Spray‐coated Hard Carbon Composite Anodes for Sodium‐Ion Insertion

Sodium-ion batteries are among the most promising alternatives to lithium-ion batteries. Hard carbon (HC) electrodes have been recognized as suitable active anode material for mono-valent ion batteries. Here, we present a simple and cost-effective spray-coating process to prepare HC composite electrodes on copper current collectors with different binder (sodium carboxymethyl cellulose, CMC) content and different HC particle sizes. The spray-coated electrodes were evaluated and tested in 1 M sodium perchlorate (NaClO$_4$) in propylene carbonate (PC) in dependence of the CMC content with and without fluoroethylene carbonate (FEC) as additive, and the performance was also compared to doctor bladed HC electrodes. Spray-coated anodes in Na half-cells revealed improved capacity during the first cycles compared with doctor bladed anodes with similar thicknesses. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) studies were performed, which revealed a significant increase of inorganic fluoro-compounds in the formed solid electrolyte interphase (SEI) when FEC was present as additive. In addition, first single electrode microcalorimetry studies on spray-coated thin HC composite electrodes yielded an entropy of the sodiation process of 80 J mol$^{−1}$ K$^{−1}$ at high state of charge (SoC), comparable to that of bulk Na deposition

Strontium substitution of gelatin modified calcium hydrogen phosphates as porous hard tissue substitutes

Aiming at the generation of a high strontium-containing degradable bone substitute, the exchange of calcium with strontium in gelatin-modified brushite was investigated. The ion substitution showed two mineral groups, the high-calcium containing minerals with a maximum measured molar Ca/Sr ratio of 80%/20% (mass ratio 63%/37%) and the high-strontium containing ones with a maximum measured molar Ca/Sr ratio of 21%/79% (mass ratio 10%/90%). In contrast to the high-strontium mineral phases, a high mass loss was observed for the calcium-based minerals during incubation in cell culture medium (alpha-MEM), but also an increase in strength owing to dissolution and re-precipitation. This resulted for the former in a decrease of cation concentration (Ca + Sr) in the medium, while the pH value decreased and the phosphate ion concentration rose significantly. The latter group of materials, the high-strontium containing ones, showed only a moderate change in mass and a decrease in strength, but the Ca + Sr concentration remained permanently above the initial calcium concentration in the medium. This might be advantageous for a future planned application by supporting bone regeneration on the cellular level. © 2020 The Authors. Journal of Biomedical Materials Research Part A published by Wiley Periodicals LLC

Deposition of Sodium Metal at the Copper‐NaSICON Interface for Reservoir‐Free Solid‐State Sodium Batteries

“Anode-free” solid-state battery concepts are explored extensively as they promise a higher energy density with less material consumption and simple anode processing. Here, the homogeneous and uniform electrochemical deposition of alkali metal at the interface between current collector and solid electrolyte plays the central role to form a metal anode within the first cycle. While the cathodic deposition of lithium has been studied intensively, knowledge on sodium deposition is scarce. In this work, dense and uniform sodium layers of several microns thickness are deposited at the Cu|Na$_{3.4}$Zr$_2$Si$_{2.4}$P$_{0.6}$O$_{12}$ interface with high reproducibility. At current densities of ≈1 mA∙cm$^{−2}$, relatively uniform coverage is achieved underneath the current collector, as shown by electrochemical impedance spectroscopy and 3D confocal microscopy. In contrast, only slight variations of the coverage are observed at different stack pressures. Early stages of the sodium metal growth are analyzed by in situ transmission electron microscopy revealing oriented growth of sodium. The results demonstrate that reservoir-free (“anode-free”) sodium-based batteries are feasible and may stimulate further research efforts in sodium-based solid-state batteries

Impact of the Chlorination of Lithium Argyrodites on the Electrolyte/Cathode Interface in Solid‐State Batteries

Lithium argyrodite-type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li6PS5Cl and Li5.5PS4.5Cl1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time-of-flight secondary ion mass spectrometry indicate that the Li5.5PS4.5Cl1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance

Role of Excess Bi on the Properties and Performance of BiFeO₃ Thin-Film Photocathodes

