this manuscript provides exemplary alternative solutions

Fully sp²‐carbon‐linked crystalline two‐dimensional conjugated polymers: insight into 2D poly(phenylenecyanovinylene) formation and their optoelectronic properties

Cyano‐substituted polyphenylene vinylenes (PPVs) have been in the focus of research for several decades due to their interesting optoelectronic properties and potential applications in organic electronics. With the advent of organic two‐dimensional (2D) crystals, the question arose how the chemical and optoelectronic advantages of PPVs evolve in 2D compared to their linear counterparts. In this work, we present the efficent synthesis of two novel 2D fully sp²‐carbon‐linked crystalline PPVs and investigate the essentiality of inorganic bases for their catalytic formation. Notably, among all bases screened, cesium carbonate (Cs₂CO₃) plays a crucial role and enables reversibility in the first step with subsequent structure locking by formation of a C=C double bond to maintain crystallinity, which is supported by density functional theory (DFT) calculation. We propose a quantifiable energy diagram of a “quasi‐reversible reaction” which allows to identify further suitable C‐C bond formation reactions for 2D polymerizations. Moreover, we delineate the narrowing of the HOMO‐LUMO gap by expanding conjugation into two dimensions. To enable environmentally benign processing, we further perform the post‐modification of 2D PPVs, which renders stable dispersions in the aqueous phase

An efficient two-polymer binder for high-performance silicon nanoparticle-based lithium-ion batteries: A systematic case study with commercial polyacrylic acid and polyvinyl butyral polymers

Silicon is one of the most promising anode materials for high energy density lithium ion batteries (LIBs) due to its high theoretical capacity and natural abundance. Unfortunately, significant challenges arise due to the large volume change of silicon upon lithiation/delithiation which inhibit its broad commercialization. An advanced binder can, in principle, reversibly buffer the volume change, and maintain strong adhesion toward various components as well as the current collector. In this work, we present the first report on the applicability of polyvinyl butyral (PVB) polymer as a binder component for silicon nanoparticles-based LIBs. Characteristic binder properties of commercial PVB and polyacrylic acid (PAA) polymers are compared. The work focuses on polymer mixtures of PVB polymers with PAA, for an improved binder composition which incorporates their individual advantages. Different ratios of polymers are systematically studied to understand the effect of particular polymer chains, functional groups and mass fractions, on the electrochemical performance. We demonstrate a high-performance polymer mixture which exhibits good binder-particle interaction and strong adhesion to Cu-foil. PAA/PVB-based electrode with a Si loading of ∼1 mg/cm2 tested between 0.01 and 1.2 V vs. Li/Li+ demonstrate specific capacities as high as 2170 mAh/g after the first hundred cycles. © The Author(s) 2019

The impact of surface morphology on the magnetovolume transition in magnetocaloric LaFe_11.8Si_1.2

First order magnetocaloric materials reach high entropy changes but at the same time exhibit hysteresis losses which depend on the sample’s microstructure. We use non-destructive 3D X-ray microtomography to understand the role of surface morphology for the magnetovolume transition of LaFe11.8Si1.2. The technique provides unique information on the spatial distribution of the volume change at the transition and its relationship with the surface morphology. Complementary Hall probe imaging confirms that on a morphologically complex surface minimization of strain energy dominates. Our findings sketch the way for a tailored surface morphology with low hysteresis without changing the underlying phase transition

Predicted risks of radiogenic cardiac toxicity in two pediatric patients undergoing photon or proton radiotherapy

BACKGROUND: Hodgkin disease (HD) and medulloblastoma (MB) are common malignancies found in children and young adults, and radiotherapy is part of the standard treatment. It was reported that these patients who received radiation therapy have an increased risk of cardiovascular late effects. We compared the predicted risk of developing radiogenic cardiac toxicity after photon versus proton radiotherapies for a pediatric patient with HD and a pediatric patient with MB. METHODS: In the treatment plans, each patient’s heart was contoured in fine detail, including substructures of the pericardium and myocardium. Risk calculations took into account both therapeutic and stray radiation doses. We calculated the relative risk (RR) of cardiac toxicity using a linear risk model and the normal tissue complication probability (NTCP) values using relative seriality and Lyman models. Uncertainty analyses were also performed. RESULTS: The RR values of cardiac toxicity for the HD patient were 7.27 (proton) and 8.37 (photon), respectively; the RR values for the MB patient were 1.28 (proton) and 8.39 (photon), respectively. The predicted NTCP values for the HD patient were 2.17% (proton) and 2.67% (photon) for the myocardium, and were 2.11% (proton) and 1.92% (photon) for the whole heart. The predicted ratios of NTCP values (proton/photon) for the MB patient were much less than unity. Uncertainty analyses revealed that the predicted ratio of risk between proton and photon therapies was sensitive to uncertainties in the NTCP model parameters and the mean radiation weighting factor for neutrons, but was not sensitive to heart structure contours. The qualitative findings of the study were not sensitive to uncertainties in these factors. CONCLUSIONS: We conclude that proton and photon radiotherapies confer similar predicted risks of cardiac toxicity for the HD patient in this study, and that proton therapy reduced the predicted risk for the MB patient in this study

Amphiphiles with polyethyleneoxide-polyethylenecarbonate chains for hydrophilic coating of iron oxide cores, loading by Gd(III) ions and tuning R2/R1 ratio

© 2015 Elsevier B.V. The present work is aimed at the synthesis of hydrophilic colloids with convenient transverse and longitudinal NMR-relaxation times. Core-shell morphology with iron oxide cores and hydrophilic shell enriched by Gd(III) ions is the basis for the colloids with dual-mode relaxivities. Polyethyleneoxide-polyethylenecarbonate derivatives of p-tert-butylphenols are introduced as amphiphiles for efficient hydrophilization of oleate-stabilized iron oxide nanoparticles. The obtained results reveal the easy variation of the synthetic conditions as the route to switch from the recoating to the dissolution of the oleate-stabilized iron-oxide nanoparticles. The length of ethylenecarbonate chains is highlighted as the factor affecting the transverse relaxivity (R2) and the colloid properties of the synthesized colloids, evaluated from DLS data. The complex ability of ethylenecarbonate chains is the reason for loading of the synthesized colloids by Gd(III) ions in aqueous dispersions at specific conditions. These conditions are introduced herein as a route of gaining in longitudinal relaxivity (R1) and tuning R2/R1 ratio