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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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Development of lithium ion conducting interface between lithium metal and a lithium ion conducting ceramic using block polymers

The lithium-air (Li-air) technology developed by EDF uses an air electrode which works with an aqueous electrolyte, which prevent the use of unprotected lithium metal electrode. A Li+ ionic conductor glass ceramic is used to separate the aqueous electrolyte compartment from the negative lithium electrode. However, this glass-ceramic is not stable in contact with lithium, it is thus necessary to add a protective buffer layer. In another hand, this protection should ideally resist to lithium dendritic growth. It is in this context that this research project which has as goal the development of a protective buffer layer based on block copolymer electrolytes (BCE) between the lithium metal and the lithium ionic conductor ceramic, for lithium-air battery. In a first part, the BCE is studied in lithium-lithium symmetric cells, in order to determine their electrochemical properties such as ionic conductivity, steady state transference number, and finally their resistance to dendritic growth during cycling. Several characterization techniques were employed and especially hard X-ray micro-tomography to analyze the lithium morphology before and after cycling. For single-ion BCE, we expect to suppress dendritic growth, however, we report here for the first time, the visualization of a homogeneous growth of lithium but the formation of dense lithium objects. In another part, the composite BCE-ceramic is studied by electrochemical impedance spectroscopy (EIS). The cycling of lithium-composite-lithium symmetric cells and the analysis of the EIS measurement after each cycle permit to determine if the dendrites have cross the protective layer and are in contact with the ceramic. Besides, the quantification of the polarization loss at the interface polymer-ceramic is evaluated by polarization experiments. This contribution is found to be small.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C

Abstract The open circuit potential (OCP) established by the quasi-equilibrated electrode reaction of H 2 and H 3 O + (hydr.) , complicates catalytic reactions significantly. The hydrogenolysis rate of benzylic alcohol on Pd/C increases 2-3 orders of magnitude with the pH decreasing from 7 to 0.6. The reaction follows a pathway of protonated benzyl alcohol dehydration to a benzylic carbenium ion, followed by a hydride addition to form toluene. The dehydration of protonated benzyl alcohol is kinetic relevent, thus, being enhanced at lower pH. The OCP stabilizes all cationic species in the elementary steps. Particularly, the initial state (benzyl alcohol oxonium ion) is less stabilized than the dehydration transition state and the product (benzylic carbenium), thus, lowering the free energy barrier of the rate-determining step. In accordance, the rate increased with increasingly negative OCP. Beside OCP, an external negative electric potential in an electrocatlaytic system was also demonstrated to enhance the rate in the same way.

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

Ferroelectric polarization retention with scaling of Hf 0.5 Zr 0.5 O 2 on silicon

In this paper, we investigate the polarization retention of Hf 0.5 Zr 0.5 O 2 (HZO)-based metal–ferroelectric–insulator–Si (MFIS) capacitors with scaling of the ferroelectric (FE) layer thickness from 5 nm to 20 nm. The capacitors have a constant interface layer capacitance of ~24 μF/cm 2 , developed due to the integration of HZO on a degenerated Si as a bottom conducting electrode. It is observed that 20 nm HZO films show a small change (~5%) in FE polarization (P FE ) between short (10 μs) and long (6 s) retention time, while 5-nm-thick films exhibit a large difference (~90%). Furthermore, the dependence of P FE retention loss on the FE thickness can be understood by the presence of a built-in electric field in the FE layer, generated due to charge continuity between the FE and the interface layers in the ground state without any external bias. A direct experimental observation also confirms that a residual voltage is developed at the node between the metal–ferroelectric–metal and metal–oxide–semiconductor capacitors connected in series, in the ground state with zero external bias. It is expected that a proper understanding of the built-in field developed in the FE layer in an MFIS stack is crucial for FE memory retention characteristics.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Aerobijels: Ultralight Carbon Monoliths from Cocontinuous Emulsions

