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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 73 records · Page 4

In-situ thermophysical measurement of flowing molten chloride salt using modulated photothermal radiometry

Molten salts are leading candidates for high-temperature heat transfer fluids (HTFs) for thermal energy storage and conversion systems in concentrated solar power (CSP) and nuclear energy power plants. The ability to probe molten salt thermal transport properties in both stationary and flowing status is important for the evaluation of their heat transfer performance under realistic operational conditions, including the temperature range and potential degradation due to corrosion and contamination. However, accurate thermal transport properties are usually challenging to obtain even for stagnant molten salts due to different sources of errors from convection, radiation, and corrosion, let alone at flowing status. To the best of authors’ knowledge, there is no available in-situ technique for measuring flowing molten salt thermal conductivity. Here, we report the first in-situ flowing molten salt thermal conductivity measurement using modulated photothermal radiometry (MPR). We could successfully perform the first in-situ thermal conductivity measurement of flowing molten NaCl-KCl-MgCl 2 in the typical operating temperature (520 and 580 °C) with flow velocities ranging from around 0.3 to 1.0 m s -1 . The relative change of the molten salt thermal conductivity was measured. Gnielinski’s correlation was also used to estimate the heat transfer coefficient h of the flowing NaCl-KCl-MgCl 2 in the given experimental condition. Furthermore, the work showed the potential of the MPR technique serving as an in-situ diagnostics tool to evaluate the heat transfer performance of flowing molten salts and other high-temperature HTFs.

14 SOLAR ENERGY↗

Watching Polarons Move in the Energy and Frequency Domains Using Color Impedance Spectroscopy

The hybrid electronic–ionic transport property of π-conjugated polymers enables new (opto)electrochemical device constructs for energy conversion and storage and biosensing applications. One major challenge is separating the energy and frequency dependence of Faradaic events–those involving charge transfer and the redox processes of the conjugated backbone–from the non-Faradaic components, such as ionic motion. Herein, we combine optical spectroscopy with electrochemical impedance spectroscopy (EIS) to resolve the frequency response of ionic–electronic coupling as a function of electrochemical doping potential. First, using EIS, we identify two different frequency regimes resulting in potential-dependent capacitive elements on the order of ~10 μF/cm 2 in a high-frequency regime and ~50–150 μF/cm 2 in a low-frequency regime. Given the larger magnitude and greater potential dependence, we posit that polaronic motion is more likely to occur at low frequencies (<1 kHz) and overlaps with ionic motion. The use of color impedance spectroscopy (CIS) enables observation of polaronic motion with frequency modulation. We observe that higher doping potentials show a greater motion of polarons above the DC-bias baseline concentration for onset in electrochemical doping, but all potentials considered demonstrate a critical frequency at which the polaronic motion is “frozen” (~40 Hz). Furthermore, this critical information obtained from CIS in highly dielectric environments offers a unique figure of merit for future studies on electronic–ionic coupling by which to compare across polymer/electrolyte interfaces, including the role of a charge-supporting electrolyte, a solvent, and alternative Faradaic processes (e.g., electrocatalysis).

36 MATERIALS SCIENCE↗

Functional Photoresists for Energy Applications. Final Report

Monolithic ultralow-density porous bulk materials have recently attracted much interest due to many emerging applications in the areas of catalysis, energy storage and conversion, and thermal insulation. They are also important components of high energy density (HED) and inertial confinement fusion (ICF) targets. However, despite tremendous progress that has been made in the synthesis of porous materials, deterministic and independent control over microscopic architecture, density and composition remain key issues, and their integration in high precision devices requires cost and time-intensive mechanical machining that not only reduces reproducibility by generating debris but also limits the complexity of the 3D shapes that can be realized. In this project, we overcame these limitations by developing a universal templating capability that provides deterministic and independent control over density, composition, architecture, and macroscopic sample shape. This was achieved by developing the technology to 1) 3D print ultrahigh resolution, ultra-high precision polymeric micro-lattice templates, 2) coat these templates with the desired materials, and 3) removing the template (Fig. 1a). Atomic layer deposition (ALD) provides the atomic scale coating thickness accuracy required for precisely controlling density. While this templating approach had been demonstrated in prior work, limitations in suitable photoresists, 3D print technologies, print design, and template removal techniques did not allow the fabrication of millimeter-sized high-precision parts with sub-micron resolution. To enable this technology, we developed 1) two-photon polymerization (TPP) print designs that enable the fabrication of millimeter-sized, mechanically robust polymeric templates with sub-micron resolution and 2) a continuum level TPP printing simulation capability for additional print design guidance; 3) atomistic models to study photoresist polymerization kinetics and network topography, 4) refractive index matched polymeric and preceramic TPP photoresists, and 5) functional TPP photoresists including porous voxel structures and self-immolative polymer photoresist chemistries; and 6) damage free template removal techniques that enable the fabrication of defect-free high-precision low-density foam components. We also developed a templating approach for pure carbon microlattices with a unique tube-in-tube ligament morphology. As a test platform, we pursued the fabrication of foam liners that promise to further increase the neutron yield in indirect drive ICF experiments by improving implosion symmetry control and coupling between the laser and the deuterium-tritium fuel. This application requires fabrication and integration of a ultra-high precision, millimeter-sized, thin-walled (200-400 micrometer thick), low-density (10-30 mg/cc), high atomic number (high Z) cylindrical foam tube into the gold hohlraum of an indirect drive ICF target (Fig. 1b). While our hohlraum liner test case will mainly find application in HED and ICF experiments, the underlying science will also directly apply to previously developed nanoparticle and additive manufacturing technologies and will advance those techniques as well.

