Nano/Submicro-Structured Iron Cobalt Oxides Based Materials for Energy Storage Application

Supercapacitors, as promising energy storage devices, have been of interest for their long lifespan compared to secondary batteries, high capacitance and excellent reliability compared to conventional dielectric capacitors. Transition metal oxides can be applied as the electrode materials for pseudocapacitors and offer a much higher specific capacitance. Co3O4 is one of the most investigated transition metal oxides for supercapacitor. Besides simple monometallic oxides, bimetallic transition oxides have recently drawn growing attention in electrochemical energy storage. They present many unique properties such as achievable oxidation states, high electrical conductivities because of the coexistence of two different cations in a single crystal structure. This study focuses on the bimetallic iron cobalt oxide based materials for the application of energy storage. We selected iron as the substituent in spinel Co3O4, by virtue of its abundant and harmless character. Four types of iron cobalt oxides based electrode materials with different morphologies and components have been synthesized for the first time. The hydrothermal method was the main strategy for the synthesis of iron cobalt based materials, which achieved the control of morphology and ratio of components. Multiple characterization methods, including SEM, TEM, XRD, XPS, TGA, BET, have been applied to study the morphologies and nano/submicron structures. The electrochemical properties of as-fabricated samples were performed by electrochemical workstation. In addition, in order to investigate the practical application of electrode materials, asymmetric supercapacitors have been assembled by using as-prepared samples as the positive electrodes and activated carbon as the negative electrodes

Bio-Inspired Synthesis Of Nanostructured Materials On Substrates For Environmental And Energy Applications

It is still a challenging task to develop simple methods for facile synthesis of functional nanostructures on substrates under mild conditions without using expensive instruments. We have successfully developed a bio-inspired method using simple diaphragm-assisted system to synthesize functional nanostructures on various substrates under mild conditions. We have systematically studied the effects of experimental parameters on the formation of nanostructures under controlled conditions. The fundamental mechanism involved has been systematically studied and revealed. By growing the unique networks of nanostructures on a piece of substrate, a double-rough surface, with structures at both nanoscale and microscale, has been achieved, showing interesting roughness-induced superhydrophobicity in air and superoleophobicity in water. The double rough substrates will find important environmental applications. Additionally, nanostructures formed on substrates have been used as integrated and binder-free electrodes for energy storage. The unique structures with a large exposed surface enable the electrodes to demonstrate dramatically improved performances. Moreover, some chemically active substrates were used to build up composite materials to enhance their applications. The method and ideas outlined in the dissertation, based on diaphragm-assisted systems, will have impacts, in principle, on the synthesis of numerous functional materials or precursors under mild conditions

