Development of membrane electrode assemblies based on electrophoretic deposition for high temperature polymer electrolyte membrane fuel cell applications

Philosophiae Doctor - PhDHigh Temperature Polymer Electrolyte Membrane Fuel Cells (HT-PEMFC) have received renewed interest in recent years due to its inherent advantages associated with the limitations faced by Low Temperature Polymer Electrolyte Membrane Fuel Cells (LT-PEMFC). The high Pt loadings required for PEMFCs have significantly hindered its commercialisation. Electrophoretic Deposition (EPD) is a promising route to reduce the noble metal loading. EPD is a method in which charged colloidal particles are deposited onto a target substrate under the force of an externally applied electric field. To effectively study the EPD method, the methodology of this study was divided into two parts: (i) the EPD method was studied via known empirical methods to fabricate, test and characterise MEAs suitable for HT-PEMFCs. The feasibility of the EPD method was determined by comparing the performance of the fabricated EPD MEAs to MEAs fabricated via spraying methods, and (ii) due to the promising results obtained in part (i) of the methodology, a theoretical model was developed to obtain a deep understanding about nature of the interactions between the Pt/C particles in a colloidal suspension. The theoretical model will serve as a foundation for future studies. In part (i) of the methodology, the Pt/C particles were studied in organic solutions (i.e. Isopropyl Alcohol, IPA) via the Zetasizer Nano ZS instrument under various salt (NaCl) concentrations and pH conditions while introducing polymeric surfactants, i.e. Nafion® ionomer and Polytetrafluoroethylene (PTFE) to the suspension. The optimum catalyst suspensions were selected to fabricate GDEs via the EPD method. Physical characterisations revealed that the EPD GDEs exhibited cracked morphology with high porosity. Electrochemical characterisations revealed that the EPD MEA showed significantly better performance (i.e. 73% higher peak power) compared to the hand vi sprayed MEA due to lower charge transfer and mass transport resistance at high current densities. Compared to the ultrasonically sprayed MEA, the EPD MEA exhibited a peak power increase of ~12% at a slightly lower Pt loading (i.e. ~4 wt%). A comparative study between the Nafion® ionomer and PTFE in the CLs of two EPD MEAs revealed superior performance for the EPD MEA with the PTFE in the CLs. Part (ii) of the methodology deals with the electrical interfacial properties of the aqueous Pt/C suspension. The study consists of two sets of measurements (i.e. electrophoretic and coagulation dynamic studies) conducted for different electrolyte compositions. A theoretical background on determining the interfacial potential and charge from electrophoretic and coagulation dynamic measurements are provided. Detailed statements of the Standard Electrokinetic and Derjaguin, Landau, Vervey and Overbeek Models are given in the forms that are capable of addressing electrophoresis and the interaction of particles for an arbitrary ratio of the particle to Debye radius, interfacial potential and electrolyte composition. The obtained experimental data were processed by using numerical algorithms based on the formulated models for obtaining the interfacial potential and charge. While analysing the dependencies of interfacial potential and charge on the electrolyte compositions charge, conclusions were made regarding the mechanisms of charge formation. It was established that the behaviour of system stability is in qualitative agreement with the results computed from the electrophoretic data. The verification of quantitative applicability of the employed models was conducted by calculating the Hamaker constant from the experimental data. It was proposed how to explain the observed variations of the predicted Hamaker constant and its unusually high value

Iridium based mixed oxides as efficient anode catalysts for Solid Polymer Electrolyte (SPE) electrolysers

>Magister Scientiae - MScThe objective of the thesis is to develop highly efficient catalysts for solid polymer electrolyte (SPE) electrolyser anodes.The anode is the primary cause of the large overpotential of SPE electrolysers and also adds significantly to the cost of the electrolysers. Currently, unsupported IrO2 is a widely used anode catalyst as it exhibits the best stability during the oxygen evolution reaction. The activity of IrO2 needs to be improved significantly to address the high cost and efficiency issues of the SPE electrolyser. Developments aimed at improving the activity of unsupported IrO2 are however limited due to the limitations of the wellknown supports under the operating conditions of electrolysers, leading to their oxidation.In this study binary metal oxides based on IrO2 were developed and optimized as anode catalysts for the SPE electrolyser and compared to the ‘state-of-art’ commercial IrO2 catalyst. The Adams fusion method was adapted and used to synthesize the catalysts.The activities of the catalysts were determined using half-cell studies. Optimum conditions for the preparation of unsupported IrO2 catalysts were found to be 350 oC and 2 hours. The resulting catalysts had twice the activity of the ‘state-of-art’ commercial IrO2 catalyst. Secondary metals were carefully selected, after carrying out both a literature study and an experimental study. Binary metal oxides were then developed using the optimum synthesis conditions. Four binary metal oxides were studied to identify the best/most efficient catalyst for electrolysis. The catalysts were characterized using XRD, TEM, SEM and EDS analyses, in efforts to understand and correlate the activity of the catalysts to its physical properties and obtain information that could be useful for the further development of efficient catalysts.Although all the binary metal oxides studied showed improved activity compared to IrO2, the catalytic activity of Ir0.7Ru0.3O2 was found to be significantly better than the commercial catalyst: it was over 5 times more active than the ‘state-of-art’ commercial IrO2 catalyst. Ir-Pd mixed oxides also proved to be highly efficient as anode catalysts for SPE electrolysers

