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DOE OSTI2025

Atomistic Insights into Lithium–Glyme Solvate Ionic Liquids: Effects of Chain Length and Anion Coordination

For this study, mixtures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in diglyme (G2), triglyme (G3) and tetraglyme (G4) at solvate ionic liquid (SIL) concentrations were investigated using classical molecular dynamics (cMD) simulations with a physically motivated force-field specifically developed for modeling these systems. The structural and dynamical properties of the mixtures were computed and analyzed. Lithium solvation shells, radial distribution functions, and X-ray structure factors were studied across the different SIL systems. Translational diffusion and rotational relaxation times were also evaluated, exhibiting similar trends with increasing glyme chain length. The results are consistent with experimental data and in good agreement with previous computational studies on G3 and G4. These findings validate the accuracy of the force field in modeling glyme systems and its use for describing the [Li(G2) 4/3 ][TFSI] mixture. Additionally, the thermal and electrochemical stability of these electrolytes were systematically examined. The thermal stability appears to be governed by cooperative interactions among glyme molecules, while the electrochemical stability is primarily influenced by Li + -anion interactions, which vary significantly with glyme chain length. Overall, the study sheds light on the crucial role of the anion in these glyme-based SILs and offers valuable insights into Li + -glyme systems at SIL concentrations, highlighting their promise as potential Li-ion battery electrolytes.

anions↗

DOE OSTI2022

On the mechanisms of ion adsorption to aqueous interfaces: air-water vs. oil-water

The adsorption of ions to water-hydrophobe interfaces influences a wide range of phenomena, including chemical reaction rates, ion transport across biological membranes, and electrochemical and many catalytic processes; hence, developing a detailed understanding of the behavior of ions at water-hydrophobe interfaces is of central interest. Here, we characterize the adsorption of the chaotropic thiocyanate anion (SCN − ) to two prototypical liquid hydrophobic surfaces, water-toluene and water-decane, by surface-sensitive nonlinear spectroscopy and compare the results against our previous studies of SCN − adsorption to the air-water interface. For these systems, we observe no spectral shift in the charge transfer to solvent spectrum of SCN − , and the Gibb’s free energies of adsorption for these three different interfaces all agree within error. We employed molecular dynamics simulations to develop a molecular-level understanding of the adsorption mechanism and found that the adsorption for SCN − to both water-toluene and water-decane interfaces is driven by an increase in entropy, with very little enthalpic contribution. This is a qualitatively different mechanism than reported for SCN − adsorption to the air-water and graphene-water interfaces, wherein a favorable enthalpy change was the main driving force, against an unfavorable entropy change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

High‐Rate Polymeric Redox in MXene‐Based Superlattice‐Like Heterostructure for Ammonium Ion Storage

Abstract Achieving both high redox activity and rapid ion transport is a critical and pervasive challenge in electrochemical energy storage applications. This challenge is significantly magnified when using large‐sized charge carriers, such as the sustainable ammonium ion (NH 4 + ). A self‐assembled MXene/n‐type conjugated polyelectrolyte (CPE) superlattice‐like heterostructure that enables redox‐active, fast, and reversible ammonium storage is reported. The superlattice‐like structure persists as the CPE:MXene ratio increases, accompanied by a linear increase in the interlayer spacing of MXene flakes and a greater overlap of CPEs. Concurrently, the redox activity per unit of CPE unexpectedly intensifies, a phenomenon that can be explained by the enhanced de‐solvation of ammonium due to the increased volume of 3 Å‐sized pores, as indicated by molecular dynamic simulations. At the maximum CPE mass loading (MXene:CPE ratio = 2:1), the heterostructure demonstrates the strongest polymeric redox activity with a high ammonium storage capacity of 126.1 C g −1 and a superior rate capability at 10 A g −1 . This work unveils an effective strategy for designing tunable superlattice‐like heterostructures to enhance redox activity and achieve rapid charge transfer for ions beyond lithium.

