Local degradation of structural, mechanical, electrical and chemical properties of membrane electrode assembly in polymer electrolyte fuel cell

Polymer electrolyte fuel cell (PEMFC) is promising source of clean power in many applications ranging from portable electronics to automotive and land-based power generation. However, widespread commercialization of PEMFC is primarily challenged by degradation. The mechanisms of fuel cell degradation are not well understood. Even though the numbers of installed units around the world continue to increase and dominate the pre-markets, the present lifetime requirements for fuel cells cannot be guarantee, creating the need for a more comprehensive knowledge of material’s ageing mechanism. The objective of this project is to conduct experiments on membrane electrode assembly (MEA) components of PEMFC to study structural, mechanical, electrical and chemical changes during ageing and understanding failure/degradation mechanism. The first part of this project was devoted to surface roughness analysis on catalyst layer (CL) and gas diffusion layer (GDL) using surface mapping microscopy. This study was motivated by the need to have a quantitative understanding of the GDL and CL surface morphology at the submicron level to predict interfacial contact resistance. Nanoindentation studies using atomic force microscope (AFM) were introduced to investigate the effect of degradation on mechanical properties of CL. The elastic modulus was decreased by 45 % in end of life (EOL) CL as compare to beginning of life (BOL) CL. In another set of experiment, conductive AFM (cAFM) was used to probe the local electric current in CL. The conductivity drops by 62 % in EOL CL. The future task will include characterization of MEA degradation using Raman and Fourier transform infrared (FTIR) spectroscopy. Raman spectroscopy will help to detect degree of structural disorder in CL during degradation. FTIR will help to study the effect of CO in CL. XRD will be used to determine Pt particle size and its crystallinity. In-situ conductive AFM studies using electrochemical cell on CL to correlate its structure with oxygen reduction reaction (ORR) reactivity

Static and dynamic contact angle measurement on rough surfaces using sessile drop profile analysis with application to water management in low temperature fuel cells

Fuel Cells are a promising alternative energy technology. One of the biggest problems that exists in fuel cell is that of water management. A better understanding of wettability characteristics in the fuel cells is needed to alleviate the problem of water management. Contact angle data on gas diffusion layers (GDL) of the fuel cells can be used to characterize the wettability of GDL in fuel cells. A contact angle measurement program has been developed to measure the contact angle of sessile drops from drop images. Digitization of drop images induces pixel errors in the contact angle measurement process. The resulting uncertainty in contact angle measurement has been analyzed. An experimental apparatus has been developed for contact angle measurements at different temperature, with the feature to measure advancing and receding contact angles on gas diffusion layers of fuel cells.

Fluidic oscillator design for water removal enhancement in a PEM fuel cell

This research initiative was triggered by the problems of water management of Polymer Electrolyte Membrane Fuel Cell (PEMFC). In low temperature fuel cells such as PEMFC, some of the water produced after the chemical reaction remains in its liquid state. Excess water produced by the fuel cell must be removed from the system to avoid flooding of the gas diffusion layers (GDL). The GDL is responsible for the transport of reactant gas to the active sites and remove the water produced from the sites. If the GDL is flooded, the supply gas will not be able to reach the reactive sites and the fuel cell fails. The choice of water removal method in this research is to exert a variable asymmetrical force on a liquid droplet. As the drop of liquid is subjected to an external vibrational force in the form of periodic wave, it will begin to oscillate. A fluidic oscillator is capable to produce a pulsating flow using simple balance of momentum fluxes between three impinging jets. By connecting the outputs of the oscillator to the gas channels of a fuel cell, a flow pulsation can be imposed on a water droplet formed within the gas channel during fuel cell operation. The lowest frequency produced by this design is approximately 202 Hz when a 20 inches feed-back port length was used and a supply pressure of 5 psig was introduced. This information was found by setting up a fluidic network with appropriate data acquisition. The components include a fluidic amplifier, valves and fittings, flow meters, a pressure gage, NI-DAQ system, Siglab®, Matlab software and four PCB microphones. The operating environment of the water droplet was reviewed, speed of the sound pressure which travels down the square channel was precisely estimated, and measurement devices were carefully selected. Applicable alternative measurement devices and its application to pressure wave measurement was considered. Methods for experimental setup and possible approaches were recommended, with some discussion of potential problems with implementation of this technique. Some computational fluid dynamic was also performed as an approach to oscillator design.

