A closed cycle for esterifying aromatic hydrocarbons with CO[subscript 2] and alcohol
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Lithium (Li)-ion batteries play a critical role in modern day technologies, but their specific energy (Wh kg-1) and energy density (Wh L-1) are approaching the maximum practically achievable values based on existing manufacturing processes with the conventional cathode and anode materials. Developing the next generation rechargeable batteries with a specific energy higher than 300 Wh kg-1, up to 500 Wh kg-1, is a significant challenge. This paper discusses the pathways to build the next generation 500 Wh kg-1 rechargeable Li battery based on Li metal anode and a high nickel-content lithium nickel-manganese-cobalt oxide (high-Ni NMC) cathode. The fundamental requirements and practical technical approaches will be explored to hopefully address this grand challenge. In particular, we discuss the detailed cell level requirements and parameters to achieve high energy density, as well as the significant scientific challenges and potential solutions, including but not limited to enable the direct utilization of Li metal anode with high efficiency and long-term cycling stability, dendrite-free Li metal deposition, high utilization of the cathode materials with high mass loading and reasonable electrode thickness along with minimum parasitic weight in the cathode side. The cell level understanding and validation of the materials properties for high performance and control of interfacial reactions across the whole cell will be explored. New concepts in emerging multifunctional materials and electrolytes/additives and their implications will also be discussed.
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V–Ce RFBs (∼100% CE and ∼70% EE over 100 cycles) using a CH 3 SO 3 H-based electrolyte and a AEM separator shows 30% higher capacity and 0.024% capacity fade/cycle vs. 5% capacity fade/cycle for H 2 SO 4 supported V–Ce ED-RFBs.
Microbial metabolism is the engine that drives global biogeochemical cycles, yet many key transformations are carried out by microbial consortia over short spatiotemporal scales that elude detection by traditional analytical approaches. We investigate syntrophic sulfur cycling in the ‘pink berry’ consortia of the Sippewissett Salt Marsh through an integrative study at the microbial scale. The pink berries are macroscopic, photosynthetic microbial aggregates composed primarily of two closely associated species: sulfide-oxidizing purple sulfur bacteria (PB-PSB1) and sulfate-reducing bacteria (PB-SRB1). Using metagenomic sequencing and 34S-enriched sulfate stable isotope probing coupled with nanoSIMS, we demonstrate interspecies transfer of reduced sulfur metabolites from PB-SRB1 to PB-PSB1. The pink berries catalyse net sulfide oxidation and maintain internal sulfide concentrations of 0–500 M. Sulfide within the berries, captured on silver wires and analysed using secondary ion mass spectrometer, increased in abundance towards the berry interior, while δ34S-sulfide decreased from 6‰ to -31‰ from the exterior to interior of the berry. These values correspond to sulfate–sulfide isotopic fractionations (15–53‰) consistent with either sulfate reduction or a mixture of reductive and oxidative metabolisms. Together this combined metagenomic and high-resolution isotopic analysis demonstrates active sulfur cycling at the microscale within well-structured macroscopic consortia consisting of sulfide-oxidizing anoxygenic phototrophs and sulfate-reducing bacteria.
Batteries which use dissolved redox-active species, such as redox flow batteries (RFBs), are often considered to be constrained in their operation and energy density by the solubility limit of the redox species. Here, we show that soluble redox active electrolytes can be reversibly cycled deeply into the precipitation regime, permitting higher effective concentrations, energy densities, and lower costs. Using aqueous sodium polysulfide negative electrolytes cycled in the nominal Na 2 S 2 to Na 2 S 4 capacity range as an example, we show that the effective solubility can be increased from 5 M in the fully-dissolved state to as much as 10 M using the precipitation strategy. Stable cycling was observed at 8 M concentration over more than 1600h at room temperature. We also analyze the range of polysulfide electrochemical stability, and characterize the precipitate composition. This enhanced effective concentration approach may be generalized to other redox chemistries that utilize solubilized reactants, and may be especially useful for long-duration storage applications where slow charge-discharge rates allow equilibration of precipitated species with the redox-active solution.
