Ultra-low emission power generation utilizing chemically stabilized waste plastics pyrolysis oil in RCCI combustion concept.

Emission standards in European Union, designed to reduce the environmental impact of power generation, present a significant challenge for fast-response distributed power generation systems based on internal combustion engines. Regulated emissions, such as NOx and particulate matter present a major concern due to their adverse number of environmental and health effects. Simultaneously, European Union strives towards sustainable management of plastic waste and seeks the ways for its upcycling and production of new fuels and chemicals. As an answer to the presented challenges, the present experimental study addresses the potential for use of chemically stabilized Waste Plastics Oil (WPO), a product of pyrolysis process of waste plastics in a Reactivity Controlled Compression Ignition (RCCI) combustion concept. To establish a reactivity-controlled combustion, the study uses a combination of methane (a model fuel for biomethane) and WPO to a) simultaneously reduce NOx and particulate matter emissions due to low local combustion temperatures and a high degree of charge homogenization and b) address waste and carbon footprint reduction challenges. Through experiments, influence of direct injection timing and energy shares of utilized fuels to in-cylinder thermodynamic parameters and engine emission response were evaluated in engine operating points at constant indicated mean effective pressure. Acquired results were deeply investigated and benchmarked against compression ignition (CI) and RCCI operation with conventional diesel fuel to determine potential for WPO utilization in an advanced low-temperature combustion concept. Results show that chemically stabilized WPO can be efficiently utilized in RCCI combustion concept without adaptation of injection parameters and that with suitable control parameters, ultra-low emissions of NOx and PM can be achieved with utilized fuels. For diesel/methane mix, NOx and PM emissions were reduced compared to conventional CI operation for 82.0% and 93.2%, respectively, whereas for WPO/methane mix, NOx and PM emissions were reduced for 88.7% and 97.6%, respectively, which can be ascribed to favourable chemical characteristics of WPO for the utilized combustion concept. In the least favourable operating point among those studied, indicated mean effective pressure covariance was kept below 2.5%, which is well below 5% being considered the limit for stable engine operation.

Investigating the Coating Effect on Charge Transfer Mechanisms in Composite Electrodes for Lithium-Ion Batteries.

The performance of lithium-ion batteries (LIBs) relies on the characteristics of the cathode material, including both intentionally applied coatings and naturally formed surface layers or binder adhesion. This study investigated the influence of the ion-permeable surface fraction, distribution, and characteristics of the coating on the performance of a lithium iron phosphate (LFP) electrode material. We developed an extended Newman-type half-cell model and examined the impact of coating parameters on the galvanostatic discharge curves of the LFP electrode material. The study found that the ion-permeable surface fraction has a significant influence on the diffusion and charge transfer characteristics of the electrode material. A decrease in the ion-permeable surface fraction leads to a decrease in the measured diffusion coefficients and to an increase in the overall coating resistance of the electrode material. Interestingly, the distribution of the ion-permeable surface also plays a role in the diffusion characteristics, with a coarsely dispersed coating resulting in lower diffusion coefficients. Additionally, the coating characteristics significantly affect the polarization and capacity of the electrode material at different C-rates. The model was used to approximate the experimental discharge curves of the LFP-based composite electrodes with two different compositions, and the simulated data showed satisfactory agreement with the experiment. Thus, we believe that the developed model and its further extension will be useful in numerical simulations that aim to facilitate the search for optimal compositions.

Entering Voltage Hysteresis in Phase-Separating Materials: Revealing the Electrochemical Signature of the Intraparticle Phase-Separated State.

Hysteresis is a general phenomenon regularly observed in various materials. Usually, hysteretic behavior is an intrinsic property that cannot be circumvented in the nonequilibrium operation of the system. Herein, it is shown that, at least with regard to the hysteretic behavior of phase-separating battery materials, it is possible to enter (deeply) the hysteretic loop at finite battery currents. This newly observed electric response of the electrode, which is inherent to phase-separating materials, is related to its microscopic origin arising from a (significant) share of the active material residing in an intraparticle phase-separated state. This intriguing observation is further generalized by revealing that a phase-separating material can feature (significantly) different chemical potentials at the same bulk lithiation level and temperature when exposed to the same finite current and external voltage hysteresis. Therefore, the intraparticle phase-separated state significantly affects the DC and AC characteristics of the battery. The experimental evidence for entering the intraparticle phase-separated state is supported by thermodynamic reasoning and advanced modeling. The current findings will help advance the understanding, control, diagnostics, and monitoring of batteries composed of phase-separating materials while also providing pertinent motivation for the enhancement of battery design and performance.

Spatially selective dilution - A novel approach for heat release control in continuous combustion.

To support the ongoing energy transition and minimize the environmental footprint of combustion related technologies, the paper presents a novel approach for combustion control in gas turbines and burners. It relies on spatially targeted injection of inert components in the spray core where existent concepts fail to deliver the desired dilution rate and are unable to fully govern the spatial distribution of heat release rates. Combustion process control is thus possible by actively adjusting the composition and mass flow of spatially selective introduction of inert species in the spray, optionally combined with classic, external exhaust gas recirculation, leading to an ultimate fuel-flexible concept which is capable of adjustments to heterogeneous fuels, their reactivity and physical properties. The proof of concept is demonstrated in a gas turbine combustion chamber first by investigating the isolated effects of spatially selective injection of inert species, its comparison to external exhaust gas recirculation and a combination of both. The results confirm the superiority of the approach as spatially selective mixture inertization is capable of 7% reduction of NO emissions with merely 3% increase of CO emissions and even 9% reduction of PM emissions. Furthermore, the concept proved transferrable together with all its benefits to combustion cycles with external exhaust gas recirculation. In this case, the 63% reduction of NO emissions with no observed CO penalty is possible. Simultaneous exploitation of spatially selective inertization, as well as external exhaust gas recirculation forms a fully controllable concept - spatially selective dilution control (SSDC), which enables extensive adjustability of dilution rates throughout the spray core and primary zone of combustion chamber. Compared to baseline case, such approach was proved to simultaneously reduce CO, NO and PM emissions normalized to fuel thermal power for 39%, 63% and 91%, respectively. The confirmation of applicability of the novel approach and its potential to influence the local conditions is opening a series of possible uses, either as an original design feature for future fuel-flexible systems or as a retrofit approach in existent combustion systems.