PROSPECTS AND ISSUES FOR FUEL CELLS WITH FREIGHT RAIL TRANSPORTATION

Recent changes in the cost and availability of natural gas (NG) as compared to diesel have sparked interest at all levels of the commercial shipping sector. In particular, Class 1 heavy-duty rail has been researching NG as a supplement to diesel combustion. This study investigates the relative economic and emissions advantage of making use of the energy efficiencies if combustion is circumvented altogether by use of fuel cell (FC) technologies applied to NG. FC technology for the transport sector has primarily been developed for the private automobile. However, FC use in the automobile sector faces considerable economic and logistical barriers such as cost, range, durability, and refueling infrastructure. The heavy-duty freight sector may be a more reasonable setting to introduce FC technology to the transportation market. The industry has shown interest in adopting NG as a potential fuel by already investing in NG infrastructure and locomotives. The two most promising FC technologies are proton exchange membrane fuel cells (PEMFCs) and solid oxide fuel cells (SOFCs). SOFCs are more efficient and capable of accepting any kind of fuel, which makes them particularly attractive. The rail industry can benefit from the adoption of FC technology through reduced costs and emissions, as well as limiting dependence on diesel, which accounts for a large portion of operation expenses for Class 1 railroads. This report provides an economic feasibility analysis comparing the use of PEMFCs and SOFCs in heavy freight rail transport applications. The scope is to provide insight into which technologies could be pursued by the industry and to prioritize technologies that need further development. Initial results do not show economic potential for NG and fuel cells in locomotion, but some minimal potential for reduced emissions is seen. Various technology configurations and market scenarios analyzed could provide savings if the price of LNG is decreased and the price of diesel increases. The most beneficial areas of needed research include technology development for the variable output of SOFCs, and hot start-up optimization.

SIZE OPTIMIZATION OF A BIOMASS TO LIQUID FUEL CONVERSION FACILITY WITHIN A BIOMASS SUPPLY CHAIN

Bioenergy and biobased products offer new opportunities for strengthening rural economies, enhancing environmental health, and providing a secure energy future. Realizing these benefits will require the development of many different biobased products and biobased production systems. The biomass feedstocks that will enable such development must be sustainable, widely available across many different regions, and compatible with industry requirements. The purpose of this research is to develop an economic model that will help decision makers identify the optimal size of a forest resource based biofuel production facility. The model must be applicable to decision makers anywhere, though the modeled case analysis will focus on a specific region; the Upper Peninsula (U.P.) of Michigan. This work will illustrate that several factors influence the optimal facility size. Further, this effort will reveal that the location of the facility does affect size. The results of the research show that an optimal facility size can be determined for a given location and are based on variables including forest biomass availability, transportation cost rate, and economy of scale factors. These variables acting alone and interacting together can influence the optimal size and the decision of where to locate the biofuel production facility. Further, adjustments to model variables like biomass resource and storage costs have no effect on facility size, but do affect the unit cost of the biofuel produced.

THERMAL CHARACTERIZATION OF A GASOLINE TURBOCHARGED DIRECT INJECTION (GTDI) ENGINE UTILIZING LEAN OPERATION AND EXHAUST GAS RECIRCULATION (EGR)

The push for improved fuel economy and reduced emissions has led to great achievements in engine performance and control. These achievements have increased the efficiency and power density of gasoline engines dramatically in the last two decades. With the added power density, thermal management of the engine has become increasingly important. Therefore it is critical to have accurate temperature and heat transfer models as well as data to validate them. With the recent adoption of the 2025 Corporate Average Fuel Economy(CAFE) standard, there has been a push to improve the thermal efficiency of internal combustion engines even further. Lean and dilute combustion regimes along with waste heat recovery systems are being explored as options for improving efficiency. In order to understand how these technologies will impact engine performance and each other, this research sought to analyze the engine from both a 1st law energy balance perspective, as well as from a 2nd law exergy analysis. This research also provided insights into the effects of various parameters on in-cylinder temperatures and heat transfer as well as provides data for validation of other models. It was found that the engine load was the dominant factor for the energy distribution, with higher loads resulting in lower coolant heat transfer and higher brake work and exhaust energy. From an exergy perspective, the exhaust system provided the best waste heat recovery potential due to its significantly higher temperatures compared to the cooling circuit. EGR and lean combustion both resulted in lower combustion chamber and exhaust temperatures; however, in most cases the increased flow rates resulted in a net increase in the energy in the exhaust. The exhaust exergy, on the other hand, was either increased or decreased depending on the location in the exhaust system and the other operating conditions. The effects of dilution from lean operation and EGR were compared using a dilution ratio, and the results showed that lean operation resulted in a larger increase in efficiency than the same amount of dilution with EGR. Finally, a method for identifying fuel spray impingement from piston surface temperature measurements was found. Note: The material contained in this section is planned for submission as part of a journal article and/or conference paper in the future.

