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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 OSTI2026

Measuring pH Changes Inside a Bipolar Membrane Junction

Here, the local pH environment within bipolar membrane (BPM) junctions is complex and not well understood, yet it is important to control for advancing the performance of BPM-based electrochemical systems. We report a voltammetric strategy using an ultrathin Ni mesh pH probe to spatially resolve pH changes in the BPM junction during model BPM electrolyzer operation. Under reverse bias, we observe depletion of OH – at the anion-exchange layer (AEL) interface, with a degree diminishing with increasing distance from the AEL. These gradients correlate with current-dependent water dissociation (WD) and are modulated by the electric field and the surface charge state of the catalyst. By correlating spatial pH profiles with the surface-charging behavior of WD catalysts, we explore a mechanism of catalyst-mediated H + and OH – transfer facilitated by hydrogen-bonding networks. These findings highlight the role of local chemistry and electrostatics in BPM performance and offer new methods to probe and engineer catalytic junctions in electrochemical energy devices.

Hou, Shujin [University of California, Berkeley, C↗
DOE OSTI2022

From lab to lamp: Understanding downconverter degradation in LED packages

Downconverters, primarily inorganic phosphors, are critical components in white solid-state LED-based lighting and liquid crystal display backlights. Research efforts have led to a fundamental understanding of a downconverter's absorption, photoluminescence, and efficiency as a function of composition, structure, and processing conditions. However, considerably less work has focused on the reliability of phosphors once they are incorporated into LED packages. Solving these issues is often the final step before the commercialization of new materials, but the significant resources and time required to evaluate and mitigate materials failure are rarely discussed in the literature. In this Perspective, we discuss the need for conducting downconverter reliability testing and the potential of accelerating, screening, and understanding downconverter failure modes. Our focus highlights the mechanisms of failure and discusses how this influences materials selection and the design of different LED packages. We also stress the potential for accelerated reliability testing protocols and note the potential role first-principles calculations and data-driven models could play in establishing the compositional-processing trends for different aspects of downconverter reliability. In conclusion, we close with possible research directions that could improve downconverter reliability and emphasize the importance of assessing a material's (chemical) stability where multiple manufacturing and processing steps can dictate system performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Electrophoretic Deposition of Platinum Nanoparticles using Ethanol-Water Mixtures Significantly Reduces Neural Electrode Impedance

We report platinum electrodes are critical components in many biomedical devices, an important example being implantable neural stimulation or recording electrodes. However, upon implantation, scar tissue forms around the electrode surface, causing unwanted deterioration of the electrical contact. We demonstrate that sub-monolayer coatings of platinum nanoparticles (PtNPs) applied to 3D neural electrodes by electrophoretic deposition (EPD) can enhance the electrode's active surface area and significantly lower its impedance. In this work we use ethanol-water mixtures as the EPD solvent, in contrast to our previous studies carried out in water. We show that EPD coating in 30 vol.% ethanol improves the device's electrochemical performance. Computational mesoscale multiparticle simulations were for the first time applied to PtNP-on-Pt EPD, revealing correlations between ethanol concentration, electrochemical properties, and coating homogeneity. Thereto, this optimum ethanol concentration (30 vol.%) balances two opposing trends: (i) the addition of ethanol reduces water splitting and gas bubble formation, which benefits surface coverage, and (ii) increased viscosity and reduced permittivity occur at high ethanol concentrations, which impair the coating quality and favoring clustering. A seven-fold increase in active surface area and significantly reduced in vitro impedance of the nano-modified neural stimulation electrode surfaces highlight the influence of ethanol-water mixtures in PtNP EPD.

