Search

Lithium-rich, cobalt-free oxides are promising potential positive electrode materials for lithium-ion batteries because of their high energy density, lower cost, and reduced environmental and ethical concerns. However, their commercial breakthrough is hindered because of their subpar electrochemical stability. This work studies the effect of aluminum doping on Li1.26Ni0.15Mn0.61O2 as a lithium-rich, cobalt-free layered oxide. Al doping suppresses voltage fade and improves the capacity retention from 46% for Li1.26Ni0.15Mn0.61O2 to 67% for Li1.26Ni0.15Mn0.56Al0.05O2 after 250 cycles at 0.2 C. The undoped material has a monoclinic Li2MnO3-type structure with spinel on the particle edges. In contrast, Al-doped materials (Li1.26Ni0.15Mn0.61-xAlxO2) consist of a more stable rhombohedral phase at the particle edges, with a monoclinic phase core. For this core-shell structure, the formation of Mn3+ is suppressed along with the material's decomposition to a disordered spinel, and the amount of the rhombohedral phase content increases during galvanostatic cycling. Whereas previous studies generally provided qualitative insight into the degradation mechanisms during electrochemical cycling, this work provides quantitative information on the stabilizing effect of the rhombohedral shell in the doped sample. As such, this study provides fundamental insight into the mechanisms through which Al doping increases the electrochemical stability of lithium-rich cobalt-free layered oxides.

Magnetic hyperthermia holds significant therapeutic potential, yet its clinical adoption faces challenges. One obstacle is the large-scale synthesis of high-quality superparamagnetic iron oxide nanoparticles (SPIONs) required for inducing hyperthermia. Robust and scalable manufacturing would ensure control over the key quality attributes of SPIONs, and facilitate clinical translation and regulatory approval. Therefore, we implemented a risk-based pharmaceutical quality by design (QbD) approach for SPION production using flame spray pyrolysis (FSP), a scalable technique with excellent batch-to-batch consistency. A design of experiments method enabled precise size control during manufacturing. Subsequent modeling linked the SPION size (6–30 nm) and composition to intrinsic loss power (ILP), a measure of hyperthermia performance. FSP successfully fine-tuned the SPION composition with dopants (Zn, Mn, Mg), at various concentrations. Hyperthermia performance showed a strong nonlinear relationship with SPION size and composition. Moreover, the ILP demonstrated a stronger correlation to coercivity and remanence than to the saturation magnetization of SPIONs. The optimal operating space identified the midsized (15–18 nm) Mn0.25Fe2.75O4 as the most promising nanoparticle for hyperthermia. The production of these nanoparticles on a pilot scale showed the feasibility of large-scale manufacturing, and cytotoxicity investigations in multiple cell lines confirmed their biocompatibility. In vitro hyperthermia studies with Caco-2 cells revealed that Mn0.25Fe2.75O4 nanoparticles induced 80% greater cell death than undoped SPIONs. The systematic QbD approach developed here incorporates process robustness, scalability, and predictability, thus, supporting the clinical translation of high-performance SPIONs for magnetic hyperthermia.

Silicon powder kerf loss from diamond wire sawing in the photovoltaic wafering industry is a highly appealing source material for use in lithium-ion battery negative electrodes. Here, it is demonstrated for the first time that the kerf particles from three independent sources contain ~50 % amorphous silicon. The crystalline phase is in the shape of nano-scale crystalline inclusions in an amorphous matrix. From literature on wafering technology looking at wafer quality, the origin and mechanisms responsible for the amorphous content in the kerf loss powder are explained. In order to better understand for which applications the material could be a valuable raw material, the amorphicity and other relevant features are thoroughly investigated by a large amount of experimental methods. Furthermore, the kerf powder was crystallized and compared to the partly amorphous sample by operando X-ray powder diffraction experiments during battery cycling, demonstrating that the powders are relevant for further investigation and development for battery applications.

