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Results for “High temperature reference electrode”

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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17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

High-Temperature Reference Electrode for Chloride Salts

The unique properties of molten salts enable their use in a wide range of applications, including metal electrodeposition, electrorefining, and as electrolytes in high-temperature batteries. Moreover, molten salts will be used as a coolant in molten salt reactors and as working media in pyrorocessing for nuclear energy applications. As a result, predicting the behavior and properties of the elements involved in the technological processes that employ molten salts is important. The activity of chloride ions in chloride molten salts has a large influence on the behavior of the salts in these applications and one of the key components in measuring the chloride activity is a stable reference electrode. This project aims to develop a reliable and convenient method for measuring chloride ion activity over a wide range of temperatures and salt compositions in chloride salt mixtures.

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

Investigation of a U(IV)/U(III) Thermodynamic Reference Electrode for High-Temperature Molten Fluoride Salts

While thermodynamic reference electrodes with known and stable potentials are common in traditional aqueous systems, the high temperature and corrosive environment of a molten fluoride salt makes achieving long term stability with a thermodynamic reference electrode challenging, especially at temperatures of 600°C or higher. In this work, a thermodynamic reference electrode consisting of U(IV)/U(III) in a boron nitride compartment was evaluated for use in FLiBe at temperatures ≥ 600°C. FLiBe used in the study was purified by AlphaTech's proprietary process and characterized by ICP-MS and square wave voltammetry. The free oxide concentration was <2 ppm. Using the purified FLiBe, the U(IV)/U(III) thermodynamic reference electrode was shown to provide a stable, well-defined, and reproducible potential for more than 600+ hours of use in different tests. Moreover, the thermodynamic reference electrode showed a consistent potential with no signs of failure, even after being cooled between tests and then reheated for reuse. Thus, the U(IV)/U(III) reference electrode is suitable for use in rigorous electrochemical studies in molten fluoride salts. As a result, it may be useful as a common standard, facilitating the advancement of nuclear applications such as isotope separation or online monitoring of reactor systems through improved certainty in the measurement of thermodynamic potentials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Stability of a Ni/NiF 2 Reference Electrode with a Metallic Membrane for Use in Molten Fluoride Salts

In this study, an experimental high-temperature fluoride salt reference electrode (RE) developed by HiFunda LLC was tested in molten FLiNaK at 550 °C. The high-temperature reference electrode (HTRE), based on the Ni/NiF 2 redox couple, was tested over a period of 13 d for short-term stability, long-term stability, and electrochemical analysis capabilities. The HTRE was tested using open circuit potentiometry (OCP), cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The HTRE reference potential was measured against changes in salt composition by increasing FeF 2 concentrations in the melt across six additions from 0 to 0.1 mol% FeF 2 . The long-term stability of the electrode was then tested over ten days at a constant composition of 0.1 mol% FeF 2 . OCP, SWV, and CV were used to calculate an average potential drift between 7–10 mV per day. Using CV and SWV, the number of electrons transferred for iron reduction and the diffusion coefficient of Fe 2+ were measured.

Electrochemistry↗
DOE OSTI2025

Challenges in selecting appropriate electrodes for high-temperature molten salt systems

Based on a specific molten salt (e.g., chloride, fluoride, iodide) investigated, different working and reference electrode materials can be selected considering the chemical and thermal stability of the electrochemical cell components. In this talk, the electrode materials and challenges encountered with a spectro-electrochemical setup installed inside a glovebox, and the solutions implemented to address these challenges, specifically for the chloride and iodide molten salts will be presented. For molten chlorides, the fundamental interactions between neodymium chloride (NdCl3) and Nd metal in lithium chloride-potassium chloride eutectic salt were investigated at 773 K. The electrochemical transitions Nd2+,3+/Nd(s) were analyzed using an inert W electrode with cyclic voltammetry and chronoamperometry techniques, coupled with in-situ UV-Vis spectroscopy to elucidate the kinetic pathways of this disproportionation reaction (eq. 1). Nd(s) + NdCl3 = NdCl2 (1) For molten iodides, the challenges related to working electrode selectivity and present spectro-electrochemical results obtained from cyclic voltammetry measurements conducted at 673 K will be discussed.