36 MATERIALS SCIENCE↗
DOE OSTI2021

(Invited) Understanding Multi-Component Transport and Reaction Phenomena in Bipolar Membranes Used for Electrosynthesis

Bipolar membranes (BPMs), which have long seen usage in electrodialysis reactors for the generation of acid and base, have recently demonstrated potential to become critical components in electrochemical synthesis devices. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM junction as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-devices for electrosynthesis applications. Prior work has modeled ion transport in bipolar membranes in neutral salt solutions for electrodialysis. However, no model exists for the BPM under the harsh applied pH gradients that would be present in electrosynthesis, and there is significant need to explore the effects of the internal hydration on the lifetime and performance of BPMs in such environments. Additionally, a mechanistic understanding of water dissociation catalysis will be required to develop interfacial catalysts that enable the high current density operation required for scalable electrosynthesis of fuels. In this talk, we discuss modeling methodologies and physics inherent in BPMs and present our recent model of ion transport and water dissociation catalysis in BPMs across the pH scale. Specifically, we simulate multi-ion transport for a BPM with various electrolyte combinations on each side of the membrane, demonstrating the significance of co- and counter-ion crossover in BPMs operating under harsh pH gradients. We then investigate effects caused by hydration gradients that occur due to internal ion-exchange and examine potential methods for improving performance and mitigating crossover. Finally, we examine the impact of the interfacial water dissociation catalyst and perform sensitivity analysis on the key properties (catalyst point of zero charge and pKa) that dictate catalyst performance. These results provide information that is critical to developing a comprehensive understanding of multi-component phenomena in BPMs and to informing the design and implementation of BPMs in next-generation devices for the numerous electrosynthesis chemistries that benefit from operation under an applied pH gradient.

Bui, Justin C↗
DOE OSTI2023

Robust highly durable solid oxide fuel cell cathodes – Improved materials compatibility & self-regulating surface chemistry

Solid oxide fuel cells (SOFCs) are electrochemical conversion devices that directly transform hydrogen or hydrocarbon fuels to electricity, with energy efficiencies as high as 90%, coupled with reduced emissions. Several factors, however, remain to be addressed when considering scale-up of SOFC technology, including the need to overcome decreased performance due to sluggish rates of the oxygen reduction reaction (ORR) at the cathode under reduced temperatures and susceptibility to degradation in performance from surface poisoning e.g. from chromia, while limiting the use of critical raw materials (lanthanides and transition metals) present in high performing mixed ionic electronic conducting electrodes like (La,Sr)CoO 3 (LSC). In this project we explored the key descriptors for determining ORR activity in SOFC electrodes and tried to recover performance degradation by applying them to SOFC electrodes. In order to do this, we first selected a model mixed ionic electronic conducting (MIEC) oxide, Pr-doped CeO 2 (Pr 0.1 Ce 0.9 O 2-δ , PCO), which is a chemically stable fluorite and free of inherent poison sources (e.g. Sr segregation in LSC) that potentially react with external impurities such as Cr-species vaporized from the interconnect. The three approaches originally planned in this project are as follows: 1) evaluation of scavenger exsolution characteristics, 2) study of scavengers gettering efficacy following Cr and Si poisoning and 3) integration of new compositions into porous electrodes. Among them, exceptional progress has been made in 2) and 3), especially understanding the role of surface infiltrants in impacting electrode performance and degradation of PCO materials. We found that the Smith acidity scale for binary oxides serves as a powerful descriptor for tuning and predicting the oxygen exchange kinetics on MIEC PCO surfaces. As a result, with infiltration with binary oxides, ranging from strongly basic (Li 2 O) to strongly acidic (SiO 2 ) onto the surface of porous PCO, it was possible to systematically vary the chemical surface exchange coefficient (k chem ) by 6 orders of magnitude! L i2 O increased k chem by nearly 1,000 times over that of pristine PCO, while SiO 2 decreased k chem by nearly the same factor. Strikingly, although the pre-exponential of k chem scales linearly with the acidity of the infiltrated binary oxide, there is nearly no change in the activation energy. With this insight, we attributed the origin of these dramatic changes in k chem values to the systematic increase and decrease in the surface electron density induced by infiltrated binary oxides. More interestingly, although both Cr 2 O 3 and SiO 2 were determined to be acidic by Smith, suggesting that this feature could likely be the primary reason that these compounds serve to poison the ORR on SOFC cathodes, the effect of poisoning could be subsequently tuned by adding multiple infiltrants and controlling their relative surface acidities. We also systematically examined the effect of serial infiltration of basic and acidic oxides. It turned out that serial infiltration of Li not only recovers approximately 20-fold degraded k chem of PCO by acidic Cr 2 O 3 but its k chem is enhanced even beyond that of the non-infiltrated PCO by more than three orders of magnitude. This was further verified with a screen-printing PCO symmetric cell in terms of the electrode performance (area-specific resistance, ASR) related to approach 3). These observations point to acidity as a key descriptor not only in tuning and predicting the ORR activity of SOFC cathodes that largely determines the overall performance of SOFC, but in mitigating and reactivating poisoned electrode performance. This work provides novel guidelines for making the electrode performance much more active and robust in SOFCs, which can further be applied to all applications requiring oxygen exchange reaction, such as electrolyzers, permeation membranes and gas sensors.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Microemulsions: Breakthrough Electrolytes for Redox Flow Batteries