Biochemical Conversions of Lignocellulosic Biomass for Sustainable Fuel-Ethanol Production in the Upper Midwest

Biofuels are an increasingly important component of worldwide energy supply. This research aims to understand the pathways and impacts of biofuels production, and to improve these processes to make them more efficient. In Chapter 2, a life cycle assessment (LCA) is presented for cellulosic ethanol production from five potential feedstocks of regional importance to the upper Midwest - hybrid poplar, hybrid willow, switchgrass, diverse prairie grasses, and logging residues - according to the requirements of Renewable Fuel Standard (RFS). Direct land use change emissions are included for the conversion of abandoned agricultural land to feedstock production, and computer models of the conversion process are used in order to determine the effect of varying biomass composition on overall life cycle impacts. All scenarios analyzed here result in greater than 60% reduction in greenhouse gas emissions relative to petroleum gasoline. Land use change effects were found to contribute significantly to the overall emissions for the first 20 years after plantation establishment. Chapter 3 is an investigation of the effects of biomass mixtures on overall sugar recovery from the combined processes of dilute acid pretreatment and enzymatic hydrolysis. Biomass mixtures studied were aspen, a hardwood species well suited to biochemical processing; balsam, a high-lignin softwood species, and switchgrass, an herbaceous energy crop with high ash content. A matrix of three different dilute acid pretreatment severities and three different enzyme loading levels was used to characterize interactions between pretreatment and enzymatic hydrolysis. Maximum glucose yield for any species was 70% oftheoretical for switchgrass, and maximum xylose yield was 99.7% of theoretical for aspen. Supplemental β-glucosidase increased glucose yield from enzymatic hydrolysis by an average of 15%, and total sugar recoveries for mixtures could be predicted to within 4% by linear interpolation of the pure species results. Chapter 4 is an evaluation of the potential for producing Trichoderma reesei cellulose hydrolases in the Kluyveromyces lactis yeast expression system. The exoglucanases Cel6A and Cel7A, and the endoglucanase Cel7B were inserted separately into the K. lactis and the enzymes were analyzed for activity on various substrates. Recombinant Cel7B was found to be active on carboxymethyl cellulose and Avicel powdered cellulose substrates. Recombinant Cel6A was also found to be active on Avicel. Recombinant Cel7A was produced, but no enzymatic activity was detected on any substrate. Chapter 5 presents a new method for enzyme improvement studies using enzyme co-expression and yeast growth rate measurements as a potential high-throughput expression and screening system in K. lactis yeast. Two different K. lactis strains were evaluated for their usefulness in growth screening studies, one wild-type strain and one strain which has had the main galactose metabolic pathway disabled. Sequential transformation and co-expression of the exoglucanase Cel6A and endoglucanase Cel7B was performed, and improved hydrolysis rates on Avicel were detectable in the cell culture supernatant. Future work should focus on hydrolysis of natural substrates, developing the growth screening method, and utilizing the K. lactis expression system for directed evolution of enzymes.

DEVELOPMENT OF CONFOCAL IMAGING TECHNIQUES FOR PROBING INTERFACIAL DYNAMICS IN MICROSCALE, GAS-LIQUID, TWO-PHASE FLOW

Micro-scale, two-phase flow is found in a variety of devices such as Lab-on-a-chip, bio-chips, micro-heat exchangers, and fuel cells. Knowledge of the fluid behavior near the dynamic gas-liquid interface is required for developing accurate predictive models. Light is distorted near a curved gas-liquid interface preventing accurate measurement of interfacial shape and internal liquid velocities. This research focused on the development of experimental methods designed to isolate and probe dynamic liquid films and measure velocity fields near a moving gas-liquid interface. A high-speed, reflectance, swept-field confocal (RSFC) imaging system was developed for imaging near curved surfaces. Experimental studies of dynamic gas-liquid interface of micro-scale, two-phase flow were conducted in three phases. Dynamic liquid film thicknesses of segmented, two-phase flow were measured using the RSFC and compared to a classic film thickness deposition model. Flow fields near a steadily moving meniscus were measured using RSFC and particle tracking velocimetry. The RSFC provided high speed imaging near the menisci without distortion caused the gas-liquid interface. Finally, interfacial morphology for internal two-phase flow and droplet evaporation were measured using interferograms produced by the RSFC imaging technique. Each technique can be used independently or simultaneously when.