36 - MATERIALS SCIENCE↗
DOE OSTI2021

Electrochemical measurement and analysis of YCl 3 , ScCl 3 , GdCl 3 and MgCl 2 in molten eutectic LiCl-KCl

For this work, electrochemical measurements of YCl 3 , ScCl 3 , GdCl 3 and MgCl 2 were obtained in molten LiCl-KCl eutectic at 773 K using a three-electrode configuration. Tungsten rods were used as the working and counter electrodes. Two quasi- and one reference electrode(s) (glassy carbon, nickel wire, and Ni/NiO) were used to collect electrochemical measurements of the analyte salts. Cyclic voltammetry data were analyzed to calculate values of diffusion coefficient, exchange current density, and charge transfer resistance and were determined to be on the order of 10 –5 cm 2 s –1 , 10 –2 A cm –2 , and 10 0 Ω; respectively. In general, the values of diffusion coefficients were found to be consistent with those reported of high-temperature molten salts. Relatively large values of exchange current density corresponded with smaller values of charge transfer resistance. These values were found to be reasonable in comparison to results available in the literature. The measured cyclic voltammograms were normalized with respect to both lithium reduction and chloride ion oxidation potentials. Such a normalization technique is effective for comparing experimentally obtained cyclic voltammetry data to those that have been published. An analysis of experimentally obtained results indicates the relation of electrode reactions (e.g., differences of reduction potentials) are independent of the choice of reference electrode. Additionally, the choice of reference electrode did not affect the electrochemical window, exchange current density, or diffusion coefficient values.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Thermal Runaway of Nonflammable Localized High‐Concentration Electrolytes for Practical LiNi 0.8 Mn 0.1 Co 0.1 O 2 |Graphite‐SiO Pouch Cells

Abstract With continuous improvement of batteries in energy density, enhancing their safety is becoming increasingly urgent. Herein, practical high energy density LiNi 0.8 Mn 0.1 Co 0.1 O 2 |graphite‐SiO pouch cell with nonflammable localized high concentration electrolyte (LHCE) is proposed that presents unique self‐discharge characteristic before thermal runaway (TR), thus effectively reducing safety hazards. Compared with the reference electrolyte, pouch cell with nonflammable LHCE can increase self‐generated heat temperature by 4.4 °C, increase TR triggering temperature by 47.3 °C, decrease the TR highest temperature by 71.8 °C, and extend the time from self‐generated heat to triggering TR by ≈8 h. In addition, the cell with nonflammable LHCE presents superior high voltage cycle stability, attributed to the formation of robust inorganic‐rich electrode–electrolyte interphase. The strategy represents a pivotal step forward for practical high energy and high safety batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2022

High temperature corrosion sensor

A high temperature corrosion sensor is provided having (i) a housing having an external wall and an internal wall, the internal wall of the housing forming a chamber of the housing, (ii) a stainless steel tube inserted into the chamber, (iii) a ceramic tube wherein at least a portion of the ceramic tube is inserted into the stainless steel tube, (iv) an airflow tube that extends through the chamber, and (v) a sensor probe having a first working electrode, a second working electrode, a reference electrode, a positive electrical resistance, a negative electrical resistance, and a thermocouple, wherein at least a portion of each are encapsulated into a ceramic casting that is located at one end of the housing. Methods of measuring corrosion within a power plant environment are provided.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Electrochemical properties of Gd(III) ions in LiCl-KCl-GdCl 3 at 723–1023 K

Electrochemical behavior of Gd(III) ions in molten LiCl-KCl-GdCl 3 was investigated at 723–1023 K via cyclic voltammetry using tungsten as a working electrode, Gd-Bi (mole fraction, x Gd = 0.16) as a reference electrode, and Gd-Bi (x Gd = 0.02) as a counter electrode. A single reduction–oxidation wave was observed, confirming a single-step, 3-electron transfer Gd(III)/Gd transition. The cathodic peak potential exhibited minimal change (<13 mV) over a wide range of scan rates (0.05–0.30 V s –1 ), indicating facile charge transfer kinetics (i.e., a reversible electrode process). A nucleation overpotential associated with solid Gd deposition was observable at low temperatures (T < 823 K). The mass transport properties of Gd(III) ions were estimated using the Berzins and Delahay relation based on diffusion-limiting peak current. The diffusivity values were determined to be D Gd(III) = 0.5–2.7 × 10 –5 cm 2 s –1 at 723–1023 K with an associated activation energy of E a = 33.9 (±1.0) kJ mol –1 . Finally, the two-phase [liquid + GdBi] Gd-Bi alloy reference electrode experienced less than 0.5 mV of drift over 5 days of repeated electrochemical measurements, indicating high stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Process Optimization of Carbon Electrode Materials Manufacturing by Experimental Study and Machine Learning Techniques

