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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 199 records · Page 11

Pigment removal from reverse-printed laminated flexible films by solvent-targeted recovery and precipitation

The solvent-targeted recovery and precipitation (STRAP) process separates and recovers the constituent resins in multilayer plastic packaging films by selective polymer dissolution. In this work, the cause of coloring in the STRAP-recycled polyethylene (PE) resins from postindustrial printed films was identified as decomposed diarylide pigments. Two different approaches are needed to completely remove the dissolved colorants during the STRAP process including (i) adding an activated carbon (AC) adsorbent to the solvent after polymer dissolution and (ii) proper mechanical filtration of the polymer-solvent cake to remove as much solvent from the cake as possible. Colorless recycled PE can be produced by a combination of the proposed approaches (choosing the proper solvent, adding an AC adsorbent, and doing proper mechanical filtration) with minimal accumulation of colorants in the recycled STRAP solvents. This study demonstrated that high-quality STRAP low-density PE can be obtained from printed plastic films, enhancing the potential circularity of these packaging materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Safe Electrolytes for Batteries

The demand for reliable and safe lithium-ion batteries (LIBs) for electric vehicles (EVs) and energy storage systems (ESS) necessitates the exploration of nonflammable phosphorus-based electrolytes as alternatives to the traditional flammable carbonate-based ones. However, integrating phosphorus-based electrolyte poses challenges, including capacity fading and compatibility issues with graphite material. Here, a high-throughput (HTP) electrochemical characterization method, similar to PH test paper, is introduced to fast screen compatible phosphorus-based electrolyte for use with graphite. Among 1,740 combinations of phosphorus-based electrolytes and graphite materials, 101 promising combinations are identified for further evaluation. These identified phosphorus-based electrolytes and graphite materials are evaluated and optimized in Li/Graphite half-cells and Graphite/LiFePO 4 (LFP) full-cells using commercial-level electrodes. The desolvation energy of a complex with one Li+ and four solvent molecules of phosphate or carbonate is calculated by density functional theory (DFT). Key parameters such as viscosity, ionic conductivity, and flammability of the electrolytes are thoroughly tested and optimized. The modified phosphate-dominant electrolyte (2 M LiFSI TEP/DME/EC (6/2/2, volume ratio) + 5 wt.% VEC + 5 wt.% FEC) demonstrates excellent thermal stability with lithiated graphite and showcases superior cycling performance in the Graphite/LFP full cell, surpassing prior research findings in phosphate-dominant electrolytes. By the rapid HTP screening and identification of compatible electrolyte-graphite combinations, this approach contributes to expediting the development of safer LIBs for EVs and ESS.

25 ENERGY STORAGE↗

Stabilizing LiCoO 2 at 4.6 V by regulating anti-oxidative solvents

For LiCoO 2 (LCO) operating at high voltages (>4.5 V vs. Li/Li + ), the intensive side reactions between LCO and traditional ethylene carbonate (EC)-based electrolytes with LiPF 6 salts can produce plenty of corrosive species (such as HF and HPO 2 F 2 ), causing severe surface degradation. Herein, anti-oxidative fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC) were selected as co-solvents to reduce the generation of corrosive species. Besides, PF 6 − anions enrich the Helmholtz plane of the LCO/electrolyte interface and promote the formation of a robust cathode/electrolyte interphase (CEI) featuring LiF/Li x PO y F z /Li 3 PO 4 inorganics and P-containing organics under the synergy of fluorinated solvents, which significantly inhibits the catalysis of highly oxidative Co 4+ /O n− (0 < n < 2). Benefiting from the reduced corrosive species and reinforced CEI, the layered structure of the LCO surface is well preserved during long-term cycling, with a highly reversible O3/H1-3 phase transition. Consequently, a LCO||graphite pouch cell exhibits a remarkable capacity retention of 85.7% after 500 cycles in 3.0–4.55 V. Furthermore, this work provides a new insight into developing advanced functional electrolytes for high-voltage lithium-ion batteries.