Aqueous and non-aqueous redox flow batteries (RFBs) have limited energy and current densities, respectively, due to the nature of the electrolytes. New approaches to electrolyte design are needed to improve the performance of RFBs. In this work, we combined a highly conductive aqueous phase and an organic redox-active phase in a microemulsion to formulate a novel RFB electrolyte. As a proof-of-concept, we demonstrate an RFB using this microemulsion electrolyte with maximum current density of 17.5 mA·cm −2 with a 0.19 M posolyte and 0.09 M negolyte at a flow rate of only ∼2.5 ml·min −1 , comparable to early vanadium electrolyte RFBs at similar flow rates on a per molar basis. The novel active negolyte component is an inexpensive oil-soluble vitamin (K 3 ). By combining aqueous and organic phases, the solvent potential window and energy density may be increased without sacrificing current density and new redox couples may be accessed. Microemulsion electrolytes show great promise for improved performance and increased energy densities in aqueous RFBs but the path forward is complex. We end with discussion of areas that need work to achieve the potential of these electrolytes.

25 ENERGY STORAGE↗
NASA NTRS1981

The chemical behavior of acidified chromium (3) solutions

A unique energy-storage system has been developed at NASA's Lewis Research Center called REDOX. This NASA-REDOX system is an electrochemical storage device that utilized the oxidation and reduction of two fully soluble redox couples for charging and discharging. The redox couples now being investigated are acidified chloride solutions of chromium (Cr(+2)/Cr(+3)) and iron (Fe(+2)/Fe(+3)).

Terman, D. K.↗
NASA NTRS2011

Evaluation of Electrochemically Generated Potable Water Disinfectants for Use on the International Space Station

Microbial contamination and subsequent growth in spacecraft water systems are constant concerns for missions involving human crews. The current potable water disinfectant is iodine; however, with the end of the Space Shuttle program, there is a need to develop redundant biocide systems which are less dependent on hardware that would need to be launched on a regular basis. Three systems for electrochemical production of potable water disinfectants are being assessed for use on the International Space Station (ISS). Since there is a wide variability in the literature with regards to efficacy in both concentration and exposure time of these disinfectants, there is a need to establish baseline efficacy values. This paper describes a series of tests performed in order to establish optimal concentrations and exposure times for four disinfectants against single and mixed species planktonic and biofilm bacteria and to determine whether these electrochemical disinfection devices are able to produce a sufficient amount of chemical in both concentration and volume to act as a biocide for potable water on ISS.