The instability of molecular electrodes under oxidative/reductive conditions and insufficient understanding of the metal oxide-based systems have slowed down the progress of H2-based fuels. Efficient regeneration of the electrode's performance after prolonged use is another bottleneck of this research. This work represents the first example of a bifunctional and electrochemically regenerable molecular electrode which can be used for the unperturbed production of H2 from water. Pyridyl linkers with flexible arms (-CH2-CH2-) on modified fluorine-doped carbon cloth (FCC) were used to anchor a highly active ruthenium electrocatalyst [RuII(mcbp)(H2O)2] (1) [mcbp2− = 2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine]. The pyridine unit of the linker replaces one of the water molecules of 1, which resulted in RuPFCC (ruthenium electrocatalyst anchored on -CH2-CH2-pyridine modified FCC), a high-performing electrode for oxygen evolution reaction [OER, overpotential of ∼215 mV] as well as hydrogen evolution reaction (HER, overpotential of ∼330 mV) at pH 7. A current density of ∼8 mA cm−2 at 2.06 V (vs. RHE) and ∼−6 mA cm−2 at −0.84 V (vs. RHE) with only 0.04 wt% loading of ruthenium was obtained. OER turnover of >7.4 × 103 at 1.81 V in 48 h and HER turnover of >3.6 × 103 at −0.79 V in 3 h were calculated. The activity of the OER anode after 48 h use could be electrochemically regenerated to ∼98% of its original activity while it serves as a HE cathode (evolving hydrogen) for 8 h. This electrode design can also be used for developing ultra-stable molecular electrodes with exciting electrochemical regeneration features, for other proton-dependent electrochemical processes., QC 20231116

Despite significant potential as energy storage materials for electric vehicles due to their combination of high energy density per unit cost and reduced environmental and ethical concerns, Co-free lithium ion batteries based on layered Mn oxides presently lack the longevity and stability of their Co-containing counterparts. Here, a reduction in this performance gap is demonstrated via chemical doping, with Li1.1Ni0.35Mn0.54Al0.01O2 achieving an initial discharge capacity of 159 mAhg−1 at C/3 rate and a corresponding capacity retention of 94.3% after 150 cycles. The nanoscale origins of this improvement are subsequently explored through a combination of advanced diffraction, spectroscopy, and electron microscopy techniques, finding that optimized doping profiles lead to an improved structural and chemical compatibility between the two constituent sub-phases that characterize the layered Mn oxide system, resulting in the formation of unobstructed lithium ion pathways between them. A structural stabilization effect of the host compound is also directly observed near the surface using aberration corrected scanning transmission electron microscopy and integrated differential phase contrast imaging.

Near-infrared (NIR) photothermal therapy by microneedles (MNs) exhibits high potential against skin diseases. However, high costs, photobleaching of organic agents, low long-term stability, and potential nanotoxicity limit the clinical translation of photothermal MNs. Here, photothermal MNs are developed by utilizing Au nanoaggregates made by flame aerosol technology and incorporated in water-insoluble polymer matrix to reduce intradermal nanoparticle (NP) deposition. The individual Au interparticle distance and plasmonic coupling within the nanoaggregates are controlled by the addition of a spacer during their synthesis rendering the Au nanoaggregates highly efficient NIR photothermal agents. In situ aerosol deposition of Au nanoaggregates on MN molds results in the fabrication of photothermal MNs with thin plasmonic layers. The photothermal performance of these MN arrays is compared to ones made by three methods utilizing NP dispersions, and it is found that similar temperatures are reached with 28-fold lower Au mass due to reduced light scattering losses of the thin layers. Finally, all developed photothermal MN arrays here cause clinically relevant hyperthermia at benign laser intensities while reducing intradermal NP deposition 127-fold compared to conventional MNs made with water-soluble polymers. Such rational design of photothermal MNs requiring low laser intensities and minimal NP intradermal accumulation sets the basis for their safe clinical translation.

