Direct View on the Origin of High Li+ Transfer Impedance in All-Solid-State Battery

Large interfacial resistance plays a dominant role in the performance of all-solid-state lithium-ion batteries. However, the mechanism of interfacial resistance has been under debate. Here, the Li⁺ transport at the interfacial region is investigated to reveal the origin of the high Li⁺ transfer impedance in a LiCoO₂(LCO)/LiPON/Pt all-solid-state battery. Both an unexpected nanocrystalline layer and a structurally disordered transition layer are discovered to be inherent to the LCO/LiPON interface. Under electrochemical conditions, the nanocrystalline layer with insufficient electrochemical stability leads to the introduction of voids during electrochemical cycles, which is the origin of the high Li⁺ transfer impedance at solid electrolyte-electrode interfaces. In addition, at relatively low temperatures, the oxygen vacancies migration in the transition layer results in the formation of Co₃O₄ nanocrystalline layer with nanovoids, which contributes to the high Li⁺ transfer impedance. This work sheds light on the mechanism for the high interfacial resistance and promotes overcoming the interfacial issues in all-solid-state batteries.     

Surfactant-free electrochemical synthesis of fluoridated hydroxyapatite nanorods for biomedical applications

Fluoridated hydroxyapatite (FHA) [Ca₁₀(PO₄)₆F_x(OH)_2−x, x = 0–2] is believed to be a promising calcium phosphate (CaP) to replace pure hydroxyapatite (HA) for next-generation implants, owing to its better biocompatibility, higher antibacterial activity, and lower solubility. Notably, the shape and size of the CaP crystals play key roles in their performance and can influence their applications. One-dimensional (1D) FHA nanorods are important CaP materials which have been widely used in regenerative medicine applications such as restorative dentistry. Unfortunately, the traditional synthesis methods for FHA nanorods either employ surfactants or take a relatively long time. In this study, we aimed to propose a facile synthesis route to fabricate FHA nanorods without any surfactants using an electrochemical deposition method for the first time. This study focused on preparing FHA nanorods without the assistance of any surfactant, unlike the traditional synthesis methods, to avoid chemical impurities. FHA nanorods with lengths of 124–2606 nm, diameters of 28–211 nm, and aspect ratios of 4.4–21.8 were synthesized using the electrochemical method, followed by a heat treatment. For the as-synthesized FHA nanorods, the Ca/P ratio was 1.60 and the atomic concentration of F was 2.06 at.%. An ultrastructure examination revealed that each FHA nanorod possessed long-range order, good crystallinity, and a defect-free lattice with a certain crystallographic plane orientation along the whole rod. In short, we propose a novel, surfactant-free, cost-saving, and more efficient route to synthesize FHA nanorods which can be widely applied in multiple biomedical applications, including drug delivery, bone repair, and restorative dentistry.     

Fabrication and optical properties of transparent LaErZr2O7 ceramic with high excess contents of La and Er

In this study, transparent LaErZr₂O₇ ceramic with high excess La and Er contents (nominally La_1.28Er_1.28Zr₂O_7.84) was successfully prepared by vacuum sintering at 1850?°C for 6?h using nanosized powder. The XRD, SEM, EDX and TEM results reveal that the single pyrochlore phase in the powder sample transforms to the coexistence of La-rich pyrochlore phase and Er-rich defect fluorite phase after high temperature sintering. The high excess amounts of La and Er favor the formation of pyrochlore structure. Despite the coexistence of two phases, the sample with 1?mm thickness shows excellent in-line transmittance in the visible to mid-infrared region (as high as 81% at 1100?nm). The upconversion and infrared emission under 980?nm exciting were measured and discussed as well.     

Enhancement of resistance to galvanic corrosion of ZE41 Mg alloy by equal channel angular pressing

The galvanic corrosion behavior of as-received and ECAPed ZE41 Mg alloy coupled with Al7075 alloy is investigated using zero resistance ammeter in three different corrosive environments, 0, 0.1, and 1 M NaCl, to mimic the conditions experienced in engineering applications. The mechanism of galvanic corrosion for the ZE41 Mg–Al7075 aluminum alloy is explained. It is observed that a robust surface film containing a composite layer of oxide/hydroxide of magnesium and aluminum is established in deionized water (0 M). However, only a single layer of magnesium oxide/hydroxide is detected in chloride-containing environments. Equal channel angular pressing (ECAP) improved the resistance to galvanic corrosion by 58% and 54% when compared with the as-cast counterparts in 0 and 1 M NaCl solution, respectively. In contrast, galvanic corrosion resistance decreased by 26% in 0.1 M NaCl after ECAP while the as-received samples evinced pits unfavorable to be used in engineering applications. ECAP is a promising method to combat galvanic corrosion encountered by ZE41 magnesium alloy used in automobiles and components of military vehicles.     

Impregnated active layer combustion synthesis of nano MgFe2O4 using green template

Nano-Magnesium ferrite (MgFe₂O₄) powders have been prepared by a modified combustion synthesis method named impregnated active layer combustion (IALC). The effects of five important parameters such as main fuel to oxidizer ratio (F/O), main fuel type, added fuel type, template type and main fuel (Added F/MF) to the added fuel ratio have been studied using Taguchi design. Xylitol, D-mannitol, ethylene diamine tetra acetic acid (EDTA) and diethylene triamine penta acetic acid (DTPA) were used as fuels. Besides, waste newspaper and Platanus orientalis leaf (POL) were used as new green templates. Samples were characterized by XRD, XRF, SEM, TEM, BET and VSM analyses. Results showed that the average crystallite size of the sample prepared under optimized condition (mixture of Xylitol and DTPA as fuel, POL as template, and Added F/MF ratio of 0.75) was 17.66?nm. The result was confirmed by TEM. The saturated magnetization of the optimum sample was 21?emu/g and the specific surface area was 15.377?m²/g.     

