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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 109 records · Page 6

Long-term cyclability of Li 4 Ti 5 O 12 /LiMn 2 O 4 cells using carbonate-based electrolytes for behind-the-meter storage applications

Li 4 Ti 5 O 12 /LiMn 2 O 4 (LTO/LMO) chemistry was evaluated as a potential candidate for behind-the-meter storage (BTMS) applications. Its long-term cycle performance at 45 °C was tested using ethylene carbonate (EC) and propylene carbonate (PC) solvent electrolytes. Over 1000 cycles, LTO/LMO cells exhibited ~80% capacity retention and Coulombic efficiency higher than 99.96%. Electrochemical test results showed the major degradation mode of LTO/LMO cells arises from continuous electrolyte decomposition at the LTO anode and loss of Li inventory. EC and PC electrolytes created distinct surface layers, where the EC reduction products were more effective in passivating the LTO electrode surface. Dissolution and migration of Mn from the cathode was probed as Mn 2+ species distributed throughout the surface layer at the anode. By utilizing a prelithiated LTO electrode, the LTO/LMO cell performance was significantly enhanced with EC electrolyte. On the other hand, PC electrolyte resulted in accelerated electrolyte decomposition at the lithiated LTO surface due to the lack of surface passivation. Thus, mitigating parasitic reactions at the LTO electrode is the key to developing successful LTO/LMO cells.

25 ENERGY STORAGE↗

Structure–Transport Relationships of Water–Organic Solvent Co-transport in Carbon Molecular Sieve (CMS) Membranes

We explore the effects of the carbon molecular sieve (CMS) microstructure on the separation performance and transport mechanism of water–organic mixtures. Specifically, we utilize PIM-1 dense films and integrally skinned asymmetric hollow fiber membranes as polymer precursors for the CMS materials. The PIM-1 membranes were pyrolyzed under several different pyrolysis atmospheres (argon, carbon dioxide, and diluted hydrogen gas) and at multiple pyrolysis temperatures. Detailed gas physisorption measurements reveal that membranes pyrolyzed under 4% H 2 and CO 2 had broadened ultramicropore distributions (pore diameter <7 Å) compared to Ar pyrolysis, and pyrolysis under CO 2 increased ultramicropore volume and broadened micropore distributions at increased pyrolysis temperatures. Gravimetric water and p-xylene sorption and diffusion measurements reveal that the PIM-1-derived CMS materials are more hydrophilic than other CMS materials that have been previously studied, which leads to sorption-diffusion estimations showing water-selective permeation. Water permeation in the vapor phase, pervaporation, and liquid-phase hydraulic permeation reveal that the isobaric permeation modes (vapor permeation and pervaporation) are reasonably well predicted by the sorption-diffusion model, whereas the hydraulic permeation mode is significantly underpredicted (>250×). Conversely, the permeation of p-xylene is well predicted by the sorption-diffusion model in all cases. The collection of pore size analysis, vapor sorption and diffusion, and permeation in different modalities creates a picture of a combined transport mechanism in which water–under high transmembrane pressures–permeates via a Poiseuille-style mechanism, whereas p-xylene solutes in the mixture permeate via sorption-diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modular Adaptive Packing for Integrally Cooled Absorbers

Process intensification is one cornerstone in ION Clean Energy’s (ION) efforts to lowering CO2 capture cost. ION has modeled, designed, and fabricated an innovative gas-liquid contactor known as Modular Adaptive Packing (MAP). During two successful SBIR Phase I and II projects entitled: “Rapid Design and Testing of Novel Gas-Liquid Contacting Devices for Post-Combustion CO2 Capture via 3D-printing”, ION developed and proved this new technology at bench scale. MAP, a 3D-printed lattice-structured packing, combines the absorber gas/liquid contactor with an innovative in-situ heat-exchanger. Thanks to the capabilities of 3D-printing, the lattice structure of MAP contains hollow channels through which coolant water can be pumped to remove the heat of reaction from CO2 absorption. ION refers to this novel method of heat exchange as intracooling. After 25.4 cm (10 in) diameter MAP modules were fabricated, ION built and tested a packing characterization rig at its pilot facility in Boulder, Colorado, U.S.A. To provide baseline results for the characterization rig, ION tested Sulzer’s Mellapak™ 250Y (MP250Y) as a standard structured packing. ION’s MAP was then compared directly to the baseline MP250Y packing to evaluate key indicators including pressure drop, liquid hold-up, and effective area. MAP has a higher pressure drop than MP250Y at the same gas velocities in addition to greater liquid holdup. However, ION found that MAP displays a higher wetting coverage of 93% compared to 65% for MP250Y and reduces shearing forces that result in undesirable droplet formation. Using Optimized Gas Treating’s (OGT) rate-based simulation software ProTreat®, a conceptual evaluation of MAP was modeled for a CO2 absorber using 30 wt% MEA solvent over a range of lean loadings at 90% CO2 capture from a coal-fired power plant. ION modeled a 25-meter column absorber for both the standard MP250Y packing and a hybrid column. The hybrid absorber contained 10 m of MP250Y packing at the top and bottom with the middle 5 meters comprised of MAP. Compared to a traditional intercooled absorber, MAP can remove 22% more heat and increase overall MEA carrying capacity by 4% without increasing overall pressure drop.

