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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 19 records

Application of Electrochemical Methods to Molten Salt Reactors: Draft TLR Documenting Assessment of Electrochemical Monitoring

Nuclear Regulatory Commission (NRC) is developing the regulatory framework and technical expertise to support regulatory review of advanced non-water reactors, including molten salt reactors (MSRs). In an MSR, it is essential that the salt chemistry be maintained in a desired range in terms of redox potential for reliable operation and mitigation of corrosion to structural materials in the reactor, particularly the reactor vessel and heater exchanger. Measuring the redox potential of the salt in the reactor would also allow for the material lifetimes to be predicted more accurately, and chemical issues to be diagnosed more quickly. In addition to the chemical composition analysis by ICP-MS, electrochemical methods including potentiometry and linear wave scanning (LSC) were also used in molten salt reactor experiment (MSRE) for redox potential monitoring purposes. Electrochemcial methods offers unique advantages such as quick turnaround in results and unique capability of in-line monitoring of redox potential, and are considered popular electroanalytical techniques that can be used to monitor redox potentials and salt chemistry including impurities. The last two decades have seen significant advances in science and engineering of electrochemical methods for potential application to molten salts. The primary goal of this report is to assist NRC in understanding the monitoring of the salt chemistry by electrochemical methods and provide NRC reviewers with necessary information and tools to support regulatory review of MSR designs. This reports consists of two majors parts—Part 1, chemical potential of molten salts and effects by fission process in MSR; Part 2, assessment of electrochemical methods for application to MSRs. The TRLs of the typical relevant electrochemical methods for molten salts were evaluated based on the DOE TRL guidelines and upon a review of the current status of the electrochemical methods for two typical salt systems, fluoride and chloride, for MSRs.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Scanning Electrochemical Microscopy: An Evolving Toolbox for Revealing the Chemistry within Electrochemical Processes

The parallel development of ultramicroelectrodes (UMEs) and groundbreaking scanning probe microscopy techniques in the late 1980s led to the development of the scanning electrochemical microscope. Scanning electrochemical microscopy (SECM) was born from the idea of using a tiny electrode to measure the local electrochemical behavior at operating electrodes. From its foundations, the technique displayed an inherent versatility in measuring sample properties beyond topography. It allowed experimenters to measure and map chemical reactions occurring at diverse interfaces, from inspecting the reversibility of redox mediators at metal electrodes, to detecting the hallmarks of cellular respiration on living plant leaves. Related but distinct electrochemical scanning probe techniques, such as electrochemical atomic force microscopy (EC-AFM), scanning ion conductance microscopy (SICM), and scanning electrochemical cell microscopy (SECCM) have developed in parallel. These techniques have demonstrated exquisite spatial resolution down to the nanoscale regime. However, it is the proposition of this review that SECM remains unmatched at revealing the chemical aspects of electrochemistry. Furthermore, it is our intention to review and demonstrate that the versatile architecture of SECM continues to evolve and address fundamental and emerging challenges in the fields of energy storage and conversion, chemical biology, materials science, and environmental chemistry, among others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Comprehensive Digital Twin of a Macro-fluidic Electrochemical Reactor to Optimize the Electrochemical-based Recovery of O2 from Metabolic CO2

Future long-duration missions will require a sustainable and efficient system capable of yielding a minimum of 75% O 2 recovery from metabolic CO 2 to achieve self-sufficiency for long space missions beyond Earth's low orbit. A Macro-fluidic Electrochemical Reactor (MFECR) development effort to electrochemically recover O 2 from CO 2 is underway at NASA Marshall Space Flight Center (MSFC) to increase current O 2 recovery efficiency and reduce air revitalization (AR) system complexity at the International Space Station (ISS) habitat and future long missions. The authors have developed and deployed a digital twin of an actual single cell of the MFECR via a comprehensive 3D multiphysics model that thoroughly replicates the exact configuration and fluid/material domains of the MFECR. This model's electrochemical physics consists of multicomponent-multiphase electrochemical-driven reactions leading to CO 2 conversion to C 2 H 4 and CO along with the formation of H 2 on the cathode in parallel with the generation of O 2 and H 2 O on the anode. This electrochemical model is coupled with all the physics phenomena involved in the process, including but not limited to fluid and non-ideal mass transfer of reactant and product species in free and porous media, convective/conduction/radiative heat transfer, and conduction of DC electrical current with Joule heating generation. The digital twin has proved to be an essential tool for performing different qualitative studies, including the effect of reducing the height (increasing the respect ratio) of the serpentine walls, leading to a further redesign of the EDU (the newly redesigned MFECR EDU has been fabricated and is expected to be used in future tests), the evaluation of setting different MFECRs connected in series, and the assessment of feeding air directly to the MFECR skipping the preceding metabolic CO 2 separation from air. The MFECR's test stand is fully automated and equipped with several inline measurements (flow, pressure, temperature, pH, component concentration) systems on all six MFECR's IO streams, allowing reliable experimental validation of the model, parametric determination of all electrochemical reactions, and process optimization.