Towards the development of a novel bipolar-based battery in aqueous electrolyte: Evaluation of the electrochemical properties of NiCu based hydroxide electrodes fabricated on Ni–mesh and graphite composite current collectors

The use of bipolar electrodes in rechargeable batteries can improve specific power, simplify cell design, and reduce manufacturing costs. However, bipolar-based batteries still suffer from many drawbacks. Therefore, developing high-performance active materials and developing improvement strategies encompassing the entire cell's design is essential. The current collector significantly impacts the viability of mass production; however, it is the most neglected feature of electrochemical energy storage devices. The current collector serves a dual purpose; it allows the movement of electrons among active electrode material and provides mechanical support. It can also act as transportation of current to terminals of the battery. This study constructed a novel bipolar battery cell utilizing graphite as a current collector, and its discharge capacities for Ni-Fe battery applications were evaluated. Monopolar NiFe cells, one using a graphite substrate current collector and the other using a Ni-mesh current collector, were used for comparison. The monopolar-based electrode coated onto a graphite substrate demonstrated a 29% (199 mAh/g) higher discharge capacity than the Ni-mesh-based electrode (142 mAh/g) after the 100th cycle. In contrast, the bipolar-based NiFe battery cell resulted in a discharge capacity of 158 mAh/g after the 100th cycle, corresponding to a coulombic efficiency of 72%

Synthesis, characterisation and evaluation of IrO2 based binary metal oxide electrocatalysts for oxygen evolution reaction

IrO2, IrxRu1-xO2, IrxSnx-1O2 and IrxTax-1O2 (1 ≥ x ≥ 0.7) were synthesized, characterised and evaluated as electrocatalysts for the oxygen evolution reaction in solid polymer electrolyte electrolysers. The electrocatalysts were synthesised by adapting the Adams fusion method. The physical properties of the electrocatalysts were characterised by scanning electron microscopy, transmission electron microscopy and x-ray diffraction. Electrochemical activity of the electrocatalysts toward the oxygen evolution reaction was evaluated by cyclic voltammetry and chronoamperometry. X-ray diffraction revealed no phase separation when RuO2 or SnO2 was introduced into the IrO2 lattice suggesting that solid solutions were formed. Transmission electron microscope analysis revealed nanosize particles for all synthesised metal oxides. Crystallinity increased with the addition of RuO2 and SnO2 while a suppression of crystal growth was observed with the addition of Ta2O5 to IrO2. Chronoamperometry revealed that the addition of all the secondary metal oxides to IrO2 resulted in improved catalytic performance. Ir0.7Ru0.3O2 was identified as the most promising electrocatalyst for the oxygen evolution reaction. Keywords:Web of Scienc

Ex-situ electrochemical characterization of iro2 synthesized by a modified Adams fusion method for the oxygen evolution reaction

The development of highly stable and active electrocatalysts for the oxygen evolution reaction (OER) has attracted significant research interest. IrO2 is known to show good stability during the OER however it is not known to be the most active. Thus, significant research has been dedicated to enhance the activity of IrO2 toward the OER. In this study, IrO2 catalysts were synthesized using a modified Adams fusion method. The Adams fusion method is simple and is shown to directly produce nano-sized metal oxides. The effect of the Ir precursor salt to the NaNO3 ratio and the fusion temperature on the OER activity of the synthesized IrO2 electrocatalysts, was investigated. The OER activity and durability of the IrO2 electrocatalysts were evaluated ex-situ via cyclic voltammetry (CV), chronopotentiometry (CP), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV)

Semi-analytic Simulations of Galactic Winds: Volume Filling Factor, Ejection of Metals and Parameter Study