20 FOSSIL-FUELED POWER PLANTS↗

Composite Solid Ion Conductor with Engineered Lithium Interface

Successful widespread commercialization of electric vehicles is contingent upon development of safe high energy density batteries capable of long cycle life. Lithium metal affords the highest theoretical capacity (3,860 mAh/g) and lowest electrochemical potential (-3.04V vs SHE), which offers the highest specific energy density of anode materials today. While Li-ion batteries are capable of delivering energy densities of 400-600 Wh/kg, the development of lithium metal batteries such as Li-S and Li-air may boost this number up to 650 and 950 Wh/kg, respectively. However, significant progress towards the passivation of lithium metal must occur before the energy density benefit can be realized. Issues with lithium dendrite formation, anode volume expansion, and continuous solid electrolyte interphase (SEI) build-up often result in significant safety concerns, high cell resistance, and poor cycle life. The intrinsic high reactivity between lithium metal with conventional lithium ion electrolytes (organic carbonate-based solvents) makes it extremely difficult to overcome these problems. In this project, Wildcat performed focused, fundamental research and development on composite polymer/ceramic electrolytes and protected lithium metal anodes to develop an all solid state lithium metal battery targeting the DOE requirements to enable commercialization. Wildcat successfully leveraged its high throughput battery platform and explored a broad composite electrolyte compositional space. Additionally, Wildcat screened large numbers of inorganic and organic coatings for lithium metal protection using in situ liquid methods and translated the best results to all solid cells. The proposed composite polymer/ceramic electrolyte and a protected lithium metal anode enabled a solid-state lithium metal battery. The ultimate targets from this effort will deliver a safe all solid-state lithium metal pouch cell with over 350 Wh/kg and over 1,000 cycles (C/3) with the cost estimate below $100/kWh. During the course of the project, we demonstrated stable cycling of 10’s of cycles with the composite SSE and our protected lithium. The work has continued after the conclusion of the DOE funding, demonstrating further improvements in catholyte composition and thinner composite solid electrolytes.

25 ENERGY STORAGE↗

Production of CO2-Negative Building Composites Development

This project will investigate and utilize the basicity and enhanced reactivity of CO2 chemically captured in PNNL’s CO2BOLs carbon capture solvents to perform the first direct carboxylation of the aromatic rings (substituted phenols) in lignin and lignite. This project aims to develop a deep decarbonization approach that can sequester millions of tonnes of CO2 annually by reacting with two large-volume products, lignin, and lignite, to enable their use as composite fillers. The goal is to demonstrate that CO2-containing composites have comparable properties to conventional synthetic materials, meeting international building codes (IBC) while being able to sequester millions of tonnes of CO2 per year.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent-Resistant, Thermally Stable Poly(Carbonate-Imides)

New polymers and copolymers based on polyimide backbone with carbonate moieties exhibit high temperature capability. Because of carbonate unit, many of these materials also exhibit high order or crystallinity. All of new imidecontaining polymers insensitive to acetone. New poly (carbonate-imide) exhibits significantly increased temperature resistance and shows less sensitivity to solvents than commercial polycarbonates.