As part of the Cyclotron Road program, Tyfast Energy Corp. aimed to investigate the Li 3 V 2 O 5 (LVO) anode material for next generation lithium batteries. State of the art and fast charging lithium-ion batteries are based on the lithium titanate or Li 4 Ti 5 O 12 (LTO) anode chemistry. LTO cells demonstrate fast charging times (<6 mins), long cycle life (>20,000 cycles), but at the expense of very low energy density (<200Wh/L, <80Wh/kg). Silicon anodes have the promise of achieving fast charging times, however, issues with cycling stability in combination with fast charging is unknown. LVO has unique properties that enable new performance window for lithium batteries. First, LVO operates at an average potential of 0.6V vs. Li/Li + , well above the Li-metal plating region allowing ultrafast charge capability without sacrificing safety. Second, the LVO has a high specific capacity of 250 mAh/g making battery pack energy density equivalent with current high-energy Li-ion chemistries.
Conventional diesel combustion, also known as Mixing-Controlled Compression Ignition (MCCI), is expected to be the primary power source for medium- and heavy-duty vehicles for decades to come. Displacing petroleum-based ultra-low-sulfur diesel (ULSD) as much as possible with low-net-carbon biofuels will become necessary to help mitigate effects on climate change. Neat biofuels may have difficulty meeting current diesel fuel standards but blends of 30% biofuel in ULSD show potential as ‘drop-in’ fuels. These blends must not make significant changes to the combustion phasing of the MCCI process if they are to be used interchangeably with neat ULSD. An important aspect of MCCI phasing is the ignition delay (ID), i.e. the time between the start of fuel injection and the initial premixed autoignition that initiates the MCCI process. Bench experiments can evaluate the expected ignition delay of a fuel via cetane number (CN) or alternative methods such as the indicated cetane number (ICN); however, neither CN nor ICN correlate perfectly with the ignition delay measured in actual engine experiments. Furthermore, there is no standardized methodology on how to quantify MCCI ignition delay from engine cylinder pressure measurements, creating difficulties in cross-study comparison. In this study, several engine ignition delay calculation methods are evaluated for robustness in deriving ignition delay on both a cycle-averaged and cycle-to-cycle basis. Eight biofuel blends with varying ICN, oxygen concentration and other fuel properties were used to study the different methods. This yields a thorough analysis of how certain biofuel blends affect ignition delay and the entire MCCI process, as well as a thorough evaluation of the differences between the ID calculation methods. Many of these methods are equally valid, but the choice of method has a significant impact on the resulting ID, which must be carefully considered when evaluating results across multiple studies.
Here, large uncertainties in land surface models (LSMs) simulations still arise from inaccurate forcing, poor description of land surface heterogeneity (soil and vegetation properties), incorrect model parameter values and incomplete representation of biogeochemical processes. The recent increase in the number and type of carbon cycle-related observations, including both in situ and remote sensing measurements, has opened a new road to optimize model parameters via robust statistical model–data integration techniques, in order to reduce the uncertainties of simulated carbon fluxes and stocks. In this study we present a carbon cycle data assimilation system that assimilates three major data streams, namely the Moderate Resolution Imaging Spectroradiometer (MODIS)-Normalized Difference Vegetation Index (NDVI) observations of vegetation activity, net ecosystem exchange (NEE) and latent heat (LE) flux measurements at more than 70 sites (FLUXNET), as well as atmospheric CO 2 concentrations at 53 surface stations, in order to optimize the main parameters (around 180 parameters in total) of the Organizing Carbon and Hydrology in Dynamics Ecosystems (ORCHIDEE) LSM (version 1.9.5 used for the Coupled Model Intercomparison Project Phase 5 (CMIP5) simulations). The system relies on a stepwise approach that assimilates each data stream in turn, propagating the information gained on the parameters from one step to the next. Overall, the ORCHIDEE model is able to achieve a consistent fit to all three data streams, which suggests that current LSMs have reached the level of development to assimilate these observations. The assimilation of MODIS-NDVI (step 1) reduced the growing season length in ORCHIDEE for temperate and boreal ecosystems, thus decreasing the global mean annual gross primary production (GPP). Using FLUXNET data (step 2) led to large improvements in the seasonal cycle of the NEE and LE fluxes for all ecosystems (i.e., increased amplitude for temperate ecosystems). The assimilation of atmospheric CO 2 , using the general circulation model (GCM) of the Laboratoire de Météorologie Dynamique (LMDz; step 3), provides an overall constraint (i.e., constraint on large-scale net CO 2 fluxes), resulting in an improvement of the fit to the observed atmospheric CO 2 growth rate. Thus, the optimized model predicts a land C (carbon) sink of around 2.2 PgC yr -1 (for the 2000–2009 period), which is more compatible with current estimates from the Global Carbon Project (GCP) than the prior value. The consistency of the stepwise approach is evaluated with back-compatibility checks. The final optimized model (after step 3) does not significantly degrade the fit to MODIS-NDVI and FLUXNET data that were assimilated in the first two steps, suggesting that a stepwise approach can be used instead of the more “challenging” implementation of a simultaneous optimization in which all data streams are assimilated together. Most parameters, including the scalar of the initial soil carbon pool size, changed during the optimization with a large error reduction. This work opens new perspectives for better predictions of the land carbon budgets.
