Browsing by Author "Schwanitz, Bernhard W"

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    Open Access
    Influence of catalyst ink mixing procedures on catalyst layer properties and in-situ PEMFC performance
    (2016) Jacobs, Clayton Jeffrey; Levecque, Pieter B J; Hussain, Nabeel; Schwanitz, Bernhard W
    Despite the benefits of fuel cell technology its advancement to being commercially functional is hindered by a number of crucial factors. These factors are often associated with the lack of appropriate materials or manufacturing routes that would enable the cost of electricity per kWh to compete with existing technology. Whilst most research efforts have been directed towards developing more active catalysts, the amount of catalyst required in the fuel cell can be further reduced by improving the platinum utilisation in the membrane electrode assembly. The platinum utilisation is a strong function of the catalyst layer preparation step and there remains significant scope for optimisation of this step. Whereas significant work has been conducted into the different components of the catalyst ink there is limited work and understanding on the influence of the mixing method of the catalyst ink. This study will focus on the influence of the mixing technique on the catalyst ink properties and on the final fuel cell performance. Specifically, the study will investigate the effect of the three different mixing techniques on (i) catalyst ink quality (ii) the physical properties of the resultant catalyst layer and (iii) the in-situ electrochemical performance of the membrane electrode assembly. A large set of characterisation techniques were chosen to effectively study the step wise processing of the catalyst layer, and fuel cell performance. The results presented here include a comparison of the various mixing techniques and a comprehensive 2 x 2 factorial design into the individual techniques. The results suggest that high energy mixing is required for effective distribution of catalyst layer components, an even catalyst layer topography and a highly functional ionomer network which consequently, enhances performance. The mixing energy referred to involves prolonged mixing time, enhanced mixing intensity or a combination of the two. During bead milling of catalyst inks, high intensity mixing seems to be beneficial however, prolonged mixing time appears to be detrimental to the ionomer film structure. During high shear stirring and ultrasonic homogenisation of catalyst inks, the ink mixture significantly heats up. It has been observed that at higher temperatures, Nafion elongates and the contact with catalyst agglomerates is enhanced. High shear stirring of catalyst inks seems to be most effective at high agitation rates. High mixing energies result in high shear forces and in addition, high mixing temperatures which appear to be beneficial to establishing an effective catalyst/Nafion interface, enhancing the three phase boundary observed during in-situ testing. Ultrasonic homogenisation seems to be more effective at prolonged sonication times. Due to the erosive nature of ultrasonic dispersion, sufficient time is required to establish a well dispersed and distributed catalyst ink. However, the nature of particle size distribution resulting from ultrasonication shows that inks are unstable and is not recommended for high throughput processing. Overall, fuel cell performance is not significantly affected by the mixing step however; mixing does have an observable impact on catalyst layer formulation. Generally, when optimizing membrane electrode assembly fabrication, mixing parameters should be carefully chosen. This goes without saying that parameters need to be effectively studied before foregoing catalyst ink processing.
