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.

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.

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.

Hollow Mesoporous Silica@Metal-Organic Framework and Applications for pH-Responsive Drug Delivery.

Metal--organic frameworks (MOFs), a new type of porous crystalline material, hold great potential in biomedical applications, such as drug delivery. However, the efficacy of drug delivery is limited by low drug loading. In this work, we synthesized hollow mesoporous silica (HMS)@MOF capsules that can be used as a pH-responsive drug delivery system for the anticancer drug doxorubicin (DOX). DOX is loaded into the inner cavity of HMS. Zeolitic imidazolate framework-8 (ZIF-8) nanoparticles are then coated on the outer surface of the DOX-loaded HMS. The obtained material is a capsule (denoted as DOX/HMS@ZIF), in which DOX is encapsulated. The DOX/HMS@ZIF can be used as an efficient pH-responsive drug delivery system. DOX is not released under physiological conditions (pH 7.4), but is released at low pH (4-6) from DOX/HMS@ZIF. The DOX/HMS@ZIF capsule shows much higher cytotoxicity than free DOX and alters the delivery pathway for DOX in cancer cells, while the drug-free HMS@ZIF shows excellent biocompatibility. This opens new opportunities to construct a safe and efficient delivery system for targeted molecules using pH-responsive release for a wide range of applications.