36 MATERIALS SCIENCE↗

Revisiting the Role of Mobile Ion Size for the Activation Barrier of Charge Transport in Single Ion Conducting Polymers

The development of polymer electrolytes for energy storage and conversion technologies requires a fundamental understanding of the material parameters controlling the energy barriers for ion transport. In glassy polymers, these activation barriers are usually extracted by using Arrhenius procedures. However, our recent studies of single ion conducting polymers reveal that this traditional Arrhenius description provides anomalously small prefactors, an issue that is widely disregarded in the literature. Here, to address it, an alternative approach was introduced for extracting the effective activation barrier E by imposing a physically valid limit (∼10 –13 s) for the ion hopping attempt time. Two consequences of this recent approach are that in polymer electrolytes (i) E is significantly (∼30–40%) lower than the barrier estimated using traditional Arrhenius fits and (ii) E displays significant temperature dependence even in the glassy state. Under these circumstances, we are revisiting the role of ion size, glass transition temperature T g , and dielectric and elastic constants of the polymer matrix on the effective activation barriers for ion transport as extracted using the recently proposed approach and highlight the differences from the picture that previously emerged based on simplistic apparent Arrhenius analysis. To this end, we investigate cation transport in three families of single ion conducting trifluoromethane sulfonimide-based polyanions with varied T g . Our results indicate that E decreases with mobile cation size and is highly sensitive to changes in the dielectric permittivity of the matrix, even for large cations. These insights call for revisions of many earlier results based on apparent Arrhenius fits as the proposed approach can provide more accurate guidance for the design of polymer electrolytes with enhanced ionic conductivity.

energy barrier↗

Hydrogen storage in complex hydrides: past activities and new trends

Abstract Intense literature and research efforts have focussed on the exploration of complex hydrides for energy storage applications over the past decades. A focus was dedicated to the determination of their thermodynamic and hydrogen storage properties, due to their high gravimetric and volumetric hydrogen storage capacities, but their application has been limited because of harsh working conditions for reversible hydrogen release and uptake. The present review aims at appraising the recent advances on different complex hydride systems, coming from the proficient collaborative activities in the past years from the research groups led by the experts of the Task 40 ‘Energy Storage and Conversion Based on Hydrogen’ of the Hydrogen Technology Collaboration Programme of the International Energy Agency. An overview of materials design, synthesis, tailoring and modelling approaches, hydrogen release and uptake mechanisms and thermodynamic aspects are reviewed to define new trends and suggest new possible applications for these highly tuneable materials.

Dematteis, Erika Michela (ORCID:0000000236804196)↗

Atomic layer deposition of sodium fluoride thin films

The need for advanced energy conversion and storage devices remains a critical challenge amid the growing worldwide demand for renewable energy. Metal fluoride thin films are of great interest for applications in lithium-ion and emerging rechargeable battery technologies, particularly for enhancing the stability of the electrode-electrolyte interface and thereby extending battery cyclability and lifetime. Reported within, sodium fluoride (NaF) thin films were synthesized via atomic layer deposition. NaF growth experiments were carried out at reactor temperatures between 175 and 250 °C using sodium tert-butoxide and HF-pyridine solution. Here, the optimal deposition temperature range was 175–200 °C, and the resulting NaF films exhibited low roughness (R q ≈ 1.6 nm for films of ~8.5 nm), nearly stoichiometric composition (Na:F = 1:1.05) and a growth per cycle value of 0.85 Å/cycle on SiO 2 substrates. These results are encouraging for future applications of NaF thin films in the development of improved energy capture and storage technologies.