Co/O loss↗

Effect of Solvents on Lignin–Surface Interactions via Molecular Dynamics Simulations

Lignin, an essential building block of lignocellulosic biomass, is a potential abundant source of aromatic monomers for the polymer and chemical industry. Reductive catalytic fractionation (RCF) is one promising process that can produce high yields of phenolic monomers and oligomers from lignin under different catalytic conditions. An important choice in optimizing RCF is the selection of solvent; however, detailed insights into solvent effects on lignin behaviors and interactions remain limited. Here, in this work, we perform all-atom molecular dynamics simulations to study the solvation of lignin, solvent-mediated conformational changes, and the interaction of solvated lignin oligomers with model surfaces. We focus on the behavior of an oligomeric lignin model compound in methanol, ethanol, a binary mixture of ethanol and water, and water at both the RCF reaction temperature (473 K) and room temperature. Analysis of structural features of lignin suggests that these three organic solvent systems favorably solvate lignin, resulting in a more extended conformation suitable for catalytic conversion to valuable chemicals. We further introduce model palladium (Pd) and carbon (C) surfaces to understand how solvent choice impacts adsorption onto a representative catalytic surface and support, and to quantify the competition among the reactant and solvent molecules for the surface. Unbiased simulations suggest strong adsorption of lignin on both Pd and C surfaces at 473 K, with notable solvent-mediated differences in adsorption energies. Additionally, our findings indicate that lignin adsorption is promoted by the entropy change resulting from the displacement of solvent molecules from the surface. This study provides a molecular perspective of adsorption of lignin onto varying surfaces, which is a step towards understanding and optimizing the catalytic conversion of lignin into valuable chemicals.

adsorption↗

Data from : "Warming promotes loss of subsoil carbon through accelerated degradation of plant-derived organic matter". Blodgett warming experiment

This dataset contains data used for the paper: Warming promotes loss of subsoil carbon through accelerated degradation of plant-derived organic matter. Soil Biology and Biochemistry 156, 108185. doi:10.1016/j.soilbio.2021.108185On April 2018 (after 4.5 years of warming), we collected O-horizon (organic horizon) material and soil core down to 90 cm depth from a whole-soil warming experiment in a mixed-coniferous temperate forest, located at the University of California Blodgett experimental forest in the foothills of the Sierra Nevada, CA USA. The goal was to assess how 4.5 years of +4 °C whole-soil warming affected the quantity and quality of soil organic matter. Cores were collected from 6 experimental plots (three replicated blocks); samples were collected in 10 cm increments from 0 to 90 cm depth.This dataset contains a compressed (.zip) archive of the data used for this manuscript. The dataset includes files in .xlsx format, which can be accessed and processed using MS Excel or R. Carbon and nitrogen concentrations, as well as stable carbon isotope composition ((δ13C) and solvent extractable lipid biomarker (alkanoic acids and alkanes) data are provided as processed data files. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy data are provided as raw output and processed data files.The dataset files "Blodgett_warming_Data" and "Blodgett_warming_raw_data.xlsx" were updated on July 7, 2021. The following updates were made: (1) specification of the units of measurements in the dataset (the unit of measurement was missing in some parameters) and (2) the column name "pulled depth" was changed to "pooled depth" in the updated data files.

54 ENVIRONMENTAL SCIENCES↗

Advanced Sensors for In-Situ Amine Degradation Monitoring in Post-Combustion Carbon Capture

In order to improve the long-term performance of post-combustion carbon capture technologies, improvements to the detection of solvent degradation or reduction in CO2 capture efficiency are necessary. A pair of sensors were deployed to the National Carbon Capture Center’s (NCCC) to monitor CO2 capture and solvent degradation. The CO2 sensors were located to measure before capture and after capture concentrations of CO2 to measure the capture efficiency of the solvent system. Amine degradation sensors were located at four locations along the main solvent lines corresponding to CO2 loading and temperature: hot rich, cold rich, hot lean, and cold lean. Experimental results from laboratory tests using the sensors are shown, along with prototype designs that were deployed to the field site.