We present a semi-analytic treatment of galactic winds within high resolution, large scale cosmological N-body simulations of a LCDM Universe. The evolution of winds is investigated by following the expansion of supernova driven superbubbles around the several hundred thousand galaxies that form in an approximately spherical region of space with diameter 52 Mpc/h and mean density close to the mean density of the Universe. We focus our attention on the impact of winds on the diffuse intergalactic medium. Initial conditions for mass loss at the base of winds are taken from Shu, Mo and Mao (2003). Results are presented for the volume filling factor and the mass fraction of the IGM affected by winds and their dependence on the model parameters is carefully investigated. The mass loading efficiency of bubbles is a key factor to determine the evolution of winds and their global impact on the IGM: the higher the mass loading, the later the IGM is enriched with metals. Galaxies with 10^9 < M_* < 10^10 M_sun are responsible for most of the metals ejected into the IGM at z=3, while galaxies with M_* < 10^9 M_sun give a non negligible contribution only at higher redshifts, when larger galaxies have not yet assembled. We find a higher mean IGM metallicity than Lyalpha forest observations suggest and we argue that the discrepancy may be explained by the high temperatures of a large fraction of the metals in winds, which may not leave detectable imprints in absorption in the Lyalpha forest.Comment: 18 pages, 15 figures. Major changes in the model. Manuscript with high resolution figures available upon request. MNRAS in pres

DNA methylation at birth and lateral ventricular volume in childhood:a neuroimaging epigenetics study

Background: Lateral ventricular volume (LVV) enlargement has been repeatedly linked to schizophrenia; yet, what biological factors shape LVV during early development remain unclear. DNA methylation (DNAm), an essential process for neurodevelopment that is altered in schizophrenia, is a key molecular system of interest. Methods:In this study, we conducted the first epigenome-wide association study of neonatal DNAm in cord blood with LVV in childhood (measured using T1-weighted brain scans at 10 years), based on data from a large population-based birth cohort, the Generation R Study (N = 840). Employing both probe-level and methylation profile score (MPS) approaches, we further examined whether epigenetic modifications identified at birth in cord blood are: (a) also observed cross-sectionally in childhood using peripheral blood DNAm at age of 10 years (Generation R, N = 370) and (b) prospectively associated with LVV measured in young adulthood in an all-male sample from the Avon Longitudinal Study of Parents and Children (ALSPAC, N = 114). Results: At birth, DNAm levels at four CpGs (annotated to potassium channel tetramerization domain containing 3, KCTD3; SHH signaling and ciliogenesis regulator, SDCCAG8; glutaredoxin, GLRX) prospectively associated with childhood LVV after genome-wide correction; these genes have been implicated in brain development and psychiatric traits including schizophrenia. An MPS capturing a broader epigenetic profile of LVV – but not individual top hits – showed significant cross-sectional associations with LVV in childhood in Generation R and prospectively associated with LVV in early adulthood within ALSPAC. Conclusions: This study finds suggestive evidence that DNAm at birth prospectively associates with LVV at different life stages, albeit with small effect sizes. The prediction of MPS on LVV in a childhood sample and an independent male adult sample further underscores the stability and reproducibility of DNAm as a potential marker for LVV. Future studies with larger samples and comparable time points across development are needed to further elucidate how DNAm associates with this clinically relevant brain structure and risk for neuropsychiatric disorders, and what factors explain the identified DNAm profile of LVV at birth.</p

A multivariate genome-wide association study of psycho-cardiometabolic multimorbidity

Coronary artery disease (CAD), type 2 diabetes (T2D) and depression are among the leading causes of chronic morbidity and mortality worldwide. Epidemiological studies indicate a substantial degree of multimorbidity, which may be explained by shared genetic influences. However, research exploring the presence of pleiotropic variants and genes common to CAD, T2D and depression is lacking. The present study aimed to identify genetic variants with effects on cross-trait liability to psycho-cardiometabolic diseases. We used genomic structural equation modelling to perform a multivariate genome-wide association study of multimorbidity (Neffective = 562,507), using summary statistics from univariate genome-wide association studies for CAD, T2D and major depression. CAD was moderately genetically correlated with T2D (rg = 0.39, P = 2e-34) and weakly correlated with depression (rg = 0.13, P = 3e-6). Depression was weakly correlated with T2D (rg = 0.15, P = 4e-15). The latent multimorbidity factor explained the largest proportion of variance in T2D (45%), followed by CAD (35%) and depression (5%). We identified 11 independent SNPs associated with multimorbidity and 18 putative multimorbidity-associated genes. We observed enrichment in immune and inflammatory pathways. A greater polygenic risk score for multimorbidity in the UK Biobank (N = 306,734) was associated with the co-occurrence of CAD, T2D and depression (OR per standard deviation = 1.91, 95% CI = 1.74–2.10, relative to the healthy group), validating this latent multimorbidity factor. Mendelian randomization analyses suggested potentially causal effects of BMI, body fat percentage, LDL cholesterol, total cholesterol, fasting insulin, income, insomnia, and childhood maltreatment. These findings advance our understanding of multimorbidity suggesting common genetic pathways.</p