Electrospun carbon fibers from coal have been investigated as electrodes for batteries and supercapacitors. Despite the excellent properties of coal-derived carbon fibers (CCNF) for energy storage devices, there still lacks systematic understanding on how various process parameters affect final electrode performances, which poses challenges to scale from pilot to high volume manufacturing. The goals of this project are twofold. First, we focuse on process optimization for converting a new precursor from powder river basin (PRB) coal, referred to as coal-based polyurethane (CPU) to CCNF using electrospinning. Second, different machine learning techniques will be examined using experimental data from this work and open literature. Specifically, for CPU the following process parameters need to be characterized and optimized in order to produce CCNFs with desirable mechanical integrity and physiochemical properties: precursor composition and viscosity, operating voltage and distance, oxidation and carbonization temperature and duration. Consequently, physiochemical properties of the fibers were characterized to correlate these process parameters with desirable electrochemical performance. Given the complex nature of the fiber production process, ML models are assessed for their ability to capture the nonlinear relationship between process parameters and the electrochemical properties in applications including supercapacitors. As such, we applied various machine learning techniques, to determine which technique produces a model that best predicts device function.

Cincotta, Robert E.F.↗
DOE OSTI2026

Cryogenic light detectors with thermal signal amplification for 0 νββ search experiments

As a step towards the realization of cryogenic-detector experiments to search for neutrinoless double-beta decay (such as CROSS, BINGO, and CUPID), we investigated a batch of 10 Ge light detectors (LDs) assisted by Neganov-Trofimov-Luke (NTL) signal amplification. Each LD was assembled with a large cubic light-emitting crystal (45 mm side) using the recently developed CROSS mechanical structure. The detector array was operated at milli-Kelvin temperatures in a pulse-tube cryostat at the Canfranc underground laboratory in Spain. We achieved good performance with scintillating bolometers from CROSS, made of Li 2 100 MoO 4 crystals and used as reference detectors of the setup, and with all LDs tested (except for a single device that encountered an electronics issue). No leakage current was observed for 8 LDs with an electrode bias up to 100 V. Operating the LDs at an 80 V electrode bias applied in parallel, we obtained a gain of around 9 in the signal-to-noise ratio of these devices, allowing us to achieve a baseline noise RMS of O(10 eV). Thanks to the strong current polarization of the temperature sensors, the time response of the devices was reduced to around half a millisecond in rise time. The achieved performance of the LDs was extrapolated via simulations of pile-up rejection capability for several configurations of the CUPID detector structure. Despite the sub-optimal noise conditions of the LDs (particularly at high frequencies), we demonstrated that the NTL technology provides a viable solution for background reduction in CUPID.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

High Temperature Steam Electrolysis Process Performance and Cost Estimates - DOE Hydrogen Program AMR Presentation

Technology readiness levels (TRLs) of electrolysis systems have dramatically increased in recent years as the interest in clean hydrogen production and decarbonization of transportation, industrial and other sectors increases across the globe. This is especially true of high temperature steam electrolysis (HTSE) / solid oxide electrolysis cell (SOEC) systems which show promise of much higher system efficiencies than other more developed electrolysis technologies. This possibility of higher efficiencies of HTSE / SOEC systems has been previously assumed to be theoretically possible but in recent years it has become less theoretical and more realistic as an increasing amount of suppliers complete lab and pilot tests showing very promising results. Research in the areas of manufacturing techniques, material selection, electrode and electrolyte compositions, and balance of plant size and integration continues at a fast pace as an increasing number of suppliers both internationally and domestically become involved. The advantages of HTSE become more pronounced when HTSE is coupled with nuclear power plants (NPPs). This is because thermal energy produced by the nuclear reactor can be used in a series of heat transfer loops and heat exchangers to vaporize HTSE feedwater, which drastically improves the economics of the process. Idaho National Laboratory (INL) has been very involved in the research and modeling of HTSE systems for a number of years, in collaboration with other national laboratories, academia, and industry stakeholders both on the hydrogen production as well as the hydrogen demand side. The modeling completed over the years on a large variety of projects has led to a wealth of knowledge at INL including in the area of the technoeconomic assessment (TEA) of HTSE systems. TEAs include process modeling of the HTSE systems to calculate system energy requirements and equipment sizing, followed by estimation of capital and operating costs to enable calculation of the levelized cost of hydrogen (LCOH). The TEA work performed has produced incremental improvements and tuning of the methods, assumptions, models, and results of the analyses as well as providing some opportunities for validating these results. The purpose of this document is to record the current baseline HTSE analyses led by INL to show the current status of assumptions and costs of these systems. Given the rapid development of this technology, the variety of suppliers entering the space, and the increasing attention government and industry are giving to such systems, this document may be updated on a periodic basis with updated analysis and assumptions. This document compiles various analyses results and approaches completed over a period of years into a single document to be used as a baseline going forward. It represents what the INL HTSE analysis group assumes to be the internal best estimate of the current operation, costs, and landscape of the HTSE industry state of the art capability for current SOEC technology in an Nth-of-a-Kind (NOAK) plant, which in this study is defined as existence of the manufacturing capacity to support previous deployment of N = 100 count of 25 MWe modular HTSE blocks (with modular equipment component cost reductions specified as following a 95% learning curve). That said, this is a public document and as such so no proprietary data was used or included in this report. There may be HTSE suppliers that have performance specifications, and cost estimates, and test data that differ from the analysis presented in this document. This document is meant to be a best conservative estimate of the technology and not an absolute reference.