St. Clair, T. L.↗

Effect of a Synchrotron X-ray Microtomography Imaging Experiment on the Amino Acid Content of a CM Chondrite

X-ray microcomputed tomography and synchrotron X-ray microcomputed tomography (μCT) are becoming popular tools for the reconnaissance imaging of chondrites. However, there are occasional concerns that the use of μCT may be detrimental to organic components of a chondrite. Soluble organic compounds represent ~2–10% of the total solvent extractable carbon in CI and CM carbonaceous chondrites and amino acids are among the most abundant compounds in the soluble organic fraction. We irradiated two samples of the Murchison CM2 carbonaceous chondrite under conditions slightly harsher (increased beam exposure time) than those typically used for x-ray μCT imaging experiments to determine if detectable changes in the amino acid abundance and distribution relative to a nonexposed control sample occurred. After subjecting two meteorite portions to ionizing radiation dosages of 1.1 kiloGray (kGy) and 1.2 kGy with 48.6 and 46.6 keV monochromatic X-rays, respectively, we analyzed the amino acid content of each sample. Within analytical errors, we found no differences in the amino acid abundances or enantiomeric ratios when comparing the control samples (nonexposed Murchison) and the irradiated samples. We show with calculations that any sample heating due to x-ray exposure is negligible. We conclude that a monochromatic synchrotron X-ray μCT experiment at beamline 13-BM-D of the Advanced Photon Source, which imparts ~1 kGy doses, has no detectable effect on the amino acid content of a carbonaceous chondrite. These results are important for the initial reconnaissance of returned samples from the OSIRIS-REx and Hayabusa 2 asteroid sample return missions.

Jon M. Friedrich↗

Molecular-Level Overhaul of y-Aminopropyl Aminosilicone/Triethylene Glycol Post-Combustion CO2-Capture Solvents

Capturing carbon dioxide (CO2) from post-combustion gas streams is an energy-intensive process that is required prior to either converting or sequestering CO2. There are a few commercial offerings of 1st and 2nd generation aqueous amine technologies, however the cost of capturing CO2 with these technologies remains high. To decrease costs of capture, researchers are designing efficient solvent systems with the goal of being drop-in replacements for 1st and 2nd generation infrastructure. One approach has seen the development of water-lean solvents that aim to increase efficiency by reducing the water content in solution. Water-lean solvents such as GE’s GAP/TEG are promising technologies, with potential to halve the parasitic load to a coal-fired power plant, only if the intrinsically high solution viscosities and hydrolysis of the siloxane moieties could be mitigated. We present here, an integrated multidisciplinary approach to overhaul the GAP/TEG solvent system at the molecular level to mitigate hydrolysis while also reducing viscosity. We present molecular-level insights into chemical speciation of CO2-containing ions, showing that co-solvents and diluents have a negligible effect on reducing viscosity and are not needed. This finding allowed for the design of singlecomponent siloxane-free diamine derivatives with site-specific incorporation of selective chemical moieties for direct placement and orientation of hydrogen bonding to reduce viscosity. Ultimately, we present new single-component diamine formulations less susceptible to hydrolysis that exhibit up to a 98% reduction in viscosity compared to the initial GAP/TEG formulation.

Cantu Cantu, David↗

Single-Step, Solvent-Free, Catalyst-Free Preparation of Holey Carbon Allotropes

Methods for forming holey carbon allotropes and graphene nanomeshes are provided by the various embodiments. The various embodiments may be applicable to a variety of carbon allotropes, such as graphene, graphene oxide, reduced graphene oxide, thermal exfoliated graphene, graphene nanoribbons, graphite, exfoliated graphite, expanded graphite, carbon nanotubes (e.g., single-walled carbon nanotubes, double-walled carbon nanotubes, few-walled carbon nanotubes, multi-walled carbon nanotubes, etc.), carbon nanofibers, carbon fibers, carbon black, amorphous carbon, fullerenes, etc. The methods may produce holey carbon allotropes without the use of solvents, catalysts, flammable gas, additional chemical agents, or electrolysis to produce the pores (e.g., holes, etc.) in the carbon allotropes. In an embodiment, a carbon allotrope may be heated at a working window temperature for a working period of time to create holes in the carbon allotrope.

Lin, Yi↗

Development and Bench-Scale Testing of a Novel Biphasic Solvent-Enabled Absorption Process for Post-Combustion Carbon Capture (Final Technical Report)