Brister, Matthew↗

Carbon Capture Design and Costing: Phase 2 (C3DC2) (Final Project Report)

ION Clean Energy’s (ION) advanced solvent is one of the leading solvent systems currently under development for post-combustion carbon dioxide (CO 2 ) capture. ION has partnered with Nebraska Power Public District (NPPD), Sargent & Lundy, Koch Modular Process Systems, and Siemens to design a commercial-scale (700 MW) capture system utilizing ION’s advanced solvent, ICE-21, retrofitted onto NPPD’s Gerald Gentleman Station in Sutherland, Nebraska, USA. The capture system was designed to take full advantage of the solvent benefits including an efficient physical plant layout, reduced energy requirements, less solvent degradation, lower emissions, and lower capital costs relative to systems built with DOE BBS case benchmark solvents. This Front-End Engineering Design (FEED) study also included an investigation of utilizing biomass co-combustion with the aim of reaching near-zero emissions for this coal-fired power generating unit. The targeted biomass was from local resources in Nebraska tied to the production of ethanol.

01 COAL, LIGNITE, AND PEAT↗

Ultrafast and Controllable Phase Evolution by Flash Joule Heating

Flash Joule heating (FJH), an advanced material synthesis technique, has been used for the production of high-quality carbon materials. Direct current discharge through the precursors by large capacitors has successfully converted carbon-based starting materials into bulk quantities of turbostratic graphene by the FJH process. However, the formation of other carbon allotropes, such as nanodiamonds and concentric carbon materials, as well as the covalent functionalization of different carbon allotropes by the FJH process, remains challenging. Here, we report the solvent-free FJH synthesis of three different fluorinated carbon allotropes: fluorinated nanodiamonds, fluorinated turbostratic graphene and fluorinated concentric carbon. This is done by millisecond flashing of organic fluorine compounds and fluoride precursors. Spectroscopic analysis confirms the modification of the electronic states and the existence of various short-range and long-range orders in the different fluorinated carbon allotropes. As a result, the flash time-dependent relationship is further demonstrated to control the phase evolution and product compositions.

01 COAL, LIGNITE, AND PEAT↗

ION Validation of Transformational CO2 Capture Solvent Technology with Revolutionary Stability: “Project Apollo”

This final report presents all the work and tests performed during ION’s carbon dioxide (CO2) capture pilot test campaign at the 0.6 MWe scale in the Pilot Solvent Test Unit (PSTU) at the National Carbon Capture Center (NCCC): “Validation of Transformational CO2 Capture Solvent Technology with Revolutionary Stability,” referred to as the “Apollo” Project (DE-FE0031727).

Meuleman, Erik↗

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Abstract Polyoxometalates (POMs, metals=V V , Nb V , Ta V , Mo VI , W VI ) are molecular metal oxides that can be isolated without capping ligands. The high negative charge of polyoxoniobates (PONb) provides strong interactions with heterocations, advantageous for electrostatic assembly of modular materials. In four single‐crystal X‐ray structures, we demonstrate that carbonate combined with the very reactive decaniobate [Nb 10 O 28 ] 6− reassembles into a new decaniobate, [Nb 10 O 25 (CO 3 ) 6 ] 12− , featuring three carbonate‐ligated Nb‐polyhedra. These Nb‐sites can be replaced by heterometals (lanthanides), and the tridentate carbonate can serve as an anchor point to build niobate‐frameworks. Small‐angle X‐ray scattering and two additional X‐ray structures reveal that the reaction pathway proceeds through a Nb 24 ‐PONb intermediate, and the obtained PONb (with or without carbonate) is counterion, temperature, and solvent‐dependent (water or mixed water‐methanol). This provides an uncommon level of control for PONb chemistry.