Application of gas-cooled Accelerator Driven System (ADS) transmutation devices to sustainable nuclear energy development

The conceptual design of a pebble bed gas-cooled transmutation device is shown with the aim to evaluate its potential for its deployment in the context of the sustainable nuclear energy development, which considers high temperature reactors for their operation in cogeneration mode, producing electricity, heat and Hydrogen. As differential characteristics our device operates in subcritical mode, driven by a neutron source activated by an accelerator that adds clear safety advantages and fuel flexibility opening the possibility to reduce the nuclear stockpile producing energy from actual LWR irradiated fuel with an efficiency of 45?46%, either in the form of Hydrogen, electricity, or both.

Influence of the composition of natural gas-hydrogen blends (HCNG) on performance an CO2 emissions of a spark ignition engine

Addition of hydrogen to natural gas could be a short-term alternative to nowadays fossil fuels as the emissions of greenhouse gases may be reduced. The aim of this study is to evaluate the performance and emissions of a park ignition engine fuelled with pure natural gas, pure hydrogen and different blends of hydrogen and natural gas (HCNG). The increase of the hydrogen fraction leads to variations in the cylinder pressure and CO2 emissions. In this work, a combustion model based on thermodynamic equations is used considering separated zones for the burned and unburned gases. The results show that the maximum cylinder pressure gets higher as the fraction of hydrogen in the blend increases. The presence of hydrogen in the blend leads to a drecrease in the CO2 emissions. Due to hydrogen properties, leaner fuel-air mixtures can be used along with the appropiate spark timing, leading to an engine emissions improvement without a performance worsening.

Sheath vaporization of a monodisperse fuel-spray jet

The group vaporization of a monodisperse fuel-spray jet discharging into a hot coflowing gaseous stream is investigated for steady flow by numerical and asymptotic methods with a two-continua formulation used for the description of the gas and liquid phases. The jet is assumed to be slender and laminar, as occurs when the Reynolds number is moderately large, so that the boundary-layer form of the conservation equations can be employed in the analysis. Two dimensionless parameters are found to control the flow structure, namely the spray dilution parameter 1, defined as the mass of liquid fuel per unit mass of gas in the spray stream, and the group vaporization parameter e, defined as the ratio of the characteristic time of spray evolution due to droplet vaporization to the characteristic diffusion time across the jet. It is observed that, for the small values of e often encountered in applications, vaporization occurs only in a thin layer separating the spray from the outer droplet-free stream. This regime of sheath vaporization, which is controlled by heat conduction, is amenable to a simplified asymptotic description, independent of ε,in which the location of the vaporization layer is determined numerically as a free boundary in a parabolic problem involving matching of the separate solutions in the external streams, with appropriate jump conditions obtained from analysis of the quasi-steady vaporization front. Separate consideration of dilute and dense sprays, corresponding, respectively, to the asymptotic limits λ<<1 and λ>>1, enables simplified descriptions to be obtained for the different flow variables, including explicit analytic expressions for the spray penetration distance.

Source terms for calculations of vaporizing and burning fuel sprays with non-unity Lewis numbers in gases with temperature-dependent thermal conductivities

Liquid-fueled burners are used in a number of propulsion devices ranging from internal combustion engines to gas turbines. The structure of spray flames is quite complex and involves a wide range of time and spatial scales in both premixed and non-premixed modes (Williams 1965; Luo et al. 2011). A number of spray-combustion regimes can be observed experimentally in canonical scenarios of practical relevance such as counterflow diffusion flames (Li 1997), as sketched in figure 1, and for which different microscalemodelling strategies are needed. In this study, source terms for the conservation equations are calculated for heating, vaporizing and burning sprays in the single-droplet combustion regime. The present analysis provides extended formulation for source terms, which include non-unity Lewis numbers and variable thermal conductivities.

Life cycle assessment of concentrated solar power (CSP) and the influence of hybridising with natural gas