Holistic approach to chemical degradation of Nafion membranes in fuel cells: modelling and predictions.

The state of health of polyfluorinated sulfonic-acid ionomer membranes (e.g. Nafion®) in low-temperature proton exchange membrane fuel cells (LT-PEMFCs) is negatively influenced by degradation phenomena occurring during their operation. As a consequence, the performance and durability of the membrane are decreased. In this article, we focus on simulating and predicting chemical membrane degradation phenomena using a holistic zero-dimensional kinetic framework. The knowledge of chemical degradation mechanisms is widely spread. We have collected and evaluated an extensive set of chemical mechanisms to achieve a holistic approach. This yields a set of 23 coupled chemical equations, which provide the whole cause and effect chain of chemical degradation in LT-PEMFCs (based on the Fenton reaction between Fe2+ and H2O2via the attack of hydroxyl radicals on the membrane, loss of ionomer moieties and emission of fluoride). Our kinetic framework allows the reproduction of experimentally accessible data such as fluoride emission rates and concentrations of ionomer moieties (from both in situ and ex situ tests). We present an approach, which allows estimations of the membrane lifetime based on fluoride emission rates. In addition, we outline the demetallation of Fe-N-C catalysts as a source of additional harmful iron species, which accelerate chemical membrane degradation. To demonstrate the expandability and versatility of the kinetic framework, a set of five chemical equations describing the radical scavenging properties of cerium agents is coupled to the main framework and its influence on membrane degradation is analysed. An automated solving routine for the system of coupled chemical equations on the basis of the chemical kinetic simulation tool COPASI has been developed and is freely accessible online ().

Thermodynamically consistent derivation of chemical potential of a battery solid particle from the regular solution theory applied to LiFePO4.

The chemical potential of lithium in LixFePO4 active cathode nanoparticles and the surface free energy between LixFePO4 and electrolyte were determined with the novel thermodynamically consistent application of the regular solution theory. Innovative consideration of crystal anisotropy accounts for the consistent determination of the dependency of the chemical potential on the mechanistically derived enthalpy of mixing and the phase boundary gradient penalty. This enabled the analytic, thermodynamically consistent determination of the phase boundary thickness between LiFePO4 and FePO4, which is in good agreement with experimental observations. The obtained explicit functional dependency of the surface free energy on the lithium concentration enables adequate simulation of the initiation of the phase transition from FePO4 to LiFePO4 at the surface of active cathode particles. To validate the plausibility of the newly developed approaches, lithium intercalation into the LixFePO4 nanoparticles from electrolyte was modeled by solving the Cahn-Hilliard equation in a quasi-two-dimensional domain.

Designing the microturbine engine for waste-derived fuels.

Presented paper deals with adaptation procedure of a microturbine (MGT) for exploitation of refuse derived fuels (RDF). RDF often possess significantly different properties than conventional fuels and usually require at least some adaptations of internal combustion systems to obtain full functionality. With the methodology, developed in the paper it is possible to evaluate the extent of required adaptations by performing a thorough analysis of fuel combustion properties in a dedicated experimental rig suitable for testing of wide-variety of waste and biomass derived fuels. In the first part key turbine components are analyzed followed by cause and effect analysis of interaction between different fuel properties and design parameters of the components. The data are then used to build a dedicated test system where two fuels with diametric physical and chemical properties are tested - liquefied biomass waste (LW) and waste tire pyrolysis oil (TPO). The analysis suggests that exploitation of LW requires higher complexity of target MGT system as stable combustion can be achieved only with regenerative thermodynamic cycle, high fuel preheat temperatures and optimized fuel injection nozzle. Contrary, TPO requires less complex MGT design and sufficient operational stability is achieved already with simple cycle MGT and conventional fuel system. The presented approach of testing can significantly reduce the extent and cost of required adaptations of commercial system as pre-selection procedure of suitable MGT is done in developed test system. The obtained data can at the same time serve as an input for fine-tuning the processes for RDF production.

An innovative hybrid 3D analytic-numerical model for air breathing parallel channel counter-flow PEM fuel cells.

The parallel straight channel PEM fuel cell model presented in this paper extends the innovative hybrid 3D analytic-numerical (HAN) approach previously published by the authors with capabilities to address ternary diffusion systems and counter-flow configurations. The model's core principle is modelling species transport by obtaining a 2D analytic solution for species concentration distribution in the plane perpendicular to the cannel gas-flow and coupling consecutive 2D solutions by means of a 1D numerical pipe-flow model. Electrochemical and other nonlinear phenomena are coupled to the species transport by a routine that uses derivative approximation with prediction-iteration. The latter is also the core of the counter-flow computation algorithm. A HAN model of a laboratory test fuel cell is presented and evaluated against a professional 3D CFD simulation tool showing very good agreement between results of the presented model and those of the CFD simulation. Furthermore, high accuracy results are achieved at moderate computational times, which is owed to the semi-analytic nature and to the efficient computational coupling of electrochemical kinetics and species transport.