Vega, Leticia↗
NASA NTRS2022

Lunar Equator Regenerative Fuel Cell System Efficiency Analysis

It is expected that future NASA mission energy storage requirements can be adequately met by regenerative fuel cells (RFCs). Aerospace RFCs are likely to package proton exchange membrane electrochemical conversion devices based on hydrogen, oxygen, and water. To optimize system designs and direct further development, the most useful system metric is round-trip efficiency (RTE). Improving RTE generally increases specific energy and reduces system mass. The following analysis models the impact of several factors on RTE for RFCs scaling from 0.1 to 50 kW. The analysis demonstrates that higher electrolyzer (EZ) operational pressure most negatively impacts both RFC RTE and specific energy. Reactant storage heating and power management losses are significant for RFCs of any scale, but solenoid valve power becomes a noticeable parasitic load for smaller RFCs. Spherical gas storage vessels benefit RTE by only 2 to 4 percentage points but increase specific energy by ~50 percent. Cryogenic reactant storage is shown to depress RTE to below 15 percent in all cases. For a given RFC scale, there is an RTE benefit to specifying larger EZs and recharging at higher rates—if the RFC can be coupled with a corresponding power source. Although fuel cell (FC) operation is less impactful on RTE than EZ factors, efficiency is maximized by sizing the FCs relatively large and keeping current density low. RFC design is a balance of many interrelated factors, but this analysis provides a starting point for difficult decisions that must be made when designing a lunar equator RFC.

regenerative fuel cell↗
NASA NTRSDate not supplied

Lunar South Pole Regenerative Fuel Cell System Efficiency Analysis

It is expected that future NASA mission energy storage needs can be adequately met by regenerative fuel cells (RFCs). Aerospace RFCs package proton exchange membrane (PEM) electrochemical conversion devices based on hydrogen, oxygen, and water. To optimize system designs and direct further development, the most useful system metric is round-trip efficiency (RTE). Improving RTE generally increases specific energy and reduces system mass. The following analysis models the impact of several factors on RTE for RFCs at the lunar south pole scaling from 0.1 kW to 50 kW. The analysis demonstrates that higher electrolyzer operational pressure most negatively impacts both RFC RTE and specific energy. Optimal electrolyzer membrane thickness is evaluated as a function of operational current density and pressure. Reactant storage heating and power management losses are significant for RFCs of any scale but are reduced in impact at the south pole compared to colder equator applications. Solenoid valve power remains a noticeable parasitic load for smaller RFCs. Larger electrolyzers enable higher peak theoretical efficiencies when recharging at higher rates, if the RFC can be coupled with a corresponding higher power source. RFC design is a compromise of many interrelated factors, but this analysis provides a starting point for difficult decisions that must be made when designing a lunar south pole RFC.

regenerative fuel cell↗
DOE OSTI2020

Low Threshold Voltages Electrochemically Drive Gold Migration in Halide Perovskite Devices

The constituent ions of halide perovskite materials are mobile in the solid state and known to participate in reduction/oxidation reactions. Yet few parameters related to electrochemical processes occurring within devices have been carefully determined. Here, we characterize such reactions in model MAPbI3 perovskite devices, and we quantify threshold voltages for key reactions. Gold is oxidized and mobilized under nitrogen, in the dark, at the MAPbI3/Au interface at 0.8 V. When this interface is buffered with the organic hole transport material (HTM), 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamino)-9,9'-spirobifluorene, MAPbI3 begins to degrade at 1.2 V; degradation liberates ions that subsequently enable Au migration. Thresholds are insensitive to MAPbI3 thickness or choice of organic HTM or oxide cathode, which suggests that these reactions are driven electrochemically; the electric field across the device is less important. These results have profound implications for understanding in operando degradation pathways of optoelectronic perovskite devices that are varied in terms of interface structures, active material compositions, and ranges of external stressors.

42 ENGINEERING↗
DOE OSTI2021

Probing the electronic properties of the electrified silicon/water interface by combining simulations and experiments.