36 MATERIALS SCIENCE↗

NASA NTRS2008

Lithium-Ion Battery Demonstrated for NASA Desert Research and Technology Studies

Lithium-ion batteries have attractive performance characteristics that are well suited to a number of NASA applications. These rechargeable batteries produce compact, lightweight energy-storage systems with excellent cycle life, high charge/discharge efficiency, and low self-discharge rate. NASA Glenn Research Center's Electrochemistry Branch designed and produced five lithium-ion battery packs configured to power the liquid-air backpack (LAB) on spacesuit simulators. The demonstration batteries incorporated advanced, NASA-developed electrolytes with enhanced low-temperature performance characteristics. The objectives of this effort were to (1) demonstrate practical battery performance under field-test conditions and (2) supply laboratory performance data under controlled laboratory conditions. Advanced electrolyte development is being conducted under the Exploration Technology Development Program by the NASA Jet Propulsion Laboratory. Three field trials were successfully completed at Cinder Lake from September 10 to 12, 2007. Extravehicular activities of up to 1 hr and 50 min were supported, with residual battery capacity sufficient for 30 min of additional run time. Additional laboratory testing of batteries and cells is underway at Glenn s Electrochemical Branch.

Bennett, William R.↗

DOE OSTI2025

Lignin-Derived Methoxyterephthalates for Performance-Advantaged Polymers and Plasticizers

Lignin-derived aromatic carboxylic acids can be produced from oxidative catalytic processes and are promising building blocks for performance-advantaged bioproducts that leverage their inherent heteroatom functionalities. Here, we synthesize 2-methoxyterephthalate and 2,6-dimethoxyterephthalate derivatives by electrochemical carboxylation of guaiacyl- and syringyl-derived lignin monomers obtained from the oxidative deconstruction of lignin. These methoxylated terephthalates are evaluated as comonomers in poly(ethylene terephthalate) (PET) and as plasticizers that could replace petrochemically-derived isophthalate and phthalate, respectively. Specifically, we copolymerize 2-methoxy- and 2,6-dimethoxyterephthalate with dimethyl terephthalate to form several PET copolymers, both of which enable the properties of PET to be tuned, with an incorporation beyond 25% producing amorphous polyesters. At 10 mol % loading in the copolymers, we demonstrate that the bioderived comonomers exhibit comparable behavior to isophthalic acid, a commonly used comonomer in PET, by lowering the crystallinity and melting temperature. Moreover, methoxyterephthalate esters (2-ethylhexyl and butyl) are compared to phthalate and terephthalate ester counterparts used as poly(vinyl chloride) (PVC) plasticizers. The bioderived plasticizers are comparable to the petroleum-derived incumbents in reducing the glass transition temperature and increasing the thermal stability of PVC. Furthermore, the dimethoxyterephthalic esters are expected to have an extended lifetime in the polymer matrix due to their lower volatility and lower diffusion coefficients calculated by molecular dynamic simulations. These results demonstrate that the isophthalate and phthalate components in polyesters and plasticizers, respectively, could be substituted with biobased methoxyterephthalate derivatives.

09 BIOMASS FUELS↗

NASA NTRS2018

GT SUITE Fuel Cell Model Validation with Power Module Test Data

The AES Modular Power Systems (AMPS) Fuel Cell team at the NASA Glenn Research Center (GRC) has created a Microsoft Excel model of a regenerative fuel cell (RFC) system for potential lunar and Martian applications. Due to some limitations of this model, including the ability to predict transient effects in the thermal and fluidic performance of the system, a system-level transient thermal/fluids model was desired. GT-SUITE is a transient multi-physics simulation tool that is popular in the automotive industry and has a built in template for proton exchange membrane (PEM) fuel cells. However, terrestrial fuel cells used in the automotive industry vary significantly from aerospace fuel cells. A validation effort was undertaken to compare GT SUITE model results to actual data collected during the 2015 AMPS Power Module Demonstration in which the AMPS team used a PEM fuel cell system to power a 478 kg rover assembly at the Dunes test site located at GRC. The purpose of the model was to evaluate the efficacy of using GT SUITE to model a non-flow through PEM fuel cell system. The validation effort examined electrochemical performance including fuel cell stack voltage and power supplied, the thermal performance of the stack namely stack temperature and heat rejection rates, and the fluidic performance of the system including pressures, reactant consumption, and water production rates.