The Open-Cycle Gas Turbine/Steam Turbine Combined Cycle can be an effective energy conversion system for converting coal to electricity. The intermediate step in this energy conversion process is to convert the coal into a fuel acceptable to a gas turbine. This can be accomplished by producing a synthetic gas or liquid, and by removing, in the fuel conversion step, the elements in the fuel that would be harmful to the environment if combusted. In this paper, two open-cycle gas turbine combined systems are evaluated: one employing an integrated low-Btu gasifier, and one utilizing a semi-clean liquid fuel. A consistent technical/economic information base is developed for these two systems, and is compared with a reference steam plant burning coal directly in a conventional furnace.
Dynamic Dielectric measurements made over a wide range of frequency provide a sensitive and convenient means for monitoring the cure process in thermosets and thermoplastics. The measurement of dielectric relaxation is one of only a few instrumental techniques available for studying molecular properties in both the liquid and solid states. Furthermore, it is probably the only convenient experimental technique for studying the polymerization process of going from a monomeric liquid of varying viscosity to a crosslinked, insoluble, high temperature solid. The objective of the research is to develop on-line dielectric instrumentation for quantitative nondestructive material evaluation and closed loop smart cure cycle control. The key is to relate the chemistry of the cure cycle process to the dielectric properties of the polymer system by correlating the time, temperature, and frequency dependent dielectric measurements with chemical characterization measurements. Measurement of the wide variation in magnitude of the complex permittivity with both frequency and state of cure, coupled with chemical characterization work, have been shown in the laboratory to have the potential to determine: resin quality, composition and age; cure cycle window boundaries; onset of flow and point of maximum flow; extent of and completion of reaction; evolution of volatiles; T sub g; and, crosslinking and molecular weight buildup.
The development of methodology for a probabilistic material strength degradation is described. The probabilistic model, in the form of a postulated randomized multifactor equation, provides for quantification of uncertainty in the lifetime material strength of aerospace propulsion system components subjected to a number of diverse random effects. This model is embodied in the computer program entitled PROMISS, which can include up to eighteen different effects. Presently, the model includes five effects that typically reduce lifetime strength: high temperature, high-cycle mechanical fatigue, low-cycle mechanical fatigue, creep and thermal fatigue. Results, in the form of cumulative distribution functions, illustrated the sensitivity of lifetime strength to any current value of an effect. In addition, verification studies comparing predictions of high-cycle mechanical fatigue and high temperature effects with experiments are presented. Results from this limited verification study strongly supported that material degradation can be represented by randomized multifactor interaction models.
Thick thermal barrier coating systems in a diesel engine experience severe thermal low cycle fatigue (LCF) and high cycle fatigue (HCF) during engine operation. In this paper, the mechanisms of fatigue crack initiation and propagation in a ZrO2-8wt.% Y2O3 thermal barrier coating, under simulated engine thermal LCF and HCF conditions, are investigated using a high power CO2 laser. Experiments showed that the combined LCF/HCF tests induced more severe coating surface cracking, microspallation and accelerated crack growth, as compared to the pure LCF test. Lateral crack branching and the ceramic/bond coat interface delaminations were also facilitated by HCF thermal loads, even in the absence of severe interfacial oxidation. Fatigue damages at crack wake surfaces, due to such phenomena as asperity/debris contact induced cracking and splat pull-out bending during cycling, were observed especially for the combined LCF/HCF tests. It is found that the failure associated with LCF is closely related to coating sintering and creep at high temperatures, which induce tensile stresses in the coating after cooling. The failure associated with HCF process, however, is mainly associated with a surface wedging mechanism. The interaction between the LCF, HCF and ceramic coating creep, and the relative importance of LCF and HCF in crack propagation are also discussed based on the experimental evidence.
