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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Molecular and morphological characterization of midblock-sulfonated styrenic triblock copolymers

Midblock-sulfonated triblock copolymers afford a desirable opportunity to generate network-forming amphiphilic materials that are suitable for use in a wide range of emerging technologies as fuel-cell, water-desalination, ion-exchange, photovoltaic, or electroactive membranes. Employing a previously reported synthetic strategy wherein poly( p - tert -butylstyrene) remains unreactive, we have selectively sulfonated the styrenic midblock of a poly( p - tert -butylstyrene- b -styrene- b - p - tert - butylstyrene) (TST) triblock copolymer to different extents. Comparison of the resulting sulfonated copolymers with results from our prior study provides favorable quantitative agreement and suggests that a shortened reaction time is advantageous. An ongoing challenge regarding the morphological development of charged block copolymers is the competition between microphase separation of the incompatible blocks and physical cross-linking of ionic clusters, with the latter often hindering the former. Here, we expose the sulfonated TST copolymers to solvent-vapor annealing to promote nanostructural refinement. Furthermore, the effect of such annealing on morphological characteristics, as well as on molecular free volume, is explored.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Electrochemistry of Thin Films with In Situ/Operando Grazing Incidence X-Ray Scattering: Bypassing Electrolyte Scattering for High Fidelity Time Resolved Studies

Electroactive polymer thin films undergo repeated reversible structural change during operation in electrochemical applications. While synchrotron X-ray scattering is powerful for the characterization of stand-alone and ex situ organic thin films, in situ/operando structural characterization has been underutilized-in large part due to complications arising from supporting electrolyte scattering. This has greatly hampered the development of application relevant structure property relationships. Therefore, a new methodology for in situ/operando X-ray characterization that separates the incident and scattered X-ray beam path from the electrolyte is developed. As a proof of concept, the operando structural characterization of weakly-scattering, organic mixed conducting thin films in an aqueous electrolyte environment is demonstrated, accessing previously unexplored changes in the $\pi-\pi$ peak and diffuse scatter, while capturing the solvent swollen thin film structure which is inaccessible in previous ex situ studies. These in situ/operando measurements improve the sensitivity to structural changes, capturing minute changes not possible ex situ, and have multimodal potential such as combined Raman measurements that also serve to validate the true in situ/operando conditions of the cell. Finally, new directions enabled by this in situ/operando cell design are examined and state of the art measurements are compared.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Recent Developments and Trends in Redox Flow Batteries

Stationary energy storage systems are needed to facilitate the widespread integration of intermittent renewable electricity generators, such as solar photovoltaic and wind turbines, and to improve the energy efficiency of the electrical grid. While no single technology can meet all needs, redox flow batteries (RFBs) have shown a favorable balance of cost, safety, and performance for many high-value applications. RFBs are rechargeable electrochemical devices that utilize the reversible redox reactions of two soluble electroactive species for energy storage. A compelling feature of the RFB configuration is the independent scaling of power and energy which enables cost-effective implementation of electrochemical couples with low energy density. Aqueous RFBs have been the subject of the vast majority of research efforts to date, which have yielded industry-level demonstrations. By comparison, non-aqueous RFBs are still in their infancy but have the potential for high energy density due to the extended stability window of non-aqueous electrolytes and the enriched selection of redox materials due to the broad variety of organic solvents. This chapter aims to introduce emerging, potentially transformative, strategies for enhancing RFB technologies through molecular design, electrolyte development, and cell-level engineering. Detailed discussions focus on recent developments in redox active materials (inorganic – aqueous, organic – aqueous, inorganic – non-aqueous, and organic – non-aqueous) and in system design (interdigitated flow fields, semi-solid flow cells, and hybrid flow cells). Future research directions and key challenges for RFB technologies are also highlighted.

Su, Liang↗
DOE OSTI2018

Yttria-Stabilized Zirconia Aided Electrochemical Investigation on Ferric Ions in Mixed Molten Calcium and Sodium Chlorides