Application of vertical seismic profiling for the characterisation of hard rock

Seismic imaging in hard rock environments is gaining wider acceptance as a mineral exploration technique and as a mine-planning tool. However, the seismic images generated from hard rock targets are complex due to high rock velocities, low contrasts in elastic rock properties, fractionated geology, complicated steep dipping structures and mineralogical alterations. In order to comprehend the complexity and utilise seismic images for structural mapping and rock characterisation, it is essential to correlate these images to known geology. An ideal tool for this purpose is Vertical Seismic Profiling or VSP. The VSP method can provide not only a means to correlate seismic images to geology but also to study the properties of the transmitted seismic field as it is modified by different rock formations, the origin of the reflected events and the corresponding reflector geometry. However, the VSP technique is rarely used in hard rock environments because of the cost and operational issues related to using clamping geophones in exploration boreholes, which are 96 mm or less in diameter. Consequently the main objective of this research is to produce an efficient VSP methodology that can be readily deployed for mineral exploration.An alternative to the clamping geophone is the hydrophone. Hydrophones are suspended in, and acoustically coupled to the borehole wall through, the borehole fluid. Borehole acoustic modes known as "tube-waves" are generated by seismic body waves passing the water column and are guided in the borehole due to the high acoustic impedance contrast between the rock and fluid. Tube-waves are 1-2 orders in magnitude higher in amplitude than seismic signal and mask reflected energy in hydrophone VSP profiles. As such the use of borehole hydrophone arrays to date has been restricted to direct body wave measurements only. I have effectively mitigated tube-waves in hydrophone VSP surveys with specific acquisition methodologies and refined signal processing techniques. The success of wavefield separation of tubewaves from hydrophone data depends critically upon; having high signal to noise ratio, well sampled data, pre-conditioning of the field data and processing in the field record (FFID) domain. Improvements in data quality through the use of high viscosity drilling fluids and baffle systems have been tested and developed. The increased signal to noise ratio and suppression of tube-wave energy through these technologies greatly enhances the performance of hydrophone VSP imaging.Non-standard wavefield separation techniques successfully removed strong coherent tube-wave noise. The additional wavefield separation steps required to remove high amplitude tube-waves does degrade the overall result with some fidelity and coherency being lost. However, a direct comparison of hydrophone and borehole clamping geophone VSP surveys has been conducted in the Kambalda nickel district and the two methodologies produced comparable results. The difference was that the hydrophone data were collected in a fraction of the time compared to clamping geophone equipment with significantly less risk of equipment loss and with reduced cost.The results of these field experiments and the data processing methodology used, demonstrate the potential of hydrophone VSP surveys in the small diameter boreholes typical of hard rock exploration. Thus, these results show that hydrophone VSP is a viable, cost effective and efficient solution that should be employed more routinely in hard rock environments in order to enhance the value of the surface seismic datasets being acquired

Single-Crystalline Graphene by Low-Pressure CVD Method: Nucleation Limited Growth, Transfer, and Characterization

Graphene has attracted enormous attention due to its unique characteristics. However, the LPCVD graphene grown on copper turns out to be polycrystalline because of the high nucleation density (ND) on the copper foil surface. In order to realize better quality LPCVD graphene, this ND needs to be significantly reduced. Based on the observations from our initial graphene growths on as-received copper, we figured that the uneven Cu surfaces with defects produce large NDs. At a large ND, the graphene flakes nucleated at different sites coalesced to produce polycrystalline graphene. Due to such issues, we have implemented an electropolishing technique to smoothen the native surface of the copper foil. We will discuss the successful implementation of the surface smoothening process to reduce nucleation site formation while limiting the surface defects (which leads to wrinkle formation). The annealing process was also helpful to flatten the surface during the growth process further. We have also observed that graphene grows across Cu grain boundaries and, in the process, produces an additional surface area for graphene growth. That later causes to form wrinkles, which affect graphene properties negatively. In the next project, the effect of multi-step copper surface oxidization, base pressure vacuum in the middle of the process, and integration of Cu enclosures on suppressing the ND will be discussed. The technique is based on the self-cleaning characteristics of copper oxides and the metal evaporation in a high vacuum at high temperatures. The ND has reduced to ~5 nucleation/cm2 on average (an improvement compared to the previously reported minimum value, ten nucleation/cm2 which was obtained using copper enclosures), and the graphene/copper surface has become smoother. The self-aligned graphene island geometry and shape of the flakes have reflected the symmetry and the single crystallinity of graphene. The final project will discuss the growth of cm-scale graphene flakes on Cu and 3D-multilayered graphene on 3D-Ni foams and used Ni\u27s gettering carbon diffusion effect to make the Cu foil carbon-free. The Ni-foam/Cu enclosure was oxidized in situ to assist with the self-cleaning process of metal oxides. The ND has been reduced to ~0.57 nucleation/cm2 and obtained cm-scale graphene flakes

Brain activity on encoding different textures EEG signal acquisition with ExoAtlet®

