Electrochemical Synthesis and Carbon Doping of Nanostructured Iron Fluorides from the Selection of Metal Current Collectors in Lithium-Ion Batteries

Abstract

The use of materials that rely on conversion reactions as electrodes in lithium-ion batteries is extensively investigated due to their potential for enhanced capacity compared to traditional electrode materials. Iron fluorides, in particular, present a promising alternative in terms of specific capacity. However, these materials often face challenges related to low intrinsic conductivity. This issue is typically addressed in the literature by doping the active material with carbon particles and reducing the particle size of the active material. This study explores the feasibility of directly integrating conductive carbon from the substrate into the fluoride-based active material during the synthesis process. The synthesis employs a simple anodic method conducted directly on the chosen metallic substrate, which then functions as the current collector in the devices. This approach simplifies the synthesis process, reduces processing time, and eliminates the need for additives and binders at the conventional active material-current collector interface. Two FeF₃ layers were electrochemically synthesized on steel substrates with different carbon contents. These layers were evaluated as cathode-active materials for rechargeable lithium-ion batteries. The influence of carbon on the conductivity of the conversion layer was assessed using Electrochemical Impedance Spectroscopy (EIS) with a model based on conductive porous electrodes. Morphological and thickness analyses of the layers showed a strong correlation between increased pore size and layer thickness and the carbon content in the metallic substrate. The optimal performance was observed with the layer on the substrate with higher carbon content. The electrochemical performance of the active material was further evaluated using electrochemical impedance spectroscopy and galvanostatic tests in pouch cells. The conversion layers derived from carbon steel exhibited reduced resistivity and enhanced specific capacitance and cyclability compared to layers formed on pure iron.