Purpose Concentrating Solar Power (CSP) plants based on parabolic troughs utilize auxiliary fuels (usually natural gas) to facilitate start-up operations, avoid freezing of HTF and increase power output. This practice has a significant effect on the environmental performance of the technology. The aim of this paper is to quantify the sustainability of CSP and to analyse how this is affected by hybridisation with different natural gas (NG) inputs. Methods A complete Life Cycle (LC) inventory was gathered for a commercial wet-cooled 50 MWe CSP plant based on parabolic troughs. A sensitivity analysis was conducted to evaluate the environmental performance of the plant operating with different NG inputs (between 0 and 35% of gross electricity generation). ReCiPe Europe (H) was used as LCA methodology. CML 2 baseline 2000 World and ReCiPe Europe E were used for comparative purposes. Cumulative Energy Demands (CED) and Energy Payback Times (EPT) were also determined for each scenario. Results and discussion Operation of CSP using solar energy only produced the following environmental profile: climate change 26.6 kg CO2 eq/KWh, human toxicity 13.1 kg 1,4-DB eq/KWh, marine ecotoxicity 276 g 1,4-DB eq/KWh, natural land transformation 0.005 m2/KWh, eutrophication 10.1 g P eq/KWh, acidification 166 g SO2 eq/KWh. Most of these impacts are associated with extraction of raw materials and manufacturing of plant components. The utilization NG transformed the environmental profile of the technology, placing increasing weight on impacts related to its operation and maintenance. Significantly higher impacts were observed on categories like climate change (311 kg CO2 eq/MWh when using 35 % NG), natural land transformation, terrestrial acidification and fossil depletion. Despite its fossil nature, the use of NG had a beneficial effect on other impact categories (human and marine toxicity, freshwater eutrophication and natural land transformation) due to the higher electricity output achieved. The overall environmental performance of CSP significantly deteriorated with the use of NG (single score 3.52 pt in solar only operation compared to 36.1 pt when using 35 % NG). Other sustainability parameters like EPT and CED also increased substantially as a result of higher NG inputs. Quasilinear second-degree polynomial relationships were calculated between various environmental performance parameters and NG contributions. Conclusions Energy input from auxiliary NG determines the environmental profile of the CSP plant. Aggregated analysis shows a deleterious effect on the overall environmental performance of the technology as a result of NG utilization. This is due primarily to higher impacts on environmental categories like climate change, natural land transformation, fossil fuel depletion and terrestrial acidification. NG may be used in a more sustainable and cost-effective manner in combined cycle power plants, which achieve higher energy conversion efficiencies.

Hybridizing concentrated solar power (CSP) with biogas and biomethane as an alternative to natural gas: Analysis of environmental performance using LCA

Concentrating Solar Power (CSP) plants typically incorporate one or various auxiliary boilers operating in parallel to the solar field to facilitate start up operations, provide system stability, avoid freezing of heat transfer fluid (HTF) and increase generation capacity. The environmental performance of these plants is highly influenced by the energy input and the type of auxiliary fuel, which in most cases is natural gas (NG). Replacing the NG with biogas or biomethane (BM) in commercial CSP installations is being considered as a means to produce electricity that is fully renewable and free from fossil inputs. Despite their renewable nature, the use of these biofuels also generates environmental impacts that need to be adequately identified and quantified. This paper investigates the environmental performance of a commercial wet-cooled parabolic trough 50 MWe CSP plant in Spain operating according to two strategies: solar-only, with minimum technically viable energy non-solar contribution; and hybrid operation, where 12 % of the electricity derives from auxiliary fuels (as permitted by Spanish legislation). The analysis was based on standard Life Cycle Assessment (LCA) methodology (ISO 14040-14040). The technical viability and the environmental profile of operating the CSP plant with different auxiliary fuels was evaluated, including: NG; biogas from an adjacent plant; and BM withdrawn from the gas network. The effect of using different substrates (biowaste, sewage sludge, grass and a mix of biowaste with animal manure) for the production of the biofuels was also investigated. The results showed that NG is responsible for most of the environmental damage associated with the operation of the plant in hybrid mode. Replacing NG with biogas resulted in a significant improvement of the environmental performance of the installation, primarily due to reduced impact in the following categories: natural land transformation, depletion of fossil resources, and climate change. However, despite the renewable nature of the biofuels, other environmental categories like human toxicity, eutrophication, acidification and marine ecotoxicity scored higher when using biogas and BM.

The ‘Unknown Knowns’ of the Global Gas Market. CEPS Essay No. 16, 16 October 2014

Energy markets evolve at least as quickly as the economies they fuel. But development unfolds at an irregular pace, with starts and stops often precipitated by seemingly unpredictable dynamics. Is it really impossible to forecast these ‘revolutions’, if the past can be seen as prologue? The answer might be in the way we look at future events; even if we accept that some events are unpredictable, we may be able to infer much more about the future trends through a broader reading of available data, thus revealing ‘unknown knowns’ that may be useful in understanding paradigm shifts ahead. This paper presents an analysis of the global gas market, offering views on what the most relevant ‘unknown knowns’ of today look like, and hypotheses about some of the possible game-changing events that the market is likely to face in the short to medium term.