RESUMEN
The trade-off between energy density and power capabilities is a challenge for Li-ion battery design as it highly depends on the complex porous structures that holds the liquid electrolyte. Specifically, mass-transport limitations lead to large concentration gradients in the solution-phase and subsequently to crippling overpotentials. The direct study of these solution-phase concentration profiles in Li-ion battery positive electrodes has been elusive, in part because they are shielded by an opaque and paramagnetic matrix. Herein we present a new methodology employing synchrotron hard X-ray fluorescence to observe the concentration gradient formation within Li-ion battery electrodes in operando. This methodology is substantiated with data collected on a model LiFePO4/Li cell using a 1 M LiAsF6 in 1:1 ethylene carbonate/dimethyl carbonate (EC/DMC) electrolyte under galvanostatic and intermittent charge profiles. As such, the technique holds great promise for optimization of new composite electrodes and for numerical model validation.
RESUMEN
Composite electrodes can significantly improve the performance of an electrochemical device by maximizing surface area and active material loading. Typically, additives such as carbon are used to improve conductivity and a polymer is used as a binder, leading to a heterogeneous surface film with thickness on the order of 10s of micrometers. For such composite electrodes, good ionic conduction within the film is critical to capitalize on the increased loading of active material and surface area. Ionic conductivity within a film can be tricky to measure directly, and homogenization models based on porosity are often used as a proxy. SICM has traditionally been a topography-mapping microscopy method for which we here outline a new function and demonstrate its capacity for measuring ion conductivity within a lithium-ion battery film.
RESUMEN
A Mn(i) tris(2-pyridylmethyl)amine complex fac-[Mn(κ3-tpa) (CO)3]+OTf- carries out electrocatalytic hydrogen evolution from neutral water in acetonitrile. Bulk electrocatalytic studies showed that the catalyst functions with a moderate Faradaic efficiency and turn over frequency. DFT computations support the role of the tpa ligand as a shuttle to transfer of protons to the metal center.