A new class of biphasic solvents was developed, and the concept of the enabled carbon dioxide (CO 2 ) absorption process was tested for post-combustion carbon capture in our previous lab-scale research. The primary goals of this project were to advance the development of the novel biphasic CO 2 absorption process (BiCAP) and validate its technical advantages by testing the integrated technology at a 40 kWe bench-scale with actual coal-derived flue gas in a power plant environment. The project was led by the University of Illinois at Urban-Champaign (UIUC), and Trimeric Corporation served as a sub-awardee providing support in basic design and techno-economic studies. To achieve the project goals and objectives, solvent management studies, process modeling and optimization, bench-scale equipment design, construction and testing, and technical, economic and environmental assessments have been conducted. The two top-performing biphasic solvents developed in our previous research were used in this project. Biphasic solvent emissions and control were investigated in the laboratory. The emissions of the biphasic solvents from the absorber were comparable to or lower than the reference 30 wt% monoethanolamine (MEA) solution, while they could be more effectively removed in the water wash column. Lab-scale testing of solvent degradation reclamation has revealed that vacuum distillation was feasible for biphasic solvent reclamation. Aspen Plus models were used to optimize the BiCAP, and a CO 2 stripping configuration introducing a secondary cold solvent feed to the stripper was identified to be the most energy efficient. A 40 kWe bench-scale, integrated BiCAP system was successfully designed, fabricated, and installed at the UIUC’s Abbott Power Plant. Parametric testing with synthetic flue gas has demonstrated that the two biphasic solvents required a more than 40% lower heat duty for CO 2 desorption as compared to the reference MEA tested on the same bench-scale skid. Slipstream testing with actual coal flue gas for a total of 31 days in two test campaigns has further demonstrated stable operation of the bench-scale skid. During the first campaign targeting 90% CO 2 removal, the heat duty averaged at 2,183 MJ/tonne of CO 2 captured and during the second campaign targeting 95% removal, the heat duty averaged at 2,450 MJ/tonne of CO 2 captured. A techno-economic analysis has revealed that for integration of the BiCAP into a 650-MWe pulverized coal-fired power plant, the parasitic power loss was reduced by ~20%, and the cost of CO 2 capture was reduced by ~21% ($36.3/tonne on a December 2018 dollar basis) compared to the U.S. Department of Energy (DOE)’s baseline Case B12B. As progression from this bench-scale development effort, a new project “Engineering-Scale Testing of the Biphasic Solvent Based CO 2 Absorption Capture Technology at a Covanta Waste-to-Energy Facility” was awarded by the DOE, launched in February 2023, to allow the team to further test the technology and demonstrate its technical and economic advantages at a pilot scale.

20 FOSSIL-FUELED POWER PLANTS↗

Modeling, Design, and Testing of a Novel Biphasic Solvent-Enabled Absorption System for Post-Combustion Carbon Capture

A novel absorption process enabled by a new class of biphasic solvents for post-combustion carbon capture (BiCAP) is presently being developed at the University of Illinois at Urbana-Champaign. The new biphasic solvents are water-lean solvent blends that develop dual liquid phases with the absorbed CO2 highly enriched in one of the phases. These solvents are superior in CO2 capacity and have high thermal and oxidative stability compared to MEA. The BiCAP technology features a unique process configuration of multi-stage CO2 absorption and liquid–liquid phase separation during CO2 absorption, allowing continual separation and removal of the CO2-enriched liquid phase for maintaining low solvent viscosity and a fast absorption rate. A 40 kWe-scale skid has recently been constructed at the Abbott Power Plant in Champaign, IL, to test the BiCAP solvent in continuous operation with a slipstream of real post-combustion flue gas. Along with improvements in the stripping configuration including cold feed bypass, the process is expected to achieve a minimum reboiler duty of 2,210 kJ/kg CO2 captured at a stripper operating pressure of 6 bar.

20 FOSSIL-FUELED POWER PLANTS↗

Structure–performance relationships of lithium-ion battery cathodes revealed by contrast-variation small-angle neutron scattering

Lithium-ion battery cathodes are porous composites of active material, conductive carbon, and polymer binder. Controlling the cathode microstructure is key to achieving high energy density and cycling stability. Current characterization techniques lack the nanoscale resolution over representative volumes necessary to relate cathode microstructure to cycling performance. To address this challenge, we utilize contrast-variation small-angle neutron scattering to quantify the chemical and structural features of cathodes wet by dimethyl carbonate, representing a relevant solvent environment. Using neutron scattering measurements, we identify an expansion in carbon and polymer structures that arises after calendering and wetting with solvent. Further, we deconvolute the carbon and binder phases to obtain the solvent-accessible carbon black surface area, which we correlate to diminished capacity retention driven by electrolyte decomposition on exposed carbon. This technique provides nanoscale insight into composite cathode microstructures and resulting cycling performance, promising future applications to a broad range of porous materials that exist in energy storage systems.

25 ENERGY STORAGE↗