BiFeO3 (BFO) has recently been identified as a promising photocathode material for photoelectrochemical (PEC) water splitting due to its light absorption and photoelectrochemical properties. The performance-limiting factors, in particular the impact of stoichiometry on the performance, still need to be understood. The effect of the ratio of Bi/Fe in the precursor solution for sol-gel synthesis on the properties and performance of BFO thin films is investigated in this study. Thin films with a stoichiometric Bi/Fe ratio and with a 10% excess of Bi are prepared on fluorine-doped tin-oxide substrates. While bulk characterization techniques show the formation of phase-pure BFO, surface characterization techniques indicate Bi enrichment on the surface. Light absorption and band gap do not change with excess Bi, whereas the current density is two times higher for Bi excess films compared to stoichiometric films at 0.6 V vs RHE. Electrochemical impedance spectroscopy attributes this improved performance of excess Bi thin films to a lower recombination rate and a lower charge transfer resistance. The lower recombination rate is attributed to fewer Bi and O vacancies, which can act as recombination centers. Therefore, adjusting the Bi/Fe ratio is an effective strategy to enhance the PEC performance of BFO photocathodes.</p

The Impact of Microstructure on Filament Growth at the Sodium Metal Anode in All‐Solid‐State Sodium Batteries

In recent years, all-solid-state batteries (ASSBs) with metal anodes have witnessed significant developments due to their high energy and powerdensity as well as their excellent safety record. While intergranular dendriticlithium growth in inorganic solid electrolytes (SEs) has been extensively studied for lithium ASSBs, comparable knowledge is missing forsodium-based ASSBs. Therefore, polycrystalline Na-′′-alumina is employedas a SE model material to investigate the microstructural influence on sodiumfilament growth during deposition of sodium metal at the anode. The research focuses on the relationship between the microstructure, in particular grainboundary (GB) type and orientation, sodium filament growth, and sodium iontransport, utilizing in situ transmission electron microscopy (TEM) measurements in combination with crystal orientation analysis. The effect ofthe anisotropic sodium ion transport at/across GBs depending on theorientation of the sodium ion transport planes and the applied electric field on the current distribution and the position of sodium filament growth is explored. The in situ TEM analysis is validated by large field of viewpost-mortem secondary ion mass spectrometer (SIMS) analysis, in which sodium filament growth within voids and along grain boundaries is observed, contributing to the sodium network formation potentially leading to failure of batteries

Functionalization of Ti-40Nb implant material with strontium by reactive sputtering

Background: Surface functionalization of orthopedic implants with pharmaceutically active agents is a modern approach to enhance osseointegration in systemically altered bone. A local release of strontium, a verified bone building therapeutic agent, at the fracture site would diminish side effects, which could occur otherwise by oral administration. Strontium surface functionalization of specially designed titanium-niobium (Ti-40Nb) implant alloy would provide an advanced implant system that is mechanically adapted to altered bone with the ability to stimulate bone formation. Methods: Strontium-containing coatings were prepared by reactive sputtering of strontium chloride (SrCl2) in a self-constructed capacitively coupled radio frequency (RF) plasma reactor. Film morphology, structure and composition were investigated by scanning electron microscopy (SEM), time of flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). High-resolution transmission electron microscopy (HR-TEM) was used for the investigation of thickness and growth direction of the product layer. TEM lamellae were prepared using the focused ion beam (FIB) technique. Bioactivity of the surface coatings was tested by cultivation of primary human osteoblasts and subsequent analysis of cell morphology, viability, proliferation and differentiation. The results are correlated with the amount of strontium that is released from the coating in biomedical buffer solution, quantified by inductively coupled plasma mass spectrometry (ICP-MS). Results: Dense coatings, consisting of SrOxCly, of more than 100 nm thickness and columnar structure, were prepared. TEM images of cross sections clearly show an incoherent but well-structured interface between coating and substrate without any cracks. Sr2+ is released from the SrOxCly coating into physiological solution as proven by ICP-MS analysis. Cell culture studies showed excellent biocompatibility of the functionalized alloy. Conclusions: Ti-40Nb alloy, a potential orthopedic implant material for osteoporosis patients, could be successfully plasma coated with a dense SrOxCly film. The material performed well in in vitro tests. Nevertheless, the Sr2+ release must be optimized in future work to meet the requirements of an effective drug delivery system