Carbon content-dependent microstructures,surface characteristics and thermal stability of mechanical alloying derived SiBCN powders

Three types of SiBCN: carbon-lean, -moderate and -rich powders with the same Si/B/N mole ratio were subjected to high-energy ball milling to yield an amorphous structure. The effects of carbon content on microstructures, solid-state amorphization, surface characteristics and thermal stability of the as-milled powders were studied in detail. Results showed that the increases in carbon content can drive solid-state amorphization accompanied by strain-induced, crystallite refinement-induced and/or chemical composition-induced nucleation of nano-SiC from an amorphous body. The specific surface area increases as carbon content increases. The amorphous networks of Si–C, C–B/C–C, C–N, B–N and C–B–N bonds that compose the amorphous nature, but the species and contents of the chemical bonds are carbon content-dependent. Carbon-moderate powders possess satisfying thermal stability while carbon-rich ones perform the worst. Mechanical alloying derived SiBCN powders have outstanding oxidation resistance below 800 °C; however only carbon-moderate powders show desirable anti-oxidation ability at higher temperatures. Thus, mechanical alloying of SiBCN appears a suitable technique for developing amorphous matrix materials for practical applications.     

In-situ TEM study of the aging micromechanisms in a BaTiO3-based lead-free piezoelectric ceramic

Aging and fatigue are the two main concerns regarding the performance reliability of piezoelectric ceramics. Compared with fatigue, less efforts have been made towards clarifying the micromechanisms of aging. In this report, we employ electric field in-situ transmission electron microscopy (TEM) to directly visualize the domain structure evolution during fatigue and the subsequent aging process in the 0.5Ba(Zr_0.2Ti_0.8)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ (BZT–BCT) polycrystalline ceramic. The macroscopic aging behaviors, including the development of internal bias field (E_bias) and the degradation in switchable polarization (2P_r), are correlated with the microscopic domain wall clamping and domain disruption resulted from the redistribution of oxygen vacancies driven by depolarization field.     

Damage microstructure evolution of helium ion irradiated SiC under fusion relevant temperatures

In-situ transmission electron microscopy (TEM) with ion irradiation has been used to study the damage microstructure evolution of He ion irradiated 4-H SiC at nuclear fusion relevant temperatures. The SiC samples were irradiated with 20?keV He ions at 25, 400, 800 and 1200?°C to a dose of 5.0 displacements per atom (DPA). At 25?°C, the material fully amorphises at 1.5 DPA and no He bubble nucleation occurs up to the doses studied. At 400 and 800?°C, He bubble nucleation occurs and the material remains crystalline. Bubble nucleation occurs at 2.0?DPA at 400?°C but occurs at only 0.5?DPA at 1200?°C. This is attributed the He atoms de-trapping from vacancies and migrating interstitially to larger He-vacancy clusters at higher temperatures, leading to faster nucleation of observable He bubbles. Helium platelets form at an irradiation temperature of 1200?°C at 0.5?DPA showing a preference for nucleation between the {0001} basal planes.     

Mullite-bonded SiC-whisker-reinforced SiC matrix composites: Preparation,characterization, and toughening mechanisms

A novel mullite-bonded SiC-whisker-reinforced SiC matrix composite (SiCw/SiC, SiC whisker-to-SiC powder mass ratio of 1:9) was designed and successfully prepared. Before preparing the composite, the inexpensive lab-made SiCw was first modified by an oxidation/leaching process and then coated with Al₂O₃. The kinetics results indicate that the oxidation process can be described by improved shrinking-cylinder models. The aspect ratio of SiCw improved after modification. Subsequently, raw materials with a SiC–SiO₂–Al₂O₃ triple-layered structure were obtained after the Al₂O₃-coating process and used as feedstocks during the subsequent hot-pressing sintering. Finally, the characterization of the composites indicates that the mullite-bonded sample performs better (relative density of 93.8?±?1.4%, flexural strength of 533.3?±?18.2?MPa, fracture toughness of 13.6?±?2.1?MPa?m^1/2, and Vickers hardness of 20.6?±?2.5?GPa) than the reference sample without the mullite interface. The improved toughness could essentially be attributed to the moderately strong interface bonding and effective load transfer effects of the mullite interface.     

Determination and identification of titanium dioxide nanoparticles in confectionery foods,marketed in South Korea,using inductively coupled plasma optical emission spectrometry and transmission electron microscopy

Food-grade titanium dioxide (TiO₂) is a common and widespread food additive in many processed foods, personal care products, and other industrial categories as it boosts the brightness and whiteness of colours. Although it is generally recognised as safe for humans, there is a growing interest in the health risks associated with its oral intake. This study quantified and identified TiO₂ nanoparticles present in confectionery foods, which are children’s favourite foods, with inductively coupled plasma optical emission spectrometry (ICP-OES) and transmission electron microscopy (TEM). A reliable digestion method using hot sulphuric acid and a digestion catalyst (K₂SO₄:CuSO₄ = 9:1) was suggested for titanium analysis. Validations of the experimental method were quite acceptable in terms of linearity, recoveries, detection limits, and quantification limits. Of all the 88 analysed foods, TiO₂ was detected in 19 products, all except three declared TiO₂ in their labelling. The mean TiO₂ content of candies, chewing gums, and chocolates were 0.36 mg g^?1, 0.04 mg g^?1, and 0.81 mg g^?1, respectively. Whitish particles isolated from the confectionery foods were confirmed as TiO₂ nanoparticles via TEM and energy dispersive X-ray spectroscopy (EDX), in which nanosized particles (<100 nm) were identified.