Jesus A Dominguez

Solid‐State Prealkylation of Electrode Architectures (SPEAR): Direct Control of Prelithiation Levels in Silicon Anodes and Electrochemical Cycling

The Solid-state Prealkylation of Electrode ARchitectures (SPEAR) is different than traditional electrochemical prealkylation processes. Through SPEAR, alkylation is driven by solid-state diffusion without the simultaneous SEI formation concomitant with polarization. Here, we investigate the prelithiation of 80 wt. % Si-based anodes to varying amounts (up to Li 1.38 Si) to understand the trade-off between improved Li capacity and expansion-induced stress. Through dilatometry, we found that solid-state lithiation led to filling of the electrode pores through silicon expansion. This swelling changed the SEI formation process and accessibility of the silicon compared to an electrochemically lithiated electrode. Indeed, optimal prelithiation to Li 0.82 Si increases the initial C/3 cycling capacity post-SEI formation up to 43%, consistent with deeper Si activation through the electrode bulk. Prelithiation and cycling cells prelithiated beyond Li 0.82 Si results in a state of charge (SOC) close to 100% which facilitates parasitic degradation mechanisms and volume expansion of the Si electrode. The results demonstrate a pathway to modify silicon activation/SEI formation to enable high-energy electrodes.

Musgrove, Amanda L. [Oak Ridge National Laboratory

Electrochemical and Hydrodynamic Interferences on the Performances of an Oxygen Microsensor with Built-in Electrochemical Microactuator

A concept of novel electrochemical in situ self-calibration technique for an oxygen microsensor has been proposed to devise a convenient calibration method without an externally coupled apparatus. Systemic investigations on the influences of various electrochemical (pH) and hydrodynamic (solution stirring) conditions on the proposed microsensor performances are presented. The results suggest that: 1) The calibrating microenvironments can be manipulated with carefully engineered sensor designs and optimized generating signals; 2) The external oxygen permeable membrane is needed to minimize the electrochemical and hydrodynamic interferences.

Kim, Chang-Soo

Assessing the Long-Term Stability of Anion Exchange Membranes for Electrochemical CO 2 Reduction

Materials and cell components used in CO 2 electrolysis have largely been adapted from technologies initially developed for water electrolysis and fuel cells. However, electrochemical CO 2 reduction introduces distinct material challenges due to the unique chemical environment in this process. Here, in this study, we conducted ex-situ 1000 h stability tests on commonly used anion exchange membranes, exposing them exclusively to electrolytes and organic molecules used or produced during CO 2 electrolysis, at concentrations relevant to and compatible with postseparation processes. Notably, 15% w/w n-propanol and 5 M acetic acid caused complete dissolution or partial disintegration of the membranes unless cross-linking was present and remained stable throughout the test. When the membranes stayed physically intact, most of them exhibited excellent chemical stability in alkaline medium containing alcohols or formic acid, which was confirmed by vibrational spectroscopy and ion exchange capacity measurements. However, exposure to alcohol-and acid-containing solutions led to a substantial increase in swelling and water uptake, with potential implications for mechanical stability, ion/product crossover, and compression management of adjacent components. The potential effects of CO 2 electroreduction products on membrane stability, their subsequent impact on electrolyzer performance, and mitigation strategies are discussed.