Thick thermal barrier coating systems in a diesel engine experience severe thermal low cycle fatigue (LCF) and high cycle fatigue (HCF) during engine operation. In this paper, the mechanisms of fatigue crack initiation and propagation in a ZrO2-8wt% Y2O3 thermal barrier coating, under simulated engine thermal LCF and HCF conditions, are investigated using a high power CO2 laser. Experiments showed that the combined LCF-HCF tests induced more severe coating surface cracking, microspallation and accelerated crack growth, as compared to the pure LCF test. Lateral crack branching and the ceramic/bond coat interface delaminations were also facilitated by HCF thermal loads, even in the absence of severe interfacial oxidation. Fatigue damage at crack wake surfaces, due to such phenomena as asperity/debris contact induced cracking and splat pull-out bending during cycling, was observed especially for the combined LCF-HCF tests. It is found that the failure associated with LCF is closely related to coating sintering and creep at high temperatures, which induce tensile stresses in the coating after cooling. The failure associated with HCF process, however, is mainly associated with a surface wedging mechanism. The interaction between the LCF, HCF and ceramic coating creep, and the relative importance of LCF and HCF in crack propagation are also discussed based on the experimental evidence.
A dual expander cycle (DEC) rocket engine with an intermediate closed-cycle heat exchanger is provided. A conventional DEC rocket engine has a closed-cycle heat exchanger thermally coupled thereto. The heat exchanger utilizes heat extracted from the engine's fuel circuit to drive the engine's oxidizer turbomachinery.
We report on the prolonged solar-maximum conditions until late 2015 at the north-polar region of the Sun indicated by the occurrence of high-latitude prominence eruptions (PEs) and microwave brightness temperature close to the quiet-Sun level. These two aspects of solar activity indicate that the polarity reversal was completed by mid-2014 in the south and late 2015 in the north. The microwave brightness in the south-polar region has increased to a level exceeding the level of the Cycle 23/24 minimum, but just started to increase in the north. The northsouth asymmetry in the polarity reversal has switched from that in Cycle 23. These observations lead us to the hypothesis that the onset of Cycle 25 in the northern hemisphere is likely to be delayed with respect to that in the southern hemisphere. We find that the unusual condition in the north is a direct consequence of the arrival of poleward surges of opposite polarity from the active region belt. We also find that multiple rush-to-the-pole episodes were indicated by the PE locations that lined up at the boundary between opposite-polarity surges. The high-latitude PEs occurred in the boundary between the incumbent polar flux and the insurgent flux of opposite polarity.
Soil emissions have been inadequately characterized in life cycle assessment of biofuels (see section 3.2.3). This project measures the net differences in field-level greenhouse gas emissions (CO 2 , N 2 O, and CH 4 ) due to corn residue removal for cellulosic ethanol production. Gas measurements are then incorporated into life cycle assessment of the final biofuel product to determine whether it is in compliance with federal greenhouse gas emissions standards for biofuels (Renewable Fuel Standard 2, RFS2). The field measurements have been conducted over three years on two, quarter-section, production-scale, irrigated corn fields (both roughly 50 hectares, as this size of field is necessary for reproducible eddy covariance flux measurements of CO 2 ; chamber measurements are used to determine N 2 O and CH 4 emissions). Due to a large hail storm in 2010, estimates of the emission from residue could not be separated from the total CO 2 flux in 2011. This led us to develop soil organic carbon (SOC) modeling techniques to estimate changes in CO 2 emissions from residue removal. Modeling has predicted emissions of CO 2 from oxidation of SOC that are consistent (<12%) with 9 years of CO 2 flux measurements at the two production field sites, and modeling is also consistent with other field measurements (Liska et al., submitted). The model was then used to estimate the average change in SOC and CO 2 emissions from nine years of simulated residue removal (6 Mg biomass per hectare per year) at the sites; a loss of 0.43 Mg C ha -1 yr -1 resulted. The model was then used to estimate SOC changes over 10 years across Nebraska using supercomputing, based on 61 million, 30 x 30 meter, grid cells to account for regional variability in initial SOC, crop yield, and temperature; an average loss of 0.47 Mg C ha -1 yr -1 resulted. When these CO 2 emissions are included in simple life cycle assessment calculations, emissions from cellulosic ethanol from crop residue are above mandated levels of 60% reduction compared to gasoline (Liska, in press). These approaches are both technically effective and economically feasible. This work has been extensively peer reviewed.