Electrolytic reduction of dissolved iron oxide to metal iron in molten salts with an inert anode is an alternative short route for steelmaking without CO{sub 2} emissions. A novel and simple integrated yttria-stabilized zirconia (YSZ) cell was constructed from a YSZ tube with a closed end. The YSZ tube played multiple functions, including the container for the molten salts, the solid electrolyte membrane in the O{sup 2−}|YSZ|Pt|O{sub 2} (air) reference electrode (RE), and the solid electrolyte membrane between the working and counter electrodes (WE and CE). Electrochemical behavior of ferric ions (Fe{sup 3+}) that were formed by dissolution of 0.5 wt pct Fe{sub 2}O{sub 3} in the molten CaCl{sub 2}-NaCl eutectic mixture was investigated on a Pt WE at 1273 K by various electrochemical techniques including cyclic voltammetry, linear scan voltammetry, square wave voltammetry, chronopotentiometry, chronoamperometry, and potentiostatic electrolysis. Analysis of the mechanism of electrode reactions was further assisted by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. Some electrochemical parameters were obtained, including the number of exchanged electrons and the diffusion coefficient of ferric ions in the mixed molten salts. The results from various electrochemical techniques are in good agreement with each other, and show that the electrochemical reduction of Fe{sup 3+} to Fe in the molten salt mixture could be a single three-electron transfer step and diffusion-controlled reaction that was also possibly reversible. This work may form the foundation for extraction of iron and alloys from molten salts and also provide a stable O{sup 2−}|YSZ|Pt|O{sub 2} (air) RE with wide applicability for investigation on electrochemical properties of other electroactive metal oxides in molten salts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

MOF-Transformed In 2 O 3-x @C Nanocorn Electrocatalyst for Efficient CO 2 Reduction to HCOOH

For electrochemical CO 2 reduction to HCOOH, an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density (J HCOOH ) at a low overpotential. Indium oxide is good HCOOH production catalyst but with low conductivity. In this work, we report a unique corn design of In 2 O 3-x @C nanocatalyst, wherein In 2 O 3-x nanocube as the fine grains dispersed uniformly on the carbon nanorod cob, resulting in the enhanced conductivity. Excellent performance is achieved with 84% Faradaic efficiency (FE) and 11 mA cm –2 J HCOOH at a low potential of – 0.4 V versus RHE. At the current density of 100 mA cm –2 , the applied potential remained stable for more than 120 h with the FE above 90%. Density functional theory calculations reveal that the abundant oxygen vacancy in In 2 O 3-x has exposed more In 3+ sites with activated electroactivity, which facilitates the formation of HCOO* intermediate. Operando X-ray absorption spectroscopy also confirms In 3+ as the active site and the key intermediate of HCOO* during the process of CO 2 reduction to HCOOH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Manipulating cobalt oxide on N-doped aligned electrospun carbon nanofibers towards instant electrochemical detection of dopamine secreted by living cells

A demand exists for the development of miniaturized biosensors with high sensitivity and a wide dynamic range for rapid detecting dopamine (DA) levels. Here, an electrochemical sensor is created by decorating closely packed cobalt oxide (Co 3 O 4 ) nanograins on nitrogen-doped electrospun carbon nanofibers (NECNFs) via a facile electrodeposition method. The carbon nanofiber matrix provides both a scaffold with ultrahigh surface area for homogeneous dispersion of cobalt oxide nanostructures and facilitates the electrochemical conductivity for the hybrid electrode. The sensing principle is based on the redox reaction between DA and DA quinone that generates electrical signal, which is detectable via differential pulse voltammetry (DPV) and chronoamperometry (CA). Owing to a high electroactive surface area and facilitating electron transfer between electrode surface and the target molecule, the electrical sensing platform exhibits superior sensitivity and selectivity toward DA, with an excellent limit of detection (9 nM) over a wide range of concentrations (0.01 to 100 μM). Moreover, based on its excellent sensing properties and biocompatibility, the sensor has been used for the real-time monitoring exogeneous DA released from pheochromocytoma (PC12) cells. This work demonstrates promise of a novel sensor technology that may render rapid point-of-care testing of DA towards early clinical diagnosis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Effect of fed-batch vs. continuous mode of operation on microbial fuel cell performance treating biorefinery wastewater