Silicon (Si) is broadly used in electrochemical and photoelectrochemical devices, where the capacitive and Faradaic reactions at the Si/water interfaces are critical for signal transduction or noise generation. However, probing the electrified Si/water interface at the microscopic level remains a challenging task. Here we focus on hydrogenated Si surfaces in contact with water, relevant to transient electronics and photoelectrochemical modulation of biological cells and tissues. We show that by carrying out first principles molecular dynamics simulations of the Si(100)/water interface in the presence of an electric field we can realistically correlate the computed flat-band potential and tunneling current images at the interface with experimentally measured capacitive and Faradaic currents. Specifically, we validate our simulations in the presence of bias by performing pulsed chronoamperometry measurements on Si wafers in solution. Consistent with prior experiments, our measurements and simulations indicate the presence of voltage-dependent capacitive currents at the interface. We also find that Faradaic currents are weakly dependent on the applied bias, which we relate to surface defects present in newly prepared samples.

Ye, Zifan↗
DOE OSTI2022

Advanced metal hydride heat transfer system utilizing an electrochemical hydrogen compressor

An electrochemical heat transfer device for a hot water tank utilizes an electrochemical hydrogen compressor to pump hydrogen into and out of a tank having a metal hydride forming alloy therein. The absorption of hydrogen by the metal hydride forming alloy is exothermic, produces heat, and the desorption of the hydrogen from the metal hydride forming alloy is endothermic and draws heat in. An electrochemical hydrogen compressor may be configured between to tanks and pump hydrogen back and forth to form a heat transfer device, such as a hot water heater. A heat transfer device may be coupled with the tank or may comprise the outer surface of the tank to transfer heat to an object or to the surroundings. A closed loop may be configured having two tanks and one or two electrochemical hydrogen compressors to pump the hydrogen in a loop around the system.

Bahar, Bamdad↗
DOE OSTI2024

Switchable Charge Storage Mechanism via in Situ Activation of MXene Enables High Capacitance and Stability in Aqueous Electrolytes

The need for reliable renewable energy storage devices has become increasingly important. However, the performance of current electrochemical energy storage devices is limited by either low energy or power densities and short lifespans. Herein, we report the synthesis and characterization of multilayer Ti 4 N 3 T x MXene in various aqueous electrolytes. We demonstrate that Ti 4 N 3 T x can be electrochemically activated through continuous cation intercalation over a 10 day period using cyclic voltammetry. A wide operating window of 2 V is maintained throughout activation. After activation, capacitance at 2 mV s -1 increases by 300%, 140%, and 500% in 1 M H2SO4, 1 M MgSO4, and 1 M KOH, respectively, while maintaining ~600 F g -1 at 2 mV s–1 after 50000 cycles in 1 M H 2 SO 4 . This activation process is possibly attributed to the unique morphology of the multilayered material, allowing cation intercalation to increase access to redox-active sites between layers. This work adds to the growing repository of electrochemically stable MXenes reported for aqueous energy storage applications. These findings offer a reliable option for reliable energy storage devices with potential applications in large-scale grid storage and electric vehicles.

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

Discovering Reactant Supply Pathways at Electrode/PEM Reaction Interfaces Via a Tailored Interface-Visible Characterization Cell

In situ and micro-scale visualization of electrochemical reactions and multiphase transports on the interface of porous transport electrode (PTE) materials and solid polymer electrolyte (SPE) has been one of the greatest challenges for electrochemical energy conversion devices, such as proton exchange membrane electrolyzer cells (PEMECs), CO 2 reduction electrolyzers, PEM fuel cells, etc. Here, an interface-visible characterization cell (IV-CC) is developed to in situ visualize micro-scaled and rapid electrochemical reactions and transports in PTE/SPE interfaces. Taking the PEMEC of a green hydrogen generator as a study case, the unanticipated local gas blockage, micro water droplets, and their evolution processes are successfully visualized on PTE/PEM interfaces in a practical PEMEC device, indicating the existence of unconventional reactant supply pathways in PEMs. Further comprehensive results reveal that PEM water supplies to reaction interfaces are significantly impacted with current densities. Here these results provide critical insights about the reaction interface optimization and mass transport enhancement in various electrochemical energy conversion devices.

30 DIRECT ENERGY CONVERSION↗