Gilligan, Ryan↗

DOE OSTI2020

Ultra-efficient polymer binder for silicon anode in high-capacity lithium-ion batteries

As a highly promising anode material for high-capacity lithium-ion batteries (LIBs), the low electronic conductivity and large volume variation of silicon (Si) make the slurry-coating Si based electrode requiring high content of “inert” materials and suffering rapid capacity fading. In this work, a polyimine, synthesized via one-step condensation reaction, has been demonstrated as an ultra-efficient polymer binder that can resolve the above issues. The polyimine binder containing Si electrode delivers superior electrochemical performance: a delithiation specific capacity of 804.4 mAh g –1 with capacity retention of 82.4% after 1000 cycles at the current density of 2 A g –1 . The high efficiency of polyimine binder for Si electrode has also been demonstrated with ultrahigh weight ratio of “active” material to “inert” material (R A/I ). The electrode with 95 wt% of Si (95Si/Polyimine, R A/I = 19) reveals a reversible delithiation capacity of 2114 mAh g –1 (capacity retention ~ 80.4%) over 200 cycles at the current density of 400 mA g –1 . Even at the high current density of 2 A g –1 , a delithiation capacity of 1087.8 mAh g –1 after 500 cycles can be obtained. Molecular simulations and atomic force microscopy (AFM) indentation are utilized to investigate the ultra-efficiency of polyimine binder. With simple manufacturing process and ultra-efficient binder performance, the designed polyimine binder will be definitely meaningful in achieving low-cost and high-capacity LIBs with prolonged cycle life.

25 ENERGY STORAGE↗

DOE OSTI2024

Force Fields for High Concentration Aqueous KOH Solutions and Zincate Ions

Motivated by increasing interest in electrochemical devices that include highly alkaline electrolytes, we investigated two force fields for potassium hydroxide (KOH) at high concentrations in water. The “FNB” model uses the SPC/E water model, while the “FHM” model uses the TIP4P/2005 water model. Here, we also developed parameters to describe zincate ions in these solutions. The density and viscosity of KOH using the FHM model are in better agreement with experiment than the values from the FNB model. Comparing the properties of the zincate solutions to the available experimental data, we find that both force fields agree reasonably well, although the FHM parameters give a better prediction of the viscosity. The developed force field parameters can be used in future simulations of zincate/KOH solutions in combination with other species of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Unraveling interphase-driven failure pathways in LiMn0.6Fe0.4PO4/graphite pouch cells

LiMnxFe1−xPO4 (LMFP) is a promising high-voltage, thermally stable, and earth-abundant cathode material, yet its practical application is limited by interphase instability and Mn dissolution. In this work, we systematically evaluate LiMn0.6Fe0.4PO4/graphite pouch cells using three electrolyte formulations including control carbonate electrolyte, control + 2 wt% vinylene carbonate (VC), and control + 2 wt% VC + 1 wt% 1,3,2-dioxathiolane 2,2-dioxide (DTD), to establish how electrolyte composition governs interphase chemistry and long-term degradation. Electrochemical testing shows that both additives are preferentially reduced prior to ethylene carbonate (EC) during cell formation, generating robust cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) layers that suppress gas evolution and raise the first-cycle coulombic efficiency to 89.3%. Additionally, the dual-additive electrolyte delivers the most stable performance, retaining over 85% capacity after 600 cycles while minimizing impedance growth under long-term cycling at C/3 and 40 °C. Soft X-ray absorption spectroscopy confirms that VC + DTD effectively suppresses electrolyte oxidation at the cathode surface, and micro-X-ray fluorescence shows substantially reduced Mn dissolution and deposition on the graphite anode. Density functional theory simulations further provided insights into the structural and energetic influences of alkoxide species on the cathode surface, proposing a Mn2+ extraction mechanism. The combined experimental and computational findings establish a mechanistic link between electrolyte composition and interphase evolution, highlighting the effectiveness of electrolyte engineering for extending the operational lifetime of LMFP-based lithium-ion batteries.

Chak, Chanmonirath Michael↗

DOE OSTI2025

Development of a Robust Reference Electrode in Aggressive Chemical and Radiation Environments in the Hanford Waste Tanks

The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.