Bioelectrochemical systems have been shown to treat low-value biorefinery streams while recovering energy, however, low current densities and anode conversion efficiencies (ACE) limit their application. A bioanode was developed via enrichment of electroactive biofilm under fed-batch and continuous feeding conditions using corn stover-derived waste stream. The continuously-fed MFC exhibited a current density of 5.8±0.06 A/m 2 and an ACE of 39%±4. The fed-batch MFC achieved a similar current density and an ACE of 19.2%, however, its performance dropped after 36 days of operation to 1.1 A/m 2 and 0.5%, respectively. In comparison, the ACE of the continuously-fed MFC remained stable achieving an ACE of 30% ± 3 after 48 days of operation. An MFC treating a biorefinery stream post fuel separation achieved a current density of 10.7±0.1 A/m 2 and an ACE of 57% ± 9 at an organic loading of 12.5 g COD/L-day. Characterization of the microbial communities indicate higher abundance of Firmicutes and Proteobacteria and lower abundance of Bacteriodetes and a higher level of Geobacter spp. (1.4% vs. 0.2%) in continuously-fed MFC vs. fed-batch MFC. Finally, the results demonstrate that limiting substrate to the equivalent maximum current that the anode can generate, maintains MFC performance over a long term for high strength wastewaters, such as those generated in the biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2020

Keratin-derived functional carbon with superior charge storage and transport for high-performance supercapacitors

In this work, we report a scalable method to synthesize hierarchically porous, hetero-atom doped activated carbon nanosheet from waste biomass-human hair, and demonstrates the use of this carbon as an ultra-high performance electrode material for supercapacitor applications. Microscopic analyses reveal that sheet size ranges from 50 to 200 nm having a thickness of 15–27 nm. As-synthesized, carbon nanosheets possess a hierarchical porous structure having a specific surface area of 1548 m 2 g -1 . Heteroatom concentration (nitrogen, oxygen, and sulfur) of around 25% is confirmed from XPS analysis. Therefore, the novel interconnected hierarchical porous nanosheets structure enables fast adsorption and transportation of ions during electrochemical processes. Also, the abundant chemically available electroactive heteroatom species in the material enhance the wettability of ions and contribute to pseudocapacitance. The electrochemical analyses through cyclic voltammetry and galvanostatic charge-discharge measurements in 6 M KOH reveal the quasi-EDLC behavior of the activated carbons due to the presence of heteroatoms. A reprensentative KOH activated carbon shows an excellent specific capacitance value of 999 F g -1 at a current density of 1 A g -1 . Furthermore, the symmetrically assembled two-electrode device also delivers a maximum energy density of 32 W h Kg -1 at a power density of 325 W Kg -1 . In addition, excellent cyclic stability of 98% capacitance retention is observed after 10,000 continuous GCD cycles even at a high current density of 5 A g -1 . Symmetric flexible supercapacitor device using KOH-PVA-K3FeCN6 as redox gel polymer electrolyte shows a synergistic specific capacitance of 145 mF cm -1 at a current density of 0.8 mA cm -1 exhibiting very less deviation in bending mode. Therefore, this waste biomass derived heteroatom doped hierarchical porous carbon nanosheets can be a promising material for cost-effective high- performance supercapacitor.

42 ENGINEERING↗
DOE OSTI2022

Towards fast-charging high-energy lithium-ion batteries: From nano- to micro-structuring perspectives

Electric vehicles (EVs) have been playing an indispensable role in reducing greenhouse gas emissions for our modern society. However, current EVs are difficult to meet people’s diverse travel needs, especially in long endurance and fast-charging capacities. At the heart of this issue is the physicochemical limit of current lithium-ion batteries (LIBs), which are the core parts for powering the vehicles. Hence, LIBs with simultaneous high energy and power are critically required to further promote the development of EVs. Here, in this review, we first summarize the key electrochemical processes in electrochemical reactions which lead to the corresponding overpotentials in or between multiple battery components. Furthermore, numerical simulations are employed to quantitatively analyze the effects of versatile electrode parameters on electrochemical properties in high-energy NMC811//graphite systems. On the basis of the in-depth understandings from simulation, recent experimental efforts on designing electroactive materials and electrode architectures across multiple length scales are discussed. Among them, nano-structuring can promote local mass transport and stabilize the interfaces at the particle level, while micro-structuring can establish efficient pathways for charge carriers at the electrode level. Finally, we conclude that a tight feedback loop among structure engineering, characterization and simulation should be followed to speed up the understanding of the deficiencies existing in current electrode designs as well as point out the possible electrode optimization routes for next-generation fast-charging LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Potential-induced wetting and dewetting in hydrophobic nanochannels for mass transport control