In this work, bijels are used to develop a new class of ultralight hierarchically porous aerogels exhibiting multimodal porosity across multiple length scales. Through in situ functionalization of a particle-laden liquid interface wherein binary liquid pairs are kinetically trapped out of equilibrium through interfacial jamming, monolithic and freestanding carbon electrodes are produced with prescribed bulk densities down to ≈2 mg cm -3 . Exemplary electrokinetic experiments indicate that the bicontinuity of the pore structure is essential for enhancing transport to and from the active electrode surfaces, demonstrating that these materials possess a superior ability to accumulate and transport charge when compared to analogous systems with restricted pore connectivity and fluid throughput. This approach offers a new synthetic route to bicontinuous and hierarchical aerogel materials with nested multimodal porosities. Furthermore, the flexibility of this scheme can address critical issues related to transport-limited behaviors that arise in many technological fields, ranging from energy and catalysis research to remediation and sensing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Stable Cycling with Intimate Contacts Enabled by Crystallinity–Controlled PTFE–Based Solvent–Free Cathodes in All–Solid–State Batteries

All-solid-state batteries (ASSBs) employing Li-metal anodes and inorganic solid electrolytes are attracting great attention due to high safety and energy density for next-generation energy storage devices. However, the volume change of cathode active materials can cause contact loss, resulting in charge carrier isolation, heterogeneous current distribution, and poor electrochemical properties in ASSBs. Here, a simple, yet effective, solvent-free electrode engineering approach with polytetrafluoroethylene (PTFE) as a binder for ASSBs is reported, enabling intimate contact and stable interfaces with the cathode. It is substantiated that the crystallinity of PTFE can be controlled depending on the heat history, and highly crystalline PTFE displays robust mechanical properties. High-nickel LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode prepared with crystalline PTFE show improved cycle and rate performances in ASSBs. In addition, it is revealed that the intimate contact between cathode particles with a stable cathode electrolyte layer is maintained during cycling by postmortem studies. Furthermore, this simple engineering method can be applied to prepare cathodes with a variety of active materials and solid electrolytes in ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Cryogenic electronics for noble liquid neutrino detectors

In this paper we present the general features of cryogenic (or “cold”) electronics for noble liquid time projection chambers, with design principles and details for neutrino physics, a brief history of the technology and details of recent research and development that is driving the design of the detectors under construction. Finally, some comments on future R&D envisioned and the impact of this work on other fields is described. “Cold” in the context of this work applies to CMOS devices operated at 77 K and above, at liquids temperatures of LAr (89 K), LKr (125 K) and LXe (165 K), with most of the tests performed in, or at LN 2 (77 K). Additionally, the paper is concentrated on the design of cold electronics for large liquid argon TPCs, those that have been successfully operated, MicroBooNE and ProtoDUNE, and those designed or under construction, such as SBND and DUNE first and second 10 kton modules. The high performance achieved with MicroBooNE and ProtoDUNE – a high signal-to-noise ratio combined with high stability of response – is mainly due to the integral approach to design and construction of sensing electrodes with cold readout electronics in a modular approach with the cryostat signal feed-throughs incorporating warm interface electronics into a Faraday cage with the cryostat. The integral concept is described in some detail in this paper.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Surface Engineering of Copper Catalyst through CO* Adsorbate

The electrochemical reduction of CO 2 with Cu-based catalysts depends intimately on the instantaneous local chemical environment of the catalyst-electrolyte interface. This microenvironment fluctuates according to the concentration of surface-adsorbed competing reaction intermediates and the applied electrode potential. In practice, disentangling these factors is exceedingly challenging, yet they critically determine the electrocatalyst efficiency and selectivity. Using grand canonical quantum-classical hybrid calculations, we quantify the complex interdependence between electrode potential, CO* coverage, and the interfacial field strength. Here we show that the often overlooked CO* coverage effect in fact strongly influences the field strength, with a magnitude change exceeding 1V/Å at certain potentials; among other effects, this change should lower the CO* dimerization barrier that dictates selectivity toward multi-carbon products. Beyond showcasing the importance of surface coverage for CO2 reduction, our results highlight the power of surface additives to modulate interfacial fields toward tailored electrochemical pathways.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2019

Stable Unassisted Solar Water Splitting on Semiconductor Photocathodes Protected by Multifunctional GaN Nanostructures