Surface-enhanced Raman scattering (SERS) is a powerful sensing technique. However, the employment of SERS sensors in practical applications is hindered by high fabrication costs from processes with limited scalability, poor batch-to-batch reproducibility, substrate stability, and uniformity. Here, highly scalable and reproducible flame aerosol technology is employed to rapidly self-assemble uniform SERS sensing films. Plasmonic Ag nanoparticles are deposited on substrates as nanoaggregates with fine control of their interparticle distance. The interparticle distance is tuned by adding a dielectric spacer during nanoparticle synthesis that separates the individual Ag nanoparticles within each nanoaggregate. The dielectric spacer thickness dictates the plasmonic coupling extinction of the deposited nanoaggregates and finely tunes the Raman hotspots. By systematically studying the optical and morphological properties of the developed SERS surfaces, structure–performance relationships are established and the optimal hot-spots occur for interparticle distance of 1 to 1.5 nm among the individual Ag nanoparticles, as also validated by computational modeling, are identified for the highest signal enhancement of a molecular Raman reporter. Finally, the superior stability and batch-to-batch reproducibility of the developed SERS sensors are demonstrated and their potential with a proof-of-concept practical application in food-safety diagnostics for pesticide detection on fruit surfaces is explored.

Co-free Li-rich layered oxides are gaining interest as feasible positive electrode materials in lithium-ion batteries (LIBs) in terms of energy density, cost reduction, and alleviating safety concerns. Unfortunately, their commercialization is hindered by severe structural degradation that occurs during electrochemical operation. The study at hand demonstrates advanced structural engineering of a Li-rich Co-free oxide with composition Li1.1Ni0.35Mn0.55O2 by spray pyrolysis and subsequent calcination of an aqueous precursor, creating a segregated structure of two distinct layered phases with space groups R3̅m (rhombohedral) and C2/m (monoclinic). This particular structure was investigated with powder neutron diffraction, high-resolution analytical transmission electron microscopy imaging, and electron energy loss spectroscopic characterization. This complex structure contributes to the high electrochemical stability and good rate capability observed for this compound (160 mAh/g at C/3 and 100 mAh/g at 1C). These results provide new insights into the feasibility of developing and commercializing cobalt-free positive electrode materials for LIBs.

Plasmonic nanoparticles with near-IR (NIR) light absorption are highly attractive in biomedicine for minimally invasive photothermal treatments. However, these optical properties are typically exhibited by plasmonic nanostructures with complex, nonspherical geometries that may prohibit their broad commercialization and further integration into photothermal devices. Herein, we present the single-step aerosol self-assembly of plasmonic nanoaggregates that consisted of spherical silver nanoparticles with tunable extinction from visible to NIR wavelengths. This tunable extinction was achieved by the addition of SiO2 during the flame synthesis of the nanoparticles, which acted as a dielectric spacer between the spherical silver nanoparticles and was also computationally validated by simulating the extinction spectra of similar silver nanoaggregates. These plasmonic nanoaggregates were easily deposited on silicone polymeric surfaces and further encased with a top polymer layer, forming plasmonic photothermal nanocomposite films. The photothermal properties of the NIR nanocomposite films were utilized to eradicate the established biofilms of clinically relevant Escherichia coli and Staphylococcus aureus, with a relationship observed between the final surface temperature and biofilm eradication.

Lubrication of an internal combustion engine is critical for energy and material losses. Engine lubricants contain a number of functional additives including zinc dialkyldithiophosphate, which is a commonly used antiwear additive that forms by in situ decomposition a protective interface at the metal surface. Here, we present a detailed nanoscale investigation of carbonaceous soot nanoparticles generated from real engine conditions. By combining macroscale XPS with high-resolution STEM-EELS-EDX, we reveal that such a soot nanoparticle matrix contains also 3-5 nm ZnO-based nanoparticles with additions of phosphorus and sulfur, originating from the organometallic antiwear additive. Under the consideration of the obtained chemical information on the carbonaceous matrix and (ZnO:P,S) nanoparticles and the generally known suggestion of potential toxicity for soot nanoparticles, our method allows us to predict nanoparticle-based hazards from mechanochemical applications and also their formation mechanism. These are critical information and also the basis of toxicity assessment, both for theoretical predictions and experimental testing for the estimation of overall life-cycle analysis, including the environmental impact. Our results unravel the tribofilm decomposition under real field conditions and hint toward potentially unidentified toxicological nanoparticle hazards with respect to organophosphate-containing lubricants.