Structure Engineering towards High-Performance Electrodes for Electrochemical Energy Conversion and Storage

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Zhao, Huijun

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Yang, Huagui

Yin, Huajie

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Major concerns about the effects of increasing fossil fuel consumption on the environment and energy security have prompted the development of sustainable and environmentally-friendly energy conversion and storage technologies based on electrochemical processes (e.g. water electrolysers, batteries and supercapacitors). Electrode materials are a key component of these technologies, and high-performance electrode systems are essential for the realization of a clean-energy-based economy. Numerous efforts have been made to develop advanced electrode materials for energy conversion and storage applications. However, current electrode synthesis methods are usually energy-intensive, not environmentally friendly, difficult to scale, or costly to produce. This thesis aims to utilize electrode structure engineering to develop highperformance electrodes based on earth-abundant materials via low-cost, energy-efficient and green synthesis strategies. Further, the applications of these electrodes in various energy conversion and storage applications are explored. Nickel-iron oxides or hydroxides are considered promising electrocatalysts for the oxygen evolution reaction, featuring a high activity and long cycling life in alkaline solution. A room temperature, electroless method has been developed here to grow nickel-iron hydroxides on a nickel foam current collector. The activity of nickel foam for the oxygen evolution reaction can be remarkably enhanced by simply immersing the nickel foam in a ferric nitrate solution at room temperature. During this process, the oxidation of the nickel foam surface by ferric nitrate ions increases the near-surface concentration of hydroxide ions, which results in the in situ deposition of a highly active, amorphous nickel-iron hydroxide layer. This phenomenon is described in Chapter 2 of this thesis. Carbon cloth is a widely-adopted current collector for the fabrication of electrodes. A facile, two-step method has been investigated here to turn commercial carbon cloth into a high-performance electrode for zinc-air batteries. Mild acid oxidation followed by air calcination directly activate carbon cloth to generate uniform, nanoporous and superhydrophilic surface structures with optimized, oxygen-rich functional groups and dramatically increased surface area. This two-step-activated carbon cloth exhibits superior bifunctional oxygen electrocatalytic activity and durability. A rechargeable, flexible zinc-air battery using the activated carbon cloth as a binder-free, flexible air electrode yields a remarkably high peak power density, high flexibility, and good cycling performance, with a small charge-discharge voltage gap. This work is elaborated in Chapter 3. Cost-effective synthesis of large-scale, uniform electrode materials with high activity and cycling stability is challenging. In Chapter 4, a reaction environment confinement strategy for scalable and reproducible production of nanostructured materials is proposed. Nickel foam is simply immersed in metal nitrate aqueous solution, with the volume of solution per unit area of nickel foam kept very low. A precisely designed reactor with a spiral tunnel ensures the same width of solution on each side of the nickel foam. The reaction environment is confined to ensure reproducible and uniform synthesis of nanostructured materials across the Ni foam. This approach has the largest REAVC (ratio of electrode area to precursor volume consumption) value reported so far, 2.0 cm2 mL-1. The synthesized nickel-iron hydroxides/nickel foam electrodes with uniformity in both microstructure and electrochemical properties exhibit remarkable activity for both the oxygen evolution reaction and hydrogen evolution reaction. Manganese oxides are a class of promising electrode materials for high performance supercapacitors. However, not all types of manganese oxides with different phases are electrochemically active, and their crystal structures have a considerable effect on their capacitance. In Chapter 5, a facile strategy is developed for the transformation of manganese oxide from the orthorhombic to birnessite crystal structure. The product exhibits significantly enhanced electrochemical performance as a supercapacitor electrode. This work opens up new possibilities for changing the crystal structure of manganese oxides towards optimized properties in electrochemical applications. This thesis makes significant contributions to our understanding of electrode structure engineering, materials science and electrochemical energy conversion and storage through: (i) designing novel nanostructured nickel-foam-based electrode systems with high electrocatalytic activity towards water oxidation via a simple immersion strategy at ambient temperature; (ii) developing facile activation procedures to endow commercially available, inactive carbon cloth with oxygen-rich functional groups and high oxygen electrocatalytic activity; (iii) controlling ion diffusion in a confined zone for uniform deposition of active materials over large-size electrodes, electrodes useful for various electrochemical applications; (iv) probing the phase transformation of manganese oxides from orthorhombic to birnessite, a material with enhanced electrochemical performance; (v) investigating the growth mechanisms of these advanced electrode materials to understand the origin of their exceptional activity.

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Thesis (PhD Doctorate)

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Doctor of Philosophy (PhD)


School of Environment and Sc

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electrode structure engineering

high-performance electrodes

energy conversion

energy storage

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