2024-03-29T12:57:16Zhttps://www.tdx.cat/oai/requestoai:www.tdx.cat:10803/6709222021-02-25T10:12:22Zcom_10803_1col_10803_95809
nam a 5i 4500
Col·loides
Coloides
Colloids
Electroquímica
Electroquímica
Electrochemistry
Conversió directa de l'energia
Conversión directa de la energía
Direct energy conversion
Catàlisi
Catálisis
Catalysis
Transformation of Nanocrystals in Electrochemical Energy Technologies
[Barcelona] :
Universitat de Barcelona,
2021
Accés lliure
http://hdl.handle.net/10803/670922
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Yu, Xiaoting,
autor
1 recurs en línia (186 pàgines)
Tesi realitzada a l'Institut de Recerca en Energia de Catalunya (IREC)
Tesi
Doctorat
Universitat de Barcelona. Facultat de Física
2020
Universitat de Barcelona. Facultat de Física
Tesis i dissertacions electròniques
Cabot i Codina, Andreu,
supervisor acadèmic
Luo, Zhishan,
supervisor acadèmic
Güell Vilà, Frank,
supervisor acadèmic
TDX
This thesis focuses on the synthesis of different types of NCs, their application to energy conversion and storage technologies, particularly LIBs, KIBs and DEFCs, and their structural transformation during electrochemical processes within these energy storage and conversion applications. The morphology and composition of target transition metal oxides, bimetallic NCs and phosphorous incorporated intermetallic NRs are characterized in detail to follow the alterations during application. An understanding of the correlation between structural, chemical and electrochemical properties will allow a more rational design of functional nanomaterials.
The 1st chapter gives a general introduction to the rapid development and importance of renewable energy technologies in modern human society. Among which electrochemical energy storage and conversion technologies are particularly appealing in terms of cost, safety and environmental friendliness. The basic principles of Li-, Na- and K- ion battery technologies are discussed, including the battery structures, electrode materials and working mechanisms. Additionally, I describe the working principle of DEFCs and the electrocatalytic EOR. Strategies for synthesizing high performance NCs for electrochemical energy storage and conversion applications are also explained. Finally, in this chapter I discuss the phenomenon of NCs structural and chemical evolution during electrochemical operations and how their characterization in each system is needed for a thorough understanding of nanomaterials properties and applications. Chapter 1 also includes the objectives of the thesis.
Chapter 2 describes a simple seed-mediated growth method at low temperature to grow heterstructered Mn3O4 on hollow Fe3O4 seeds. A moderate temperature (500 °C) annealing process is conducted to promote the solid-state reaction for hollow MnxFe3-xO4 NPs while conserving the original morphology. When serving as anode electrode materials, the polycrystalline shell, the internal void space and the high surface area of MnxFe3-xO4 NPs can effectively buffer the volume change of the NCs during lithiation and delithiation process to improve the stability and cycle life. The electrochemical activity of MnxFe3-xO4 NPs toward lithium reaction is evaluated and the relationship between the structure and electrochemical properties is explored. The excellent performance of hollow MnxFe3-xO4 NPs is associated with their crystal structure and composition, and with the presence of carbonized ligands, which further promote electrical conductivity and rapidly accommodate and release lithium ions while retaining a stable structure even after continuous charge/discharge cycles. This work
was published in Nano Energy in 2019.
Chapter 3 talks about the performance of bimetallic NPs as anodes in LIBs and KIBs. Monodisperse CoSn and NiSn NPs are synthesized through co-reduction and supported on commercial carbon materials. The obtained nanocomposites are tested as anode materials in half-cell LIBs, KIBs and full-cell LIBs. CoSn@C electrodes display excellent charge-discharge capacities with LIB half-cell and LIB full-cells. The capacities for KIB are stabilized at around 200 mAh g-1 with high coulombic efficiency over 400 cycles for CoSn@C and 100 mAh g-1 for NiSn@C over 300 cycles. The oxidation of NPs, the formation of SEI layer, the vast volume change during lithiation and delithiation processed caused the capacities decrease. This work was published in ACS Applied Materials & Interfaces in 2020.
In chapter 4, a simple approach to produce intermetallic Pd3Pb nanocubes with well-defined cubic geometry and average size ranged from 6 nm to 10 nm is detailed. Pd3Pb/C catalysts present improved EOR electrocatalytic activities and stabilities. The EOR activity of Pd3Pb nanocubes is investigated through CV and CA techniques, which is size-dependent. All the catalysts exhibit a pronounced current decay during the first 500 s of continuous EOR operation, which is associated to the accumulation of strongly adsorbed reaction intermediates and the related blockage of reaction sites. The catalysts can be reactivated by simply cycling to effectively remove the poisoning species adsorbed on the surface and recover the electrocatalytic activity. A reorganization of Pd and Pb elements happens on Pd3Pb nanocubes during EOR, involving an outward/inward diffusion of Pd/Pb to equilibrate the stoichiometry of the NCs surface, which is driven by the different affinity of Pb and Pd towards oxygen and possibly ethanol, and the electrochemical oxidation/reduction of Pd. This work was published in Chemistry of Materials in 2020.
Chapter 5 demonstrates the synthesis of colloidal Pd2Sn:P NRs through phosphorization of Pd2Sn NPs with a highly active reagent- hexamethylphosphorous triamide (HMPT) in a one-pot two-steps reaction. The Pd2Sn:P/C catalyst exhibits significantly enhanced activity toward EOR in alkaline media compared with Pd2Sn/C, PdP2/C and commercial Pd/C catalysts. The performance improvement is rationalized with the aid of DFT calculations considering the different phosphorous chemical environments. Depending on its oxidation state, surface phosphorus introduces sites with low energy OH- adsorption and/or strongly influences the electronic structure of palladium and tin to facilitate the oxidation of the acetyl to acetic acid, which is considered the EOR rate limiting step. The Pd2Sn:P NRs is characterized with Sn- and P-rich surface, which correlates well with the higher percentages of oxidized tin and phosphorous, and the higher tendency to oxidation of Sn compared with Pd. DFT calculations prove that the presence of P can induce a higher chemical adsorption of OH- to facilitate the formation of CH3COOH, resulting in EOR activity increase. This work was accepted in Nano Energy in 2020.
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