25 ENERGY STORAGE↗

Advanced Electrocatalysis for Energy and Environmental Sustainability via Water and Nitrogen Reactions

Abstract Clean and efficient energy storage and conversion via sustainable water and nitrogen reactions have attracted substantial attention to address the energy and environmental issues due to the overwhelming use of fossil fuels. These electrochemical reactions are crucial for desirable clean energy technologies, including advanced water electrolyzers, hydrogen fuel cells, and ammonia electrosynthesis and utilization. Their sluggish reaction kinetics lead to inefficient energy conversion. Innovative electrocatalysis, i.e., catalysis at the interface between the electrode and electrolyte to facilitate charge transfer and mass transport, plays a vital role in boosting energy conversion efficiency and providing sufficient performance and durability for these energy technologies. Herein, a comprehensive review on recent progress, achievements, and remaining challenges for these electrocatalysis processes related to water (i.e., oxygen evolution reaction, OER, and oxygen reduction reaction, ORR) and nitrogen (i.e., nitrogen reduction reaction, NRR, for ammonia synthesis and ammonia oxidation reaction, AOR, for energy utilization) is provided. Catalysts, electrolytes, and interfaces between the two within electrodes for these electrocatalysis processes are discussed. The primary emphasis is device performance of OER‐related proton exchange membrane (PEM) electrolyzers, ORR‐related PEM fuel cells, NRR‐driven ammonia electrosynthesis from water and nitrogen, and AOR‐related direct ammonia fuel cells.

Li, Yi↗

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE↗

Utilizing Conjugated Imine Polymers to Stabilize Nanoparticle Silicon Anodes

Silicon anodes provide a compelling route towards delivering high-capacity lithium-ion batteries, however they are notoriously difficult to stabilize in conventional liquid electrolytes that are compatible with high performance cathodes. Furthermore, the drastic changes in volume that occur as silicon is lithiated and delithiated can lead to rapid cell failure and novel polymeric binders are known to help mitigate mechanical issues. We have recently developed a novel method to synthesize the conjugated polymer phenylmethylimine (polyPMI) using an imine metathesis reaction. We have demonstrated that this polymer can be used to stabilize silicon nanoparticles to produce a composite lithium-ion battery anode that is electrochemically stable for hundreds of lithiation and delithiation cycles with a Coulombic efficiency that is greater than 99.95% in a traditional carbonate liquid electrolyte. This work covers the structure and properties of polyPMI within the context of the unique mechanical and electrochemical requirements of nanoparticle silicon anodes. The electrochemical behavior of this polymer also offers new opportunities as an organic lithium-coordinating material that can be used to stabilize a variety of other battery electrodes. More broadly, we posit that this solution-processed, ionically conductive, and electronically conductive polymer is applicable for a variety of energy storage and conversion technologies. Finally, this work demonstrates how this novel polymer chemistry provides additional opportunities for tuning electrode architecture to target high energy full cells.

conjugated polymers↗

A High Potential, Low Capacity Fade Rate Iron Complex Posolyte for Aqueous Organic Flow Batteries

An iron complex, tris(4,4'-bis(hydroxymethyl)-2,2'-bipyridine) iron dichloride is reported, which operates at near-neutral pH with a redox potential of 0.985 V versus SHE. This high potential compound is employed in the posolyte of an aqueous flow battery, paired with bis(3-trimethylammonio)propyl viologen tetrachloride in the negolyte, exhibiting an open-circuit voltage of 1.3 V at near-neutral pH. It demonstrates excellent cycling performance with a low temporal capacity fade rate of 0.07% per day over 35 days of cycling. The extended cycling lifetime is the result of low permeability and improved structural stability of the newly developed iron complex compared to that of the iron tris(bipyridine) complex. The combination of high redox potential and low capacity fade rate compares favorably with those of all previously demonstrated organic and organometallic aqueous posolytes. Extensive investigation into the possible degradation mechanisms, including post-mortem chemical and electrochemical analyses, indicates that stepwise ligand dissociations of the iron complex are responsible for the reported capacity loss during cell cycling. Further, this investigation provides unprecedented insight to guide further improvements of such metalorganic compounds for energy storage and conversion applications.