CO2RR

Exsolution of NiCo alloys over Ruddlesden-Popper perovskite for mild electrochemical synthesis of ammonia on protonic ceramic electrochemical cells

Ammonia synthesis from renewable energies on protonic ceramic electrochemical cells (PCECs) shows great potential. The primary challenges in ammonia synthesis on PCECs include sluggish catalytic activity, competition from the hydrogen evolution reaction, and unsatisfactory durability of the cathode, which is the active site of ammonia generation. Here, in this study, we report an elaborate design of the cathode with an intended formula of Pr 4 Ni 1.79 Co 1.2R u 0.01 O 10-δ , where NiCo alloy nanoparticles are exsolved from Ruddlesden-Popper perovskite substrates after the reduction in 5 % H 2 /Ar at 400 °C for 1 h, for electrocatalysis of the nitrogen reduction reaction to ammonia. The host material Pr 4 Ni 1.8 Co 1.2 O 10-δ with embeddable layered structure and stability was deliberately chosen to fix the Ru cation and maximize the catalytic activity of NiCo. Also, density functional theory calculations suggest that Ru doping provides an optimal balance between structural stability and redox activity, facilitating the controlled exsolution of NiCo nanoparticles and enhancing catalytic performance. As a result, the composite electrode with exsolved NiCo alloy and abundant oxygen vacancies on fuel-electrode-supported PCECs achieves a superior electrochemical activity towards ammonia synthesis: a peak ammonia formation rate of 27.84 μg h −1 cm −2 and excellent Faradaic efficiencies of 62.6 % at 350 °C.

30 DIRECT ENERGY CONVERSION

Electrochemical Conversion of CO 2 to Methyl Formate in a Flow Electrolyzer with Mixed Propylene Carbonate/Methanol Catholyte

Despite the promise of electrochemical carbon dioxide reduction as a technology for the production of clean fuels and decarbonization of the chemical industry, research has mostly focused on aqueous systems with a relatively limited set of products that have been achieved via electrosynthesis. Increasingly, CO 2 electroreduction in nonaqueous solvents is being pursued to develop new avenues for expanding the suite of products that can be made with high selectivity. CO 2 reduction in alcohols coupled with in situ esterification to produce esters is one such route that utilizes nonaqueous electrolyte. To be practical, such electrochemical syntheses need to be translated to a high-performance reactor such as a flow electrolyzer. However, many organic solvents, such as alcohols, wet and flood porous electrodes, thus impeding reactor performance. In this work, methanol was mixed with propylene carbonate as a catholyte for a gas-fed CO 2 flow electrolyzer that avoided cathode flooding. Simultaneously, a dual aqueous anolyte was used for water oxidation as a scalable and sustainable anodic half-reaction. The performance effect of methanol concentration, catholyte acidity, CO 2 flow rate, and dilute water in the catholyte were investigated. With 10 vol % methanol in 90 vol % propylene carbonate, 63% faradaic efficiency for methyl formate ester product was sustained without cathode flooding. However, improvements are still needed to lower the cell resistance and further increase the operating current density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

The Prediction of Long-Term Coating Performance from Short-Term Electrochemical Data: Comparison of Electrochemical Data to Field Exposure Results for Coatings on Steel - Part 2

The pace of coatings development is limited by the time required to assess their corrosion protection properties. This study takes a step f orward from Part I in that it correlates the corrosion performance of organic coatings assessed by a series of short-term electrochemical measurement with 18-month beachside exposure results of duplicate pan els. A series of 19 coating systems on A36 steel substrates were test ed in a completely blind study using the damage tolerance test (DTT). In the DTT, a through-film pinhole defect is created, and the electro chemical characteristics of the defect are then monitored over the ne xt 4 to 7 days while immersed in 0.SM NaCl. The open circuit potentia l, anodic potentiostatic polarization tests and electrochemical imped ance spectroscopy were used to study the corrosion behavior of the co ating systems. The beachside exposure tests were conducted at the Ken nedy Space Center according to ASTM D610-01. It was found that for 79 % of the coatings systems examined, the 18 month beachside exposure r esults could be predicted by two independent laboratory tests obtained within 7 days.

Contu, F.