Amiri, Mehran↗

Decoding the Effect of Anion Identity on the Solubility of N -(2-(2-Methoxyethoxy)ethyl)phenothiazine (MEEPT)

Variations in the solubility of redox-active organic molecules (ROM) of interest for nonaqueous redox flow batteries (RFB), especially as the ROM state-of-charge changes during charge-discharge cycling, present significant molecular design challenges. The situation is further complicated as ROM solubility can be regulated by the choice of electrolyte salt and solvent that together with the ROM comprise the catholyte or anolyte (redox electrolyte) formulation, presenting materials design challenges. The ROM N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT) is a viscous liquid at room temperature and is miscible in several organic solvents, including acetonitrile and propylene carbonate. The MEEPT radical cation (MEEPT +· ) paired with tetrafluoroborate (BF 4 - ) in acetonitrile presents a 0.5 M solubility, a dramatic decrease when compared to the viscous liquid of neutral MEEPT. Here, in this study, we present a joint experimental, regression modeling, and molecular dynamics (MD) simulations investigation to explore MEEPT-X (where X represents the counteranion) salt solubility variability as a function of concentration and counteranion chemistry in acetonitrile. We find a strong dependence of the salt solubility on the counteranion and relate these findings to explicit intermolecular interactions between MEEPT +· and the counteranion in the electrolyte solution.

Perera, Anton S. [Univ. of Kentucky, Lexington, KY↗

Engineering-Scale Test of a Water-Lean Solvent for Post-Combustion Capture

EPRI, Pacific Northwest National Laboratory, RTI International, and their project collaborators developed an engineering-scale test of a new water-lean solvent, N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA or 2-EEMPA) as a post-combustion CO 2 capture solvent for power plant applications. This test was conducted using the Pilot Solvent Test Unit at the National Carbon Capture Center. The primary objective of this test was to collect long-term data operating EEMPA with both coal- and natural gas-representative flue gases at the approximately 0.5 MW e -equivalent scale (5–10 metric tons CO 2 /day captured). This report details the activities preparing for that test, data collected during the test campaign, and analyses and interpretations of that data.

20 FOSSIL-FUELED POWER PLANTS↗

Physics-informed machine learning to predict solvatochromic parameters of designer solvents with case studies in CO 2 and lignin dissolution

The polarity of solvents plays a critical role in various research applications, particularly in their solubilities. Polarity is conveniently characterized by the Kamlet-Taft parameters that is, the hydrogen bonding acidity (α), the basicity (β), and the polarizability (π*). Obtaining Kamlet-Taft parameters is very important for designer solvents, namely ionic liquids (ILs) and deep eutectic solvents (DESs). However, given the unlimited theoretical number of combinations of ionic pairs in ILs and hydrogen-bond donor/acceptor pairs in DESs, experimental determination of their Kamlet-Taft parameters is impractical. To address this, the present study developed two different machine learning (ML) algorithms to predict Kamlet-Taft parameters for designer solvents using quantum chemically derived input features. The ML models developed in the present study showed accurate predictions with high R 2 and low RMSE values. Further, in the context of present interest in the circular bioeconomy, the relationship between the basicities and acidities of designer solvents and their ability to dissolve lignin and carbon dioxide (CO 2 ) is discussed. Our method thus guides the design of effective solvents with optimal Kamlet-Taft parameter values dissolving and converting biomass and CO 2 into valuable chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating Polymer Properties with Different Additives for Carbon Capture and Other Applications