Producing hydrogen by unassisted solar water splitting is one essential step to make direct solar fuel conversion a viable energy source. To date, however, there has been no demonstration of stable photoelectrodes for high efficiency photoelectrochemical water splitting. In this work, we report that a GaInP2/GaAs/Ge triple-junction (3J) photocathode protected by multi-functional GaN nanostructures can enable both efficient and relatively stable solar water splitting. A 12.6% solar-to-hydrogen (STH) efficiency is measured without any external bias. Of particular importance, we demonstrate relatively stable solar water splitting for 80 hours in three-electrode configuration and 57 hours in two-electrode measurement at zero bias. This is the best reported stability for multi-junction semiconductor photocathodes in two-electrode configuration to our knowledge. Here, the multifunctional GaN nanostructure significantly reduces the charge transfer resistance at semiconductor/electrolyte interface and protects III-V materials against corrosion. Such multi-functional GaN photocatalytic nanostructures provide a new pathway to improve the performance of conventional photoelectrodes to achieve both efficient and stable unassisted solar water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Old Woman Creek Wetland Sediment and Electrochemical Sensor Microbial Community, 2023

We are developing a technique to monitor microbiological activities referred to as zero resistance ammetry, which entails the deployment of graphite electrodes in sediments. Measurement of current between electrodes of contrasting redox regimes and/or predominant terminal electron accepting processes can be used as an indicator of the extents of microbiological activity. We deployed an electrode array at depths of 2 mm, 4 mm, 76 mm, 78 mm, 152 mm, 154 mm, 227 mm, and 229 mm below the wetland sediment water interface in the Old Woman Creek National Estuarine Research Center, Huron, OH, USA (Lat. = 41.380833, Long. = -82.508889). A core was collected from adjacent sediment and subsamples were collected from depth intervals of 0 – 25 mm, 25 – 127 mm, 127 – 128 mm, and below 178 mm. To determine if the microbial communities attached to the electrodes were reflective of the adjacent sediment-associated microbial community, we conducted a 16S rRNA gene-based (V4 region) survey of these respective materials. This data package contains the results of these surveys, including metadata on the depths from which samples were collected (samples.csv), DNA extraction and sequencing information (OWC_DEPTH_AMPLICON_SEQUENCING_METADATA), sequence processing information (OWC_DEPTH_BIOINFORMATIC_METADATA.csv), an operational taxonomic unit (OTU) table (OWC_DEPTH_97OTUS_TABLE.csv), and nucleotide sequences of OTUs (OWC_DEPTH_97OTUS_SEQS.fasta). All files can be opened using a text-editing application. The fasta file is compatible with bioinformatics applications.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1980

Heart rate, multiple body temperature, long-range and long-life telemetry system for free-ranging animals

The design details and rationale for a versatile, long-range, long-life telemetry data acquisition system for heart rates and body temperatures at multiple locations from free-ranging animals are presented. The design comprises an implantable transmitter for short to medium range transmission, a receiver retransmitter collar to be worn for long-range transmission, and a signal conditioner interface circuit to assist in signal discrimination and demodulation of receiver or tape-recorded audio outputs. Implanted electrodes are used to obtain an ECG, from which R-wave characteristics are selected to trigger a short RF pulse. Pulses carrying heart rate information are interrupted periodically by a series of pulse interval modulated RF pulses conveying temperature information sensed at desired locations by thermistors. Pulse duration and pulse sequencing are used to discriminate between heart rate and temperature pulses as well as radio frequency interference. The implanted transmitter may be used alone for medium and short-range tracking, or with a receiver-transmitter collar that employs commercial tracking equipment for transmissions of up to 12 km. A system prototype has been tested on a dog.

Lund, G. F.↗
DOE OSTI2024

Review—In Situ X-ray and Infrared Spectroscopic Studies of Electrochemical Systems

Despite of intense research and a wealth of data, the phenomena occurring during electrocatalysis are still a major obstacle in many chemical processes. Molecular analysis of the electrode/electrolyte interface is needed to correctly describe the reaction through identifying the species involved, their interaction with the environment and kinetics in situ, i.e. while the reaction is taking place. That can be done by coupling the electrochemical system with complementary non-electrochemical techniques. Particularly revealing are in situ X-ray spectroscopic techniques to analyze the electrode itself, providing the information on the changes in the catalyst during the reaction. The synergy of the traditional electrochemical techniques with the complementary spectroscopic methodologies offer understanding of the electrode/electrolyte interface above and beyond traditional experimental mainframe. Here we demonstrate how in situ X-ray absorption spectroscopy (XAS), in situ infrared reflection/absorption spectroscopy (IRRAS), and traditional voltammetric studies can increase our understanding of electrochemical processes during oxidation of ethanol. The results show the pronounced role of electrode surface in determining reaction kineticks and revealed the selectivity of the catalyst to complete oxidation pathway. They further provide understanding of the parameters that enhance its oxidation for future designing catalysts for alcohol oxidation fuel cells.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2019

Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

Li 7 La 3 Zr 2 O 12 (LLZO) garnet-based materials doped with Al, Nb or Ta to stabilize the Li + -conductive cubic phase are a particularly promising class of solid electrolytes for all-solid-state lithium metal batteries. Understanding of the intrinsic reactivity between solid electrolytes and relevant electrode materials is crucial to developing high voltage solid-state batteries with long lifetimes. Using a novel, surface science-based approach to characterize the intrinsic reactivity of the Li-solid electrolyte interface, we determine that, surprisingly, some degree of Zr reduction takes place for all three dopant types, with the extent of reduction increasing as Ta < Nb < Al. Significant reduction of Nb also takes place for Nb-doped LLZO, with electrochemical impedance spectroscopy (EIS) of Li||Nb-LLZO||Li symmetric cells further revealing significant increases in impedance with time and suggesting that the Nb reduction propagates into the bulk. Density functional theory (DFT) calculations reveal that Nb-doped material shows a strong preference for Nb dopants towards the interface between LLZO and Li, while Ta does not exhibit a similar preference. Furthermore EIS and DFT results, coupled with the observed reduction of Zr at the interface, are consistent with the formation of an “oxygen-deficient interphase” (ODI) layer whose structure determines the stability of the LLZO-Li interface.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tuning Catalyst Activation and Utilization Via Controlled Electrode Patterning for Low-Loading and High-Efficiency Water Electrolyzers

An anode electrode concept of thin catalyst-coated liquid/gas diffusion layers (CCLGDLs), by integrating Ir catalysts with Ti thin tunable LGDLs with facile electroplating in proton exchange membrane electrolyzer cells (PEMECs), is proposed. The CCLGDL design with only 0.08 mg Ir cm -2 can achieve comparative cell performances to the conventional commercial electrode design, saving ~97% Ir catalyst and augmenting a catalyst utilization to ~24 times. CCLGDLs with regulated patterns enable insight into how pattern morphology impacts reaction kinetics and catalyst utilization in PEMECs. A specially designed two-sided transparent reaction-visible cell assists the in situ visualization of the PEM/electrode reaction interface for the first time. Oxygen gas is observed accumulating at the reaction interface, limiting the active area and increasing the cell impedances. In this work, it is demonstrated that mass transport in PEMECs can be modified by tuning CCLGDL patterns, thus improving the catalyst activation and utilization. The CCLGDL concept promises a future electrode design strategy with a simplified fabrication process and enhanced catalyst utilization. Furthermore, the CCLGDL concept also shows great potential in being a powerful tool for in situ reaction interface research in PEMECs and other energy conversion devices with solid polymer electrolytes.

08 HYDROGEN↗
DOE OSTI2023

Infrared Spectroscopic Observation of Oxo- and Superoxo-Intermediates in the Water Oxidation Cycle of a Molecular Ir Catalyst

Molecular Ir catalysts have emerged as an important class of model catalysts for understanding structure–activity relationships in water oxidation, a reaction that is central to renewable fuel synthesis. Prior efforts have mostly focused on controlling and elucidating the emergence of active species from prepared precursors. However, the development of efficient and stable molecular Ir catalysts also necessitates probing of reaction intermediates. To date, relatively little is known about the key intermediates in the cycles of the molecular Ir catalysts. Herein, we probed the catalytic cycle of a homogeneous Ir catalyst (“blue dimer”) at a Au electrode/aqueous electrolyte interface by combining surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD). Cyclic voltammograms (CVs) from 1.4 to 1.7 VRHE (RHE = reversible hydrogen electrode) give rise to a band at ~818 cm –1 , whereas CVs from 1.4 to ≥1.85 VRHE generate an additional band at ~1146 cm –1 . Isotope labeling experiments indicate that the bands at ~818 and ~1146 cm –1 are attributable to oxo (Ir V =O) and superoxo (Ir IV –OO • ) moieties, respectively. Furthermore, this study establishes PSD-SEIRAS as a sensitive tool for probing water oxidation cycles at electrode/electrolyte interfaces and demonstrates that the relative abundance of two key intermediates can be tuned by the thermodynamic driving force of the reaction.