08 HYDROGEN↗
DOE OSTI2022

High Temperature Steam Electrolysis Process Performance and Cost Estimates

Technology readiness levels (TRLs) of electrolysis systems have dramatically increased in recent years as the interest in clean hydrogen production and decarbonization of transportation, industrial and other sectors increases across the globe. This is especially true of high temperature steam electrolysis (HTSE) / solid oxide electrolysis cell (SOEC) systems which show promise of much higher system efficiencies than other more developed electrolysis technologies. This possibility of higher efficiencies of HTSE / SOEC systems has been previously assumed to be theoretically possible but in recent years it has become less theoretical and more realistic as an increasing amount of suppliers complete lab and pilot tests showing very promising results. Research in the areas of manufacturing techniques, material selection, electrode and electrolyte compositions, and balance of plant size and integration continues at a fast pace as an increasing number of suppliers both internationally and domestically become involved. The advantages of HTSE become more pronounced when HTSE is coupled with nuclear power plants (NPPs). This is because thermal energy produced by the nuclear reactor can be used in a series of heat transfer loops and heat exchangers to vaporize HTSE feedwater, which drastically improves the economics of the process. Idaho National Laboratory (INL) has been very involved in the research and modeling of HTSE systems for a number of years, in collaboration with other national laboratories, academia, and industry stakeholders both on the hydrogen production as well as the hydrogen demand side. The modeling completed over the years on a large variety of projects has led to a wealth of knowledge at INL including in the area of the technoeconomic assessment (TEA) of HTSE systems. TEAs include process modeling of the HTSE systems to calculate system energy requirements and equipment sizing, followed by estimation of capital and operating costs to enable calculation of the levelized cost of hydrogen (LCOH). The TEA work performed has produced incremental improvements and tuning of the methods, assumptions, models, and results of the analyses as well as providing some opportunities for validating these results. The purpose of this document is to record the current baseline HTSE analyses led by INL to show the current status of assumptions and costs of these systems. Given the rapid development of this technology, the variety of suppliers entering the space, and the increasing attention government and industry are giving to such systems, this document may be updated on a periodic basis with updated analysis and assumptions. This document compiles various analyses results and approaches completed over a period of years into a single document to be used as a baseline going forward. It represents what the INL HTSE analysis group assumes to be the internal best estimate of the current operation, costs, and landscape of the HTSE industry state of the art capability for current SOEC technology in an Nth-of-a-Kind (NOAK) plant, which in this study is defined as existence of the manufacturing capacity to support previous deployment of N = 100 count of 25 MWe modular HTSE blocks (with modular equipment component cost reductions specified as following a 95% learning curve). That said, This is a public document and as such so no proprietary data was used or included in this report. There may be HTSE suppliers that have performance specifications, and cost estimates, and test data that differ from the analysis presented in this document. This document is meant to be a best conservative estimate of the technology and not an absolute reference.

08 HYDROGEN↗
DOE OSTI2022

Ultra‐Thin Single‐Particle‐Layer Sodium Beta‐Alumina‐Based Composite Polymer Electrolyte Membrane for Sodium‐Metal Batteries

Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid-state sodium-metal batteries. However, the application of CPEs for high energy density solid-state sodium-metal batteries is still limited by the low Na + conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta-alumina ceramic electrolyte (SBACE) is presented. A ceramic Na + -ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na + -ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na+-ion conductivity of 0.19 mS cm -1 and a transference number of 0.91 at room temperature, contributing to long-term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as-prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g -1 at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g -1 at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.