A multivariate genome-wide association study of psycho-cardiometabolic multimorbidity

Coronary artery disease (CAD), type 2 diabetes (T2D) and depression are among the leading causes of chronic morbidity and mortality worldwide. Epidemiological studies indicate a substantial degree of multimorbidity, which may be explained by shared genetic influences. However, research exploring the presence of pleiotropic variants and genes common to CAD, T2D and depression is lacking. The present study aimed to identify genetic variants with effects on cross-trait liability to psycho-cardiometabolic diseases. We used genomic structural equation modelling to perform a multivariate genome-wide association study of multimorbidity (Neffective = 562,507), using summary statistics from univariate genome-wide association studies for CAD, T2D and major depression. CAD was moderately genetically correlated with T2D (rg = 0.39, P = 2e-34) and weakly correlated with depression (rg = 0.13, P = 3e-6). Depression was weakly correlated with T2D (rg = 0.15, P = 4e-15). The latent multimorbidity factor explained the largest proportion of variance in T2D (45%), followed by CAD (35%) and depression (5%). We identified 11 independent SNPs associated with multimorbidity and 18 putative multimorbidity-associated genes. We observed enrichment in immune and inflammatory pathways. A greater polygenic risk score for multimorbidity in the UK Biobank (N = 306,734) was associated with the co-occurrence of CAD, T2D and depression (OR per standard deviation = 1.91, 95% CI = 1.74–2.10, relative to the healthy group), validating this latent multimorbidity factor. Mendelian randomization analyses suggested potentially causal effects of BMI, body fat percentage, LDL cholesterol, total cholesterol, fasting insulin, income, insomnia, and childhood maltreatment. These findings advance our understanding of multimorbidity suggesting common genetic pathways

Effects of Pre- and Postnatal Early-Life Stress on Internalizing, Adiposity, and Their Comorbidity

Objective: Depression and obesity are 2 highly prevalent and often comorbid conditions. Exposure to early-life stress (ELS) has been associated with both depression and obesity in adulthood, as well as their preclinical manifestations during development. However, it remains unclear whether (1) associations differ depending on the timing of stress exposure (prenatal vs postnatal), and whether (2) ELS is a shared risk factor underlying the comorbidity between the 2 conditions. Method: Leveraging data from 2 large population-based birth cohorts (ALSPAC: n = 8,428 [52% male participants]; Generation R: n = 4,268 [48% male participants]), we constructed comprehensive cumulative measures of prenatal (in utero) and postnatal (from birth to 10 years) ELS. At age 13.5 years, we assessed the following: internalizing symptoms (using maternal reports); fat mass percentage (using dual-energy X-ray absorptiometry); and their comorbidity, defined as the co-occurrence of high internalizing and high adiposity. Results: Both prenatal (total effect [95% CI] = 0.20 [0.16; 0.22]) and postnatal stress (β [95%CI] = 0.22 [0.17; 0.25]) were associated with higher internalizing symptoms, with evidence of a more prominent role of postnatal stress. A weaker association (driven primarily by prenatal stress) was observed between stress and adiposity (prenatal: 0.07 [0.05; 0.09]; postnatal: 0.04 [0.01; 0.07]). Both prenatal (odds ratio [95%CI] = 1.70 [1.47; 1.97]) and postnatal (1.87 [1.61; 2.17]) stress were associated with an increased risk of developing comorbidity. Conclusion: We found evidence of timing and shared causal effects of ELS on psycho-cardiometabolic health in adolescence; however, future research is warranted to clarify how these associations may unfold over time. Diversity &amp; Inclusion Statement: We worked to ensure sex and gender balance in the recruitment of human participants. We worked to ensure race, ethnic, and/or other types of diversity in the recruitment of human participants. We worked to ensure that the study questionnaires were prepared in an inclusive way. One or more of the authors of this paper self-identifies as a member of one or more historically underrepresented racial and/or ethnic groups in science. One or more of the authors of this paper self-identifies as a member of one or more historically underrepresented sexual and/or gender groups in science. We actively worked to promote sex and gender balance in our author group.</p