Studies on Rechargeable Fe-air electrodes in Alkaline electrolyte
Abstract: Energy storage system is an important component in the energy system based on variable renewable energy sources into the grid. Energy storage system could contribute to decarbonization, energy security, offset the demand and supply of the electricity sector, especially for the electric grid. These can be either mechanical, electrochemical, chemical, electromagnetic or thermal devices. The most important functional characteristics of an energy storage system are capital cost, roundtrip efficiency, energy and power rating, response times and cycle life. Electrochemical energy storage systems (EES) have the following edge over the other systems: fast response time, relatively short duration of storage, size, high efficiency, a decentralized installation which is closer to generation or consumption site.The focus of this thesis is on the development of cost-effective iron anode materials and electrocatalytic air electrodes for Fe-air batteries that potentially could become as an energy storage system. Iron-based systems are attractive due to their safety, cheapness, non-toxicity and ubiquitous availability of materials. However, both the anode and cathode parts have numerous drawbacks that need to be addressed. The anode exhibits poor charge efficiency, rate capability and low capacity utilization while the cathode has sluggish kinetics, poor activity, structural stability and the numbers of active non-noble metal catalysts are limited.This work utilized Cu and Sn-doped iron nanomaterials and different additives (Bi2S3, CNT, LiOH) to enhance the performance of the iron electrode. The performance of the electrodes were evaluated using the charge/discharge cycling, rate capability, cyclic voltammetry (CV), galvanostatic and potentiodynamic polarization measurements, in operando charging measurements combined with mass spectrometry. The fresh and cycled electrodes and powders were characterized by ex-situ XRD, BET, SEM, TEM , XPS and Raman spectroscopy. The most striking results are the prevention of nanoparticle agglomeration, increased charging efficiency (80-91%), effect of Cu and Sn dopants on specific capacity (367-603 mAh g-1) and improved performance of the electrodes at high charge current densities.In the subsequent air electrode part, non-precious metal La-doped CaMnOx, nano Co3O4 and NiFeOX electrocatalysts were synthesized using co-precipitation and hydrothermal methods. Both the single and mixed catalysts were used as bi-functional catalysts for oxygen reduction and evolution reactions (ORER). The catalysts were characterized by XRD, SEM, TEM, BET, Raman and XPS. The electrocatalytic activity and stability were assessed in alkaline solutions on gas diffusion electrodes and glassy carbon electrode by linear sweep voltammetry (LSV), CV and rotating disk electrode (RDE). Furthermore, the mixed catalyst and NiFeOX showed excellent bifunctional performance such as high activity and stability achieved by the hybridization of the two catalysts and the effect of catalyst loading on the electrocatalytic performance. These findings can help to develop a cost-effective material for Fe-air batteries.
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