25 ENERGY STORAGE↗
DOE OSTI2025

Examples of X-Ray Characterization Techniques in Energy Storage Research

Lithium-ion batteries have revolutionized the portable electronics and transportation sectors. Their performance is often critically dependent on the crystal structures of the anode and cathode electrode materials, which must enable the transport and reversible storage of lithium ions into and out of the lattice. Because lithium is a low-Z element, characterization of materials for lithium-ion batteries can be particularly challenging. Regardless, X-ray techniques enable analysis of material structures to better understand how battery materials perform and degrade, particularly when combined with other materials characterization and electrochemical characterization techniques. While X-ray techniques are most often used in battery research for phase identification of crystal structures, X-ray characterization techniques are also used for a wide variety of other purposes. I will discuss several examples from my research with various collaborators on several projects that highlight the impact that X-ray characterization techniques can have on battery research. The first example will focus on low-temperature microwave-assisted solvothermal synthesis of vanadium-doped LiFePO4 cathode materials for lithium-ion batteries. (1,2) Through a combination of electrochemical and materials characterization, we determined that low temperature synthesis resulted in metastable phases that enabled incorporation of higher dopant levels than resulting from high-temperature synthesis of thermodynamically stable phases. Rietveld refinement of X-ray diffraction data enabled understanding of how lattice parameters changed with doping levels and synthesis temperature. X-ray absorption near edge spectroscopy enabled understanding of the vanadium and iron oxidation states to confirm how vacancies in the structure caused by doping were charge compensated. This was important to understand because the literature suggests doping can improve LiFePO4 electrical conductivity, which improves battery charge and discharge rates. The second example will focus on understanding residual strain in lithium metal anodes. Lithium-ion batteries typically use graphite anodes, but the charge-storage capacity can be theoretically improved ~10x by using lithium metal as the anode material instead. However, lithium anodes suffer from growth of high-aspect-ratio features, such as dendrites, that can pierce nanoporous polymer separators and lead to short circuits and fires. External pressure is commonly applied to cells to enable better morphological control. We hypothesized that applied pressure may promote strain and possibly work hardening during electrochemical cycling, which motivated us to look for evidence of residual strain in lithium metal cycled under applied pressure using X-ray diffraction and sin2(..psi..) analysis. We found that lithium electrodeposited under high pressure exhibited in-plane compressive strain and that that lithium electrodeposited under low pressure did not. (3) The residual strain that accompanies electrodeposition under high pressure may lead to work hardening, which may explain how a soft metal like lithium can puncture separators and why higher pressure does not always decrease short circuits. (4-6) References: 1) Harrison, K. L.; Manthiram, A. Microwave-Assisted Solvothermal Synthesis and Characterization of Metastable LiFe1- x (VO) x PO4 Cathodes. Inorganic chemistry 2011, 50(8), 3613-3620. 2) Harrison, K. L.; Bridges, C. A.; Paranthaman, M. P.; Segre, C. U.; Katsoudas, J.; Maroni, V. A.; Idrobo, J. C.; Goodenough, J. B.; Manthiram, A. Temperature Dependence of Aliovalent-Vanadium Doping in LiFePO4 Cathodes. Chemistry of Materials 2013, 25(5), 768-781. 3) Rodriguez, M. A.; Harrison, K. L.; Goriparti, S.; Griego, J. J.; Boyce, B. L.; Perdue, B. R. Use of a Be-Dome Holder for Texture and Strain Characterization of Li Metal Thin Films via Sin2 (..psi..) Methodology. Powder Diffraction 2020, 35(2), 89-97. 4) Jungjohann, K. L.; Gannon, R. N.; Goriparti, S.; Randolph, S. J.; Merrill, L. C.; Johnson, D. C.; Zavadil, K. R.; Harris, S. J.; Harrison, K. L. Cryogenic Laser Ablation Reveals Short-Circuit Mechanism in Lithium Metal Batteries. ACS Energy Letters 2021, 6(6), 2138-2144. 5) Harrison, K. L.; Merrill, L. C.; Long, D. M.; Randolph, S. J.; Goriparti, S.; Christian, J.; Warren, B.; Roberts, S. A.; Harris, S. J.; Perry, D. L. Cryogenic Electron Microscopy Reveals That Applied Pressure Promotes Short Circuits in Li Batteries. Iscience 2021, 24(12). 6) Harrison, K. L.; Goriparti, S.; Merrill, L. C.; Long, D. M.; Warren, B.; Roberts, S. A.; Perdue, B. R.; Casias, Z.; Cuillier, P.; Boyce, B. L. Effects of Applied Interfacial Pressure on Li-Metal Cycling Performance and Morphology in 4 M LiFSI in DME. ACS Applied Materials & Interfaces 2021, 13(27), 31668-31679.

batteries↗