Influence of Lithium Diffusion into Copper Current Collectors on Lithium Electrodeposition in Anode‐Free Lithium‐Metal Batteries

The development of “anode-free” lithium-metal batteries with high energy densities is, at present, mainly limited by the poor control of the nucleation of lithium directly on the copper current collector, especially in conventional carbonate electrolytes. It is therefore essential to improve the understanding of the lithium nucleation process and its interactions with the copper substrate. In this study, it is shown that diffusion of lithium into the copper substrate, most likely via the grain boundaries, can significantly influence the nucleation process. Such diffusion makes it more difficult to obtain a great number of homogeneously distributed lithium nuclei on the copper surface and thus leads to inhomogeneous electrodeposition. It is, however, demonstrated that the nucleation of lithium on copper is significantly improved if an initial chemical prelithiation of the copper surface is performed. This prelithiation saturates the copper surface with lithium and hence decreases the influence of lithium diffusion via the grain boundaries. In this way, the lithium nucleation can be made to take place more homogenously, especially when a short potentiostatic nucleation pulse that can generate a large number of nuclei on the surface of the copper substrate is applied

Estimation of Chlorophyll-a Concentrations in the Pearl River Estuary Using In Situ Hyperspectral Data: A Case Study

Taking Pearl River Estuary (PRE), China as an example, we explored the potential of in situ hyperspectral data in estimating chlorophyll-a concentrations of turbid waters. Two cruises were conducted on August 21, 2006 and May 18, 2004 to collect the data of water quality and remote sensing reflectance (Rrs). The field surveys showed that chlorophyll-a concentration ranged from 2.97 mu g/L to 49.97 mu g/L, and turbidity 13.6-128.9 NTU. The Rrs spectra were binned to 10 nm resolution, and then processed to be first-order and second-order derivatives. A linear algorithm is developed to estimate chlorophyll-a concentrations based on second order derivative at 670 nm; its mean relative errors of estimation is less than 58% and the root mean square error is 6.69 mu g/L, which is better than other popular algorithms for turbid waters, i.e., the ratio of Rrs at 700 nm and 670 nm. The Case-I algorithm of blue-green band ratio is also proved to be a failed application in PRE, and so does the algorithm of fluorescence line height (FLH), which is questionable for its application in waters with strong light scattering and absorption. All the above work was done without classification of cloud conditions. This suggests that the second-order derivative at 670 nm could be effective for estimation of chlorophyll-a concentrations in turbid waters especially in situ

Potentials in Li-Ion Batteries Probed by Operando Ambient Pressure Photoelectron Spectroscopy

The important electrochemical processes in a battery happen at the solid/liquid interfaces. Operando ambient pressure photoelectron spectroscopy (APPES) is one tool to study these processes with chemical specificity. However, accessing this crucial interface and identifying the interface signal are not trivial. Therefore, we present a measurement setup, together with a suggested model, exemplifying how APPES can be used to probe potential differences over the electrode/electrolyte interface, even without direct access to the interface. Both the change in electron electrochemical potential over the solid/liquid interface, and the change in Li chemical potential of the working electrode (WE) surface at Li-ion equilibrium can be probed. Using a Li4Ti5O12 composite as a WE, our results show that the shifts in kinetic energy of the electrolyte measured by APPES can be correlated to the electrochemical reactions occurring at the WE/electrolyte interface. Different shifts in kinetic energy are seen depending on if a phase transition reaction occurs or if a single phase is lithiated. The developed methodology can be used to evaluate charge transfer over the WE/electrolyte interface as well as the lithiation/delithiation mechanism of the WE

Using second-derivative spectrum to estimate Chlorophyll-a concentration in turbid estuarine waters

Hyperspectral technique is considered as one promising tool to solve the problems in monitoring optically-complex waters, which can be applied in optical sensors on board bouy, plane and satellite. In order to apply the technique in the in-situ chlorophyll monitoring of estuarine turbid waters, two cruises were carried out in May, 2004 and August, 2006, respectively, in Pearl River Estuary, China. In the cruises, water samples were collected at each sample station, a portable field spectroradiometer was used simultaneously to measure the downwelling sky radiance, and upwelling radiance of water and reference plaque, and the reflectance was calculated out. Further, the original reflectance spectra with 0.38 nm spectral resolution were resampled to 10 run resolution, and then derivative spectra were processed. The results of correlation analysis between the chlorophyll-a concentrations and derivative spectra indicate that the second derivative spectra especially at 670 nm can be used to estimate chlorophyll-a concentration of turbid estuarine waters, which suggests a new way for the in-situ chlorophyll measurement in the optically-complex waters

Hollow Mesoporous Silica@Zeolitic Imidazolate Framework Capsules and Their Applications for Gentamicin Delivery

We have synthesized hollow mesoporous silica (HMS) at a zeolitic imidazolate framework (ZIF) capsule that can be used as a drug delivery system for gentamicin (GM). The GM is first loaded into HMS. Then, the outer surface of the GM/HMS is coated with uniformed ZIF nanoparticles (denoted as GM/HMS@ZIF). The GM/HMS@ZIF has been successfully prepared and acts as a capsule for GM. The GM/HMS@ZIF shows a good biocompatibility and a good cellular uptake in House Ear Institute-Organ of Corti 1 (HEI-OC1) cells. The GM is released slowly within 10 h under acidic conditions, which is used to simulate the pH of the endosome and lysosome compartments. The in vivo assay shows that the signal from fluorescein isothiocyanate (FITC) can be observed after 15 days, when the mice were injected with FITC/HMS@ZIF. This opens new opportunities to construct a delivery system for GM via one controlled low dose and sustained release for the therapy of Ménière’s disease

Investigating Surface Reactivity of a Ni-Rich Cathode Material toward CO2, H2O, and O2 Using Ambient Pressure X-ray Photoelectron Spectroscopy

Layered Ni-rich transition metal oxide materials are considered the most promising cathodes for use in commercial Li-ion batteries. Due to their instability in air, an impurity layer forms during storage under ambient conditions, and this layer increases electrochemical polarization during charging and discharging, which ultimately leads to a lower cycling capacity. In this work, we found that storage of the LiNi0.8Mn0.1Co0.1O2 (NMC 811) material in ultrahigh vacuum (UHV) can restore the surface by reducing the amount of native carbonate species in the impurity layer. In this work, in situ soft X-ray ambient pressure photoelectron spectroscopy is used to directly follow the interaction between common gases found in air and the NMC 811 surface. During gas exposure of the NMC 811 surface to pure CO2, O2, and a mixture of both pure gases, surface-adsorbed CO2 or/and O2 were detected; however, permanent changes could not be identified under UHV after the gas exposure. In contrast, a permanent increase in metal hydroxide species was observed on the sample surface following H2O vapor exposure, and an increased intensity in the carboxylate peak was observed after exposure to a mixture of CO2/O2/H2O. Thus, the irreversible degradation reaction with CO2 is triggered in the presence of H2O (on relevant time scales defined by the experiment). Additional measurements revealed that X-ray irradiation induces the formation of metal carbonate species on the NMC 811 surface under CO2 and H2O vapor pressure