Anthropogenic climate change is one of this generation’s most pressing concerns, with the potential to completely alter the delicate balance we’ve struck with nature. Already, global temperatures have risen 1.29°C, leading to disrupted weather systems, extinctions, increased risks of wildfires, and sea level rise, to name a few effects. Carbon dioxide emission from the combustion of fossil fuels and other industrial activity is a large driver of this phenomenon, as it absorbs heat before it can be radiated away from Earth, trapping it. Carbon dioxide has reached unprecedented levels in our atmosphere, showing a 50% increase from preindustrial averages to a whopping 430 ppm. Thus, reducing the amount of carbon dioxide via carbon capture technology is an important endeavor that serves to benefit everyone. The Microencapsulated CO 2 Sorbent (MECS) team at Lawrence Livermore National Laboratory (LLNL) has turned to microencapsulation to approach this endeavor. Microcapsules provide an attractive approach to carbon capture, combining large surface areas for more efficient mass transfer, regenerative abilities, reduced solvent loss, and improved handling. Additionally, while existing carbon capture technology relies on industrial plants, capsules could present a modular approach to carbon capture, reducing the need for extensive physical infrastructure. The MECS team’s design consists of a polymer membrane that contains a liquid carbon sequestering sorbent, aqueous sodium carbonate. The carbon capturing reaction occurs in three distinct steps, the first of which is the dissolution of carbon dioxide into the sorbent solution and its conversion into carbonic acid (H 2 CO 3 ), shown in equations 1 and 2 respectively. Because this step hinges upon the ability of carbon dioxide to reach the solution inside the capsule, it is necessary that the microcapsule shell is permeable to carbon dioxide gas. The MECS team produces these microcapsules using the in-air droplet encapsulation apparatus (IDEA) shown in figure 1, which can produce uniform micron-scale droplets at speeds much faster than traditional single-dispersal microfluidic-based techniques. The IDEA Is 100 times faster than these current techniques and can reach up to 1000 times their speed when incorporating a multi-nozzle design. Additionally, because droplets are produced in-air via vibration, IDEA can decrease post-processing times and material waste by 99% and can fabricate microgels that are 10 to 100 times more viscous than can be produced via traditional microfluidics. While this design represents a breakthrough in the throughput, efficiency, and tunability of microcapsule production, it imposes a major constraint on the microcapsule curing process. Because microcapsule shells are crosslinked with UV light while falling 30 cm through the air, this gives them a reaction window of approximately 0.2 seconds. Thus, the system and shell formulations must be optimized such that the shells can be fully crosslinked within this very narrow window, prompting investigations into curing behavior.

36 MATERIALS SCIENCE↗

Jacobian-based Model Diagnostics and Application to Equation Oriented Modeling of a Carbon Capture System

Equation-oriented (EO) modeling has the potential to enable the effective design and optimization of the operation of advanced energy systems. However, advanced modeling of energy systems results in a large number of variables and non-linear equations, and it can be difficult to search through these to identify the culprit(s) responsible for convergence issues. The Institute for the Design of Advanced Energy Systems Integrated Platform (IDAES-IP) contains a tool to identify poorly scaled constraints and variables by searching for rows and columns of the Jacobian matrix with small L2-norms so they can be rescaled. A further singular value decomposition can be per-formed to identify degenerate sets of equations and remaining scaling issues. This work presents an EO model of a flowsheet developed for post-combustion carbon capture using a monoethanolamine (MEA) solvent system as a case study. The IDAES diagnostics tools were successfully applied to this flowsheet to identify problems to improve model robustness and enable the optimization of process design and operating conditions of a carbon capture system.

Allan, Douglas↗

Exploring the Unusual Reactivity of the Hydrated Electron with CO 2

Many questions remain about the reactions of the hydrated electron despite decades of study. Of particular note is the fact that they do not appear to follow the Marcus theory of electron transfer reactions, a feature that has yet to be explained. To investigate these issues, we use ab initio molecular dynamics (AIMD) simulations to investigate a one of the better studied reactions, the hydrated electron reduction of CO 2 . The rate constant for the hydrated electron-CO 2 reaction complex to react to form CO 2 - is, for the first time, estimated from AIMD simulations. Results at 298 and 373 K show the rate constant is insensitive to temperature, consistent with the low measured activation energy for the reaction, and the implications of this behavior are examined. The sampling provided by the simulations yields insight into the reaction mechanism. The reaction is found to involve both solvent reorganization and changes in the carbon dioxide structure. The latter lead to significant vibrational excitation of the bending and symmetric stretch vibrations in the CO 2 - product, indicating the reaction is vibrationally nonadiabatic. The former is estimated from calculation of an approximate collective solvent coordinate and the free energy in this coordinate is determined. Furthermore, these results indicate that AIMD simulations can reasonably estimate hydrated electron reaction activation energies and provide new insight into the mechanism that can help illuminate the features of this unusual chemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