Nanostructured Metal Sulfides for Electrochemical Energy Conversion
[eng] Storing the fluctuating renewable energy into synthetic fuels or in batteries is meaningful due to the emerging energy crisis. In this thesis, four nanostructured catalysts based on two kinds of metal sulfides, namely Cu2S and SnS2, were produced and optimized to improve their performance towa...
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| Formato: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2020 |
| País: | España |
| Recursos: | Universidad de Barcelona |
| Repositorio: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/174388 |
| Acesso em linha: | https://hdl.handle.net/2445/174388 http://hdl.handle.net/10803/670925 |
| Access Level: | acceso abierto |
| Palavra-chave: | Col·loides Compostos de sofre Conversió directa de l'energia Electroquímica Colloids Sulfur compounds Direct energy conversion Electrochemistry |
| Resumo: | [eng] Storing the fluctuating renewable energy into synthetic fuels or in batteries is meaningful due to the emerging energy crisis. In this thesis, four nanostructured catalysts based on two kinds of metal sulfides, namely Cu2S and SnS2, were produced and optimized to improve their performance towards three key electrochemical energy conversion processes, namely electrochemical oxygen evolution, photoelectrochemical water splitting and lithium-ion batteries. Chapter 1 presented a general introduction to explain the motivation of the thesis topic. In chapter 2, a metallic copper substrate was used as current collector and chemical template to produce Cu2S nanorod arrays for electrochemical oxygen evolution reaction (OER). Suitable characterization tools were applied to investigate the chemical, structural and morphological transformation in OER operation, during which the initial Cu2S nanorod arrays would perform as a “pre-catalyst” that in-situ changed to CuO nanowires. Notably, the Cu2S-derived CuO showed significant improved OER performance compared with that of CuO prepared by directly annealing a Cu(OH)2 precursor, in terms of both activity and stability. Thus obtained electrocatalyst can be ranked among the best Cu-based OER catalysts reported so far. To take advantage of the unlimited solar energy, an ultrathin SnS2 NPL with a suitable band gap around 2.2 eV was produced via a hot-injection solution-based process in chapter 3. The unsatisfied photoelectrochemical (PEC) performance of bare SnS2 motivated me to deposit Pt NPs on its surface as cocatalyst via in-situ reduction of a Pt salt. The resulting SnS2-Pt heterostructures with optimal Pt amount showed significant improvement (six fold) towards PEC water oxidation. Mott-Schottky analysis and PEC impedance spectroscopy (PEIS) were used to analyze in more detail the effect of Pt on the PEC performance. The optimal SnS2-Pt heterostructure presented acceptable performance towards PEC water splitting. However, it still suffered from a moderate stability due to the peel-off of the catalyst layer from the FTO surface. To solve this problem, in chapter 4 we detailed a simple, versatile and scalable amine/thiol- based molecular ink to grow nanostructured SnS2 layers directly on conductive substrates such as FTO, stainless steel and carbon cloth. Such layers on FTO were characterized by excellent photocurrent densities. The same strategy was used to produce SnS2-graphene composites, SnS2-xSex ternary coatings and even phase pure SnSe2 layers. Finally, the potential of this precursor ink to produce gram scale amounts of unsupported SnS2 was also investigated. Apart from the application as a photocatalyst, SnS2 can also be a promising anode material for Li-ion batteries (LIB). In chapter 5, nanostructured SnS2 with different morphologies produced in chapter 3 were tested as LIB anodes firstly to find that thin SnS2 NPLs provided the highest performance. Thereafter, a colloidal synthesis strategy to grow the same SnS2 NPLs within a matrix of porous g-C3N4 (CN) and graphite plates (GPs) was developed and the obtained materials were tested for LIB application. Such hierarchical SnS2/CN/GP composites using SnS2-NPL as active materials, porous CN to provide avenues for electrolyte diffusion and ease the volumetric expansion of SnS2, and GP as “highways” for charge transport displayed excellent rate capabilities (536.5 mAh g-1 at 2.0 A g-1) and an outstanding stability (~99.7 % retention after 400 cycles), which were partially associated with a high pseudocapacitance contribution (88.8 % at 1.0 mV s-1). The excellent electrochemical properties of these nanocomposites were ascribed to the synergy created between the three components. Overall, four nanostructured catalysts based on Cu2S and SnS2 were prepared, and proper optimizations/treatments were defined to improve their catalytic performance. The results shown in this thesis demonstrate the promising application of non-toxic, low cost metal sulfides in electrochemical energy conversion technologies. |
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