Wetting and dewetting transitions play a central role in controlling the hydrophobicity of the lining of biological channels in order to regulate aqueous solution permeation. Understanding of the operational characteristics of biological nanochannels led to experimental efforts to mimic their behavior and to achieve potential-induced, repeatedly-switchable wettability transitions in synthetic nanochannels in the early 2010s. Since then, research has identified conditions needed to produce reversible wettability transitions using a number of different environmental stimuli - such as light, pH, and electrostatic charge - in addition to potential. Furthermore, nascent understanding of the underlying phenomena in synthetic nanochannels was rapidly followed by practical applications, including oil-water separations, drug release, and electroactive flow control based on switchable wettability. Furthermore, more practical applications are being developed continuously, as the physical and chemical principles that govern hydrophobic gating at the nanoscale are further elucidated, making it possible to exploit wettability as a design element in nanofluidic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ion soft landing: A unique tool for understanding electrochemical processes

Ion soft landing (SL) is a preparative mass spectrometry approach that enables deposition of mass- and charge-selected gaseous ions onto surfaces with controlled kinetic energy. The unique capabilities of SL provide an opportunity to populate electrode–electrolyte interfaces (EEIs) with well-defined intact electroactive ions of known composition, thereby facilitating the characterization of their intrinsic electrochemical properties. Here, in this perspective, we describe the SL technique and discuss how it may be used to study the effect of the charge state, stoichiometry, and composition of large redox active molecules and clusters on their electron transfer kinetics. SL has enabled the characterization of redox-active species that cannot be purified and examined using conventional bulk-phase separation and deposition approaches. Furthermore, precise control over the deposition process provides an opportunity to prepare and characterize well-defined EEIs relevant to energy storage and conversion, catalysis, and sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

An AlCl 3 based ionic liquid with a neutral substituted pyridine ligand for electrochemical deposition of aluminum

We study a new ionic liquid (IL) based on a neutral ligand, 4-propylpyridine, is obtained via complexation with AlCl 3 . It is found that the asymmetric cleavage of AlCl 3 generates AlCl 2 + and AlCl 4 , and the former is coordinated by 4-Pr-Py to produce the Al-containing cations ([AlCl 2 (4-Pr-Py) 2 ] + ). The AlCl 3 /4-propylpyridine IL with a molar ratio of 1.3/1 is highly fluidic with a viscosity of 42.8 mPa s and an ionic conductivity of 5.0 x 10 -4 S/cm at room temperature. In contrast to conventional ILs for electroplating aluminum in which the electrochemically active species are Al-containing anions (for example Al 2 Cl 7 - ), this new IL has an Al-containing cation as the electroactive species, which is beneficial to electrodeposition of aluminum.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An electrochemical study of hydrogen in molten 2LiF-BeF 2 (FLiBe) with addition of LiH

The chemical and transport behavior of hydrogen isotopes in molten 2LiF-BeF 2 (FLiBe) is of interest for the design of tritium management systems in nuclear fission and fusion reactors that use FLiBe. The chemical reaction of LiH with FLiBe is used to introduce hydrogen in the molten salt and electrochemical methods are used for in situ studies of hydrogen in FLiBe. LiH reacts with molten FLiBe to generate an electroactive species whose voltammetry peak is proportional to the added quantity of LiH. The cyclic voltammetry reaction potential of 2.009 ± 0.050 V vs Be/Be 2+ and the electron exchange of n = 0.8 ± 0.5 are consistent with the one-electron oxidation of dissolved H in the zero valence state, H o to H + . The concentration of H o is estimated by linear sweep voltammetry at 60–80% of the hydrogen introduced by the reaction of 0.42 mol% LiH with FLiBe and after eleven hours it remains above 40%. It is postulated that covalent BeH 2 is formed in FLiBe upon LiH addition, as a FLiBe-soluble quasi-stable intermediate product. Furthermore, the results provide an evaluation of LiH as a means of introducing dissolved hydrogen in FLiBe, enabling electrochemical methods as tools to advance the understanding of the chemistry of hydrogen isotopes in FLiBe.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Thermochemical measurements of FeCl 2 in LiCl via electromotive force, coulometric titration, and cyclic voltammetry

The thermochemical properties of FeCl 2 in the LiCl-FeCl 2 binary system were determined at 913 K using electromotive force (emf) cells containing pre-made and coulometrically titrated molten salt compositions. Coulometric titration to in-situ change the salt composition utilizes the multiple valences of Fe ions and the tendency of Fe 3+ ions to comproportionate with Fe metal, forming additional Fe 2+ . The emf results were used to define the compositions in which Henry’s law is applicable, up to approximately 2 mol% FeCl 2 . Thermochemical quantities were determined from emf using a Standard Lithium Chloride Electrode (SLiCE) which defines 0 V as the reduction of Li + in pure LiCl at all temperatures. Validation of emf measurements was performed by comparing the formal potential measured by using cyclic voltammetry (2.224 ± 0.013 V vs SLiCE) and emf measurements (2.236 ± 0.004 V). In conclusion, this work shows that coulometric titration of an electroactive species that undergoes comproportionation can be used to rapidly obtain granular emf data in molten salt systems.