25 ENERGY STORAGE↗

Mixed Enthalpy–Entropy Descriptor for the Rational Design of Synthesizable High-Entropy Materials Over Vast Chemical Spaces

The practically unlimited high-dimensional composition space of high-entropy materials (HEMs) has emerged as an exciting platform for functional material design and discovery. However, the identification of stable and synthesizable HEMs and robust design rules remains a daunting challenge. Here, we propose a mixed enthalpy–entropy descriptor (MEED) that enables highly efficient, robust, high-throughput prediction of synthesizable HEMs across vast chemical spaces from first-principles. The MEED is based on two parameters: the relative formation enthalpy with respect to the most stable competing compound and the spread of the point-defect formation energy spectrum. The former measures the relative synthesizability of an HEM to its most stable competing phase, going beyond the conventional thermodynamic understanding. Further, the latter gauges the relative entropy forming ability of an HEM, entailing no sampling over numerous alloy configurations. By applying the MEED to two structurally distinct representative material systems (i.e., 3D rocksalt carbides and 2D layered sulfides), we not only successfully identify all experimentally reported HEMs within these systems but also reveal a cutoff criterion for assessing their relative synthesizability within each system. By the MEED, tens of new high-entropy carbides and 2D high-entropy sulfides are also predicted, which have the potential for a wide variety of applications such as coating in aerospace devices, energy conversion and storage, and flexible electronics.

36 MATERIALS SCIENCE↗

Jianlin Li: Accelerating battery manufacturing and recycling

With continued penetration of consumer electronics and electric vehicles into the evergrowing marketplace, there is a critical need for an efficient and sustainable battery supply chain. This includes the production of raw materials, the design, development, and processing of cell materials and systems, and end-of-life product recycling. The Oak Ridge National Laboratory (ORNL) has established a research program dedicated to addressing many aspects of these key challenges. Here, we asked Jianlin Li, a Senior R&D Staff and leader of the Energy Storage and Conversion Manufacturing Group, his opinion on the role of chemistry and materials science in mitigating the impacts of critical materials in battery supply chains.

25 ENERGY STORAGE↗

Quaternized Polynorbornene Random Copolymers for Fuel Cell Devices

Quaternized polymers are critical components for various energy devices. Vinyl-addition polynorbornenes provide high mechanical strength, high ion conductivity, and chemical stability in a wide range of pH environments due to the all-C–C bond backbone. In this paper, we present the synthesis of a series of quaternized polynorbornene random copolymers via vinyl addition polymerization and elucidate the impact of polymer composition on their properties. The quaternary ammonium alkyl tether length and the ratio of n-hexylnorbornene to unsubstituted norbornene are systemically tailored. A copolymer of 5-(3-bromopropyl)-2-norbornene and norbornene with pendant trimethylammonium groups achieved hydroxide conductivity of 109 mS/cm at 80 °C with a modest water uptake of 72%. The addition of n-hexylnorbornene to the copolymer, to make a terpolymer, allows for the polymer composition to be tailored for properties, including a decrease in water uptake and higher processability, despite a slightly decreased hydroxide conductivity. Moreover, the developed membranes are chemically robust and highly mechanically stable, enabling thin membranes to be easily fabricated. This study provides insight into important design parameters for quaternized polynorbornenes for a variety of energy storage and conversion devices, especially fuel cells.

25 ENERGY STORAGE↗

Channeling Engineering of Hydroxide Ion Exchange Polymers and Reinforced Membranes

In this project, a team of researchers from Rensselaer Polytechnic Institute developed high performance alkaline conductors which can improve efficiency and lower cost of energy storage and conversion technology. The Rensselaer Polytechnic Institute team has developed a highly ion conductive, chemically stable, and mechanically durable alkaline membrane materials. Such membranes will serve as a critical component in electrochemical devices when energy was generated from renewable sources (e.g., sun and wind) or hydrogen fuel. The use of alkaline membrane in electrochemical reactions allows to replace expensive platinum catalyst to less expensive, earth abundant metals as catalysts, offering huge economic advantages in renewable energy technology.

08 HYDROGEN↗

Cyclic Olefin Copolymer based Alkaline Exchange Polymers and Reinforced Membranes

In this project, a team of researchers from Rensselaer Polytechnic Institute developed high performance, low-cost alkaline conductors which can improve efficiency and lower cost of energy storage and conversion technology. The Rensselaer Polytechnic Institute team has developed a highly ion conductive, chemically stable, and mechanically durable alkaline membrane materials. Such membranes will serve as a critical component in electrochemical devices when energy is generated from renewable sources (e.g., sun and wind) or hydrogen fuel. The use of alkaline membrane in electrochemical reactions allows us to replace expensive platinum catalysts with less expensive, earth abundant metals as catalysts, offering huge economic advantages in renewable energy technology.

30 DIRECT ENERGY CONVERSION↗