Powered exoskeletons play a crucial role in the rehabilitation field improving the quality of life for those who need them. Thus, being a major contribution for patients integration into society, providing them with more autonomy and freedom. In spite of these positive outcomes, a thorough description of the brain correlates connected to exoskeleton control is still needed. For instance, the perception of different pavement textures when wearing an exoskeleton is probably going to cause changes in cerebral activity, which could impact both sensory encoding and Brain-Computer Interface (BCI) control. Therefore, the main goal of this work is to describe the brain activity response to different textured pavements using ExoAtlet ® powered exoskeleton. In order to measure, process, analyze and classify the impact of different textures on neurophysiological rhythms, 4-minute signals were recorded by Electroencephalogram (EEG) with a 16-channel cap (actiCAP by Brain Products). Each of the three experimental subjects was instructed to walk in place on four different types of pavement (flat, carpet, foam, and rubber circles) with and without the exoskeleton, for a total of eight different experimental conditions. A counterbalanced design was applied, and informed consent was obtained from participants (Committee for Health Sciences of the Universidade Católica Portuguesa - 99/2022). Additionally, four machine learning methods, Support Vector Machine (SVM), K-Nearest Neighbors (KNN), Linear Discriminant Analysis (LDA), and Artificial Neural Network (ANN), were selected in order to analyze three distinct classification problems. This study found that there were changes associated with the delta frequency band for electrodes C3 and C4, and when comparing the classifiers performance, LDA presented the best accuracy across the three classification problems involving all subjects. Thereby, this work concludes that the results are consistent with the hypothesis that sensory processing of pavement textures during exoskeleton control induces neural changes and delta variations of the C3 and C4 electrodes. Additionally, LDA demonstrated the best performance across the three classifications of subject-independent problems.Os exoesqueletos motorizados desempenham um papel crucial no campo da reabilitação, melhorando a qualidade de vida das pessoas que deles necessitam. Deste modo, são um contributo importante para que os pacientes com condições físicas limitadas sejam mais facilmente integrados na sociedade, proporcionando-lhes mais autonomia e liberdade. Embora esta tecnologia tenha os seus aspetos positivos, ainda existe a necessidade de descrever os correlatos cerebrais direcionados para o controlo do exoesqueleto. Por exemplo, a percepção de diferentes pavimentos quando se usa um exoesqueleto vai provavelmente causar alterações na actividade cerebral, o que pode ter impacto tanto na codificação sensorial como no controlo da interface cérebro-máquina (BCI). Deste modo, o principal objetivo deste trabalho é descrever a atividade cerebral às diferentes texturas dos pavimentos, utilizando o exoesqueleto ExoAtlet ®. A fim de medir, processar, analisar e classificar o impacto de diferentes texturas em ritmos neurofisiológicos, foram registados sinais de 4 minutos atravês the Eletroencefalograma (EEG) com uma touca de 16 canais (actiCAP by Brain Products). Cada um dos três voluntários foi instruído a dar passos no lugar em quatro tipos diferentes de pavimento (plano, alcatifa, espuma, e círculos de borracha) com e sem o exosqueleto, num total de oito condições experimentais diferentes. Foi aplicado um desenho contrabalançado e foi obtido o consentimento informado dos participantes (Comissão para as Ciências da Saúde da Universidade Católica Portuguesa - 99/2022). Adicionalmente, foram selecionados quatro classificadores: máquinas de vetores de suporte (SVM), k-vizinhos mais próximos (KNN), análise discriminante linear (LDA) e redes neuronais artificiais (ANN) para analisar três problemas de classificação distintos. Os resultados obtidos por este estudo demonstraram que existiam alterações associadas à banda de frequência delta para os eléctrodos C3 e C4 e, ao comparar o desempenho dos classificadores, o LDA apresentou a melhor exatidão nos três problemas de classificação envolvendo todos os sujeitos. Assim, estes resultados são consistentes com a hipótese de que o processamento sensorial dos pavimentos durante o controlo do exoesqueleto induz alterações neuronais