Coulometric titration↗
DOE OSTI2021

Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications

Non-aqueous redox flow batteries (RFBs) have been gaining increased attention in the energy storage arena. Some of their attractive features include the promise for high energy densities, wider voltage windows compared to aqueous systems, as well as wider operating temperature ranges. One of the major challenges in the development of these systems is the lack of electroactive materials that can undergo reversible redox events within the larger potential window of organic solvents. In this paper, we present the design, synthesis, and measurement of electrochemical properties of some iron-based imine- and iminopyridine complexes as promising candidates for RFB applications. Synthesized complexes afforded three reversible redox couples over a ~3 V range. The redox events were also computationally explored and are in good agreement with experimental data. Theoretical calculations show that the redox event at the positive potential can be characterized as metal-centered event corresponding to Fe 3+ → Fe 2+ reduction, while the two redox events at negative potentials are associated with the consecutive reductions of iminopyridine or diimine moieties. This work has led to the identification of a promising anolyte material, [tris(imino)pyridine)Fe][OTf] 2 (1), which is soluble in acetonitrile and is synthesized in two simple steps. This species shows outstanding performance when cycled between 1.0 V and 2.35 V, with 93% coulombic efficiency, 84% energy efficiency, and a capacity decay rate of 0.61% per cycle at 5 mA cm –2 . Further modifications to this kind of charge carrier may lead to the development of high energy density materials for grid scale energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Comprehensive evaluation of commercially scalable atomic-layer-deposited alumina coating impact on full cell battery performance across varied test conditions

Atomic Layer Deposition (ALD) has emerged as a strategic enhancement method for lithium-ion battery (LIB) materials offering potential benefits and durability benefits for industrial battery production. However, the translation from laboratory achievements to commercial-scale applications has been limited. Here, this study aims to bridge this gap by comprehensively evaluating the effects of commercially scalable Al 2 O 3 ALD coatings using full pouch cell performance as a means to assess the ALD impact. We utilized large-scale slot-die coating techniques to ensure consistent electrode quality and tested four configurations of pouch cells to analyze the individual effects of ALD coating on anode and cathode electroactive materials. Our extensive testing matrix included long-term cycling, fast discharge, fast charge, leakage current, and high voltage tests. While at lower C-rates (<~1C), the influence of Al 2 O 3 coatings on cell performance is not significant. Fast charging conditions reveal that the anode ALD coating significantly enhances performance via a passivating effect, while on the cathode, it is detrimental, potentially due to increased resistance of the thin interfacial layer formed during the ALD processing. Leakage current and high-voltage tests show that the application of ALD coatings on either anode or cathode effectively minimizes side reactions at the electrode-electrolyte interface. Additionally, ALD coatings significantly mitigate concentrated and localized lithium plating on the anodes. These insights provide a valuable understanding of the potential of ALD technologies in LIB manufacturing to tailor cell performance, paving the way for safer, more efficient, and cost-effective battery solutions.

25 ENERGY STORAGE↗
DOE OSTI2017

Synthesis and properties of polymerized ionic liquids

Polymerization of ionic liquids results in the formation of ionic polymers, which are called poly (ionic liquid)s or polymerized ionic liquids (PIL). This is a brand new form of ionicity in polymer chains with a broad range of applications, though ionic polymers have a long history with the sub-families of polyelectrolytes and ionomers. Although mobility of ions in ionic liquids has named them as the promising candidates for various applications, their applicability is limited in many practical systems because of not having the advantages of neither liquids nor solids, suffering from both leakage issue and high viscosity. PILs perfectly fit with the practical requirements while having almost all features of ionic liquids. This review summarizes some potential applications of PILs. The architecture of PILs can be easily re-designed by both the polymer backbone and outer ion. Not only by post-polymerization but also by in situ ion exchange, the chemical and mechanical properties of PILs can be tuned. Lastly, owing to the high chemical activity and flexible architecture, PILs are the promising candidates for sensors and actuators, electroactive binders, solid and gel electrolytes, non-blocking matrix of nanocomposites, etc.

36 MATERIALS SCIENCE↗