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    Open Access
    Influence of particle size and morphology of Pt₃Co/C on the oxygen reduction reaction
    (2015) Hlabangana, Ntandoyenkosi; Levecque, Pieter B J; Schwanitz, Bernhard W
    Polymer electrolyte fuel cells have shown great potential in providing clean energy with no emissions. The kinetics of the cathode reaction, i.e. the oxygen reduction reaction (ORR) are sluggish necessitating high loadings of the catalyst metal, i.e. platinum. Platinum is a limited resource and expensive. Its price has been one of the major drawbacks in wide scale commercialisation of fuel cells. In an effort to improve the activity of the catalyst and therefore reduce Pt loadings on the catalyst, Pt can be alloyed with transition metal elements (e.g. Ni, Co and Fe) to form bimetallic catalysts. Alloying has been known to improve the activity and stability of a catalyst for the ORR. The enhanced activity of the alloys originates from the modified electronic structures of the Pt in these alloy catalysts which reduces the adsorption of spectator species therefore increasing the number of active sites for the ORR (Wang et al., 2012 (2)). The aim of this study was to gain a better understanding of the influence of Pt alloy particle size and active surface morphology on the ORR activity. The Pt alloy that was investigated was Pt₃Co/C. The surface morphology was modified by varying the Pt/Pt₃Co loading on a carbon support. The catalysts were prepared using thermally induced chemical deposition. The support used was Vulcan-XC-72R. The effects of varying the metal loadings on the ORR was investigated. The loadings that were investigated were 20, 40, 60 and 80 wt. % Pt and Pt₃Co. The alloy catalysts were subjected to annealing at 900 °C and acid leaching. The catalysts were analysed using electrochemical characterisation techniques such as cyclic voltammetry, CO stripping voltammetry, rotating disk electrode and rotating ring disk electrode. Physical characterisation of the catalysts was also implemented. The techniques used were x-ray diffraction, thermogravimetric analysis and transmission electron microscopy. The Pt particles on the carbon support were found not to agglomerate significantly despite the loading being increased. This trend was also observed for the Pt₃Co/C catalysts even after heat treatment and leaching. The lack of agglomeration was credited to a new reactor system developed in this work. The particle growth increased from low loadings to high loadings for both the Pt/C and Pt₃Co/C catalysts. Particle growth was more significant for the Pt₃Co/C catalysts at high loadings. At lower loadings (20 and 40 wt. %) the particle sizes between the Pt/C and Pt₃Co/C catalysts were comparable despite the Pt₃Co/C catalysts undergoing annealing and leaching. The mass specific activity of the Pt/C catalysts was not improved by alloying with the exception of the 20 wt. % catalyst which saw an enhancement factor of 1.66. The surface specific activity of the Pt/C catalysts was improved significantly with factors of 2.40 and 3.11 being recorded for the 20 and 80 wt. % Pt₃Co/C catalysts respectively. The enhancement factors of the intermediate loadings (40 and 60 wt. %) were lower and fairly similar at 1.30 and 1.35 respectively.
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    Preparation and characterisation of inorganic nanostructured support materials for polymer electrolyte fuel cells
    (2015) September, Caelin Gee; Levecque, Pieter B J; Schwanitz, Bernhard W
    Polymer electrolyte fuel cells (PEFCs) have been identified as a safe, clean and reliable alternative energy conversion technology to conventional, fossil fuel based, ones. However, the hindrance to worldwide commercialisation of this technology lies in the poor durability and high costs associated with the current carbon supported platinum (Pt/C) catalysts. Carbon support corrosion and Pt dissolution/aggregation on the catalyst layer within the fuel cell have been confirmed as the major contributors to the degradation of the Pt/C (Shao, et al., 2007). Attention needs to be paid to the improvement of catalyst components to produce an electrocatalyst with better degradation resistance and low Pt loading in order to overcome these two major commercialisation barriers. The physico-chemical and electronic interaction between the Pt catalyst and the support material play a crucial role in the catalytic activity and stability of the electrocatalysts (Wang, et al., 2011). A comprehensive understanding of the effects of catalyst support material and morphology on the mechanism and kinetics of the oxygen reduction reaction (ORR) needs to be developed. This study investigated alternative, novel catalyst support materials and structures for the catalyst layer as opposed to carbon for PEFC applications. This material consisted of TiB2 electrospun nanofibers, powder and crushed electrospun nanofibers. Methods used to reliably and accurately deposit Pt onto these materials were identified, developed and analysed. These methods include platinum deposited onto TiB2 powder, electrospun crushed nanofibers and nanofiber mats via DC magnetron sputter deposition and thermally induced chemical deposition (TICD). The synthesised catalysts were physically characterised using X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Inductively Coupled Plasma Optical emission spectrometry (ICP-OES). Platinum effectively deposited on the TiB2 support structures via these deposition techniques within two standard deviations of the desired Pt loadings.