25 ENERGY STORAGE↗
DOE OSTI2021

From bulk to interface: electrochemical phenomena and mechanism studies in batteries via electrochemical quartz crystal microbalance

Understanding the bulk and interfacial behaviors during the operation of batteries (e.g., Li-ion, Na-ion, Li–O 2 batteries, etc.) is of great significance for the continuing improvement of the performance. Electrochemical quartz crystal microbalance (EQCM) is a powerful tool to this end, as it enables in situ investigation into various phenomena, including ion insertion/deinsertion within electrodes, solid nucleation from the electrolyte, interphasial formation/evolution and solid–liquid coordination. As such, EQCM analysis helps to decipher the underlying mechanisms both in the bulk and at the interface. This tutorial review will present the recent progress in mechanistic studies of batteries achieved by the EQCM technology. Here, the fundamentals and unique capability of EQCM are first discussed and compared with other techniques, and then the combination of EQCM with other in situ techniques is also covered. In addition, the recent studies utilizing EQCM technologies in revealing phenomena and mechanisms of various batteries are reviewed. Perspectives regarding the future application of EQCM in battery studies are given at the end.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Overall Water Splitting with Room-Temperature Synthesized NiFe Oxyfluoride Nanoporous Films

Freestanding and lightweight thin-films were rationally designed to serve as robust electrodes for renewable energy applications. A facile and scalable nanomanufacturing process was developed to fabricate these transformative thin-film electrodes (iron group mixed oxides) that exhibit a nanoporous structure and controllable composition. More specifically, electrodeposition and anodic treatments were employed to produce freestanding and lightweight metal oxides nanoporous layers (NPL). These NPL can be directly used as flexible and additive-free electrodes for renewable energy generation (water splitting) and storage (supercapacitor) applications without requiring binders and current collector and other additives. Significantly enhanced electrochemical performance was achieved due to the unique merits of the NPL: i) highly porous structure considerably increases the electrode/electrolyte interface, which facilitate electrochemical reactions; ii) NPL substantially increase the number of active sites that are favorable in electrochemical reactions; iii) residual metal network within the NPL forms a conductive framework, drastically improving electrode strength, flexibility and conductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes

The ability to characterize bulk and interfacial transport properties of polymer electrolytes is critical to realizing their potential applications in electrochemical energy storage devices. In this paper, we leverage custom microfabricated interdigitated electrode array (IDEs) as a platform to probe ion transport properties of polymer electrolytes films through electrochemical impedance spectroscopy (EIS) measurements. Using poly(ethylene oxide) (PEO) blended with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as a model dry polymer electrolyte system, we investigate how geometric parameters of the IDEs influence the quality and analysis of EIS measurements. By focusing on films on the nanometer film thickness (ca. 50 nm), EIS measurements revealed diffusional processes near the electrode/polymer interface that may be difficult to observe with conventional thick films. Moreover, irreversible impedance spectra were observed at elevated temperatures when using IDEs with large electrode metal fractions. These irreversible processes were eliminated through passivation of the IDE with different oxides (SiO 2 , Al 2 O 3 , or TiO 2 ). Ultimately, the ionic conductivity of PEO-LiTFSI electrolytes is confidently determined when appropriate IDE geometries and equivalent circuits are used. Lastly, our work demonstrates the use of IDEs and nanothin polymer electrolytes films as a versatile platform for rapid and efficient interrogation of both bulk and interfacial electrochemical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Stress evolution in lithium metal electrodes

The potential advantages of lithium metal anodes have received widespread attention (highest capacity, lowest reduction potential, etc). However, the poor stability of Li metal / liquid electrolyte interfaces leads to chronic problems, such as dendrite formation and capacity loss. The possible impact of mechanical effects on interface stability and dendrite formation are difficult to probe directly. In this study, stress evolution during lithium plating and stripping was monitored with precise in situ measurements. The data obtained with different film thicknesses made it possible to separate the stresses associated with the lithium metal and the solid electrolyte interphase (SEI). The results show that significant stresses are created in the SEI films. Based on this, a basic model of wrinkling-ratcheting-delamination is also presented. This analysis indicates that plasticity in a growing Li film can enhance surface wrinkling, and thus lead to morphological destabilization of a planar growth front.

25 ENERGY STORAGE↗