Sykes, Kiana [Savannah River National Laboratory (↗

DOE OSTI2020

Unlocking multiphysics design guidelines on Si/C composite nanostructures for high-energy-density and robust lithium-ion battery anode

In general, current material fabrication guidance for novel designs of Si/C composite particle materials focuses on electrochemical behavior and redox reactions at the nano/micro level. However, such guidance cannot provide detailed information for predicting mechanical deformations of the composite particles, especially when the mechanical field coupled with electrochemical and thermal fields. Here, we establish an electro-chemo-mechanical model and implement it to quantitatively analyze the multiphysics behavior of five representative Si/C composite nanostructures. Modeling and computation discover that yolk-shell and dual-shell structures are more robust in terms of particle fractures. When considering electrochemical performance, the yolk-shell structure is the best among the compared five Si/C composites. Finally, we map design guidance to further illustrate quantitative structure-property relationships. This study provides novel insights on Si/C composite nanostructure anode material design and additional powerful design tools for next-generation high-energy-density lithium-ion batteries.

25 ENERGY STORAGE↗

DOE OSTI2021

Investigations of the stability of etched or platinized p-InP(100) photocathodes for solar-driven hydrogen evolution in acidic or alkaline aqueous electrolytes

Here, the stability of p-InP photocathodes performing the hydrogen-evolution reaction (HER) has been evaluated in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq), with a focus on identifying corrosion mechanisms. Stability for the solar-driven HER was evaluated using p-InP electrodes that were either etched or coated with an electrodeposited Pt catalyst (p-InP/Pt). Variables such as trace O 2 were systematically controlled during the measurements. Changes in surface characteristics after exposure to electrochemical conditions as well as electrode dissolution processes were monitored using X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). In either H 2 SO 4 or KOH, etched p-InP photoelectrodes corroded cathodically under illumination, forming metallic In 0 at the electrode surface. In contrast, electrodeposition of Pt kinetically stabilized illuminated p-InP photocathodes in both H 2 SO 4 and KOH by inhibiting the cathodic corrosion pathway. Notably, when held at 0 V vs. the reversible hydrogen electrode (RHE) in 1.0 M H 2 SO 4 (aq), p-InP/Pt exhibited a stable current density (J) of ~–18 mA cm –2 for >285 h under simulated 1 Sun illumination. The long-term current density vs. potential (J–E) behavior at pH 0 and pH 14 of p-InP/Pt photocathodes correlated with changes in the surface chemistry as well as the dissolution of p-InP. In acidic media, the J–E behavior of p-InP/Pt photocathodes remained nearly constant with time, but the surface of a p-InP/Pt electrodes gradually turned P-rich via a slow and continuous leaching of In ions. In alkaline electrolyte, the surface of p-InP/Pt electrodes was passivated by formation of an InO x layer that exhibited negligible dissolution but led to a substantial degradation in the J–E characteristics. Consequently, changes in the catalytic kinetics and surface stoichiometry are both important considerations for determining the corrosion chemistry and the long-term operational stability of InP photoelectrodes.

14 SOLAR ENERGY↗

DOE OSTI2023

Computationally Guided Design of Multiple Impurities Tolerant Cathode for Solid Oxide Fuel Cell Applications

Solid oxide fuel cells (SOFCs) have been recognized as promising candidates in the demand of reducing the dependence on fossil fuels, which is one of the solutions to the threat of global warming. It was reported that the direct chemical-to-electrical energy conversion in SOFCs comes with negligible emission of greenhouse gases and up to 60% working efficiency. SOFC has unique advantages over traditional power generation technologies and other types of fuel cells due to the use of relatively inexpensive materials, low sensitivity to poisoning impurities in fuels, relatively high conversion efficiency, and fuel flexibility (like carbon-based fuels). However, during the SOFC operation, the cathode is exposed to intrinsic and extrinsic airborne contaminants at high temperatures (600–900°C), leading to their reaction with electrode materials, irreversible chemical and structural changes, and electrochemical performance degradation. of which CO2, SO2, Cr6+ and H2O are known to be concerns. Thus, developing a comprehensive understanding of the multiple impurities poisoning of SOFC cathodes in the presence of single or multiple impurities is necessary to address the long-term degradation of the SOFC cathode systems at operating conditions. An integrated computational and experimental approach has been utilized in the current work aiming at the comprehensive investigation of the cathode materials under single or multiple impurities poisoning effects, understanding the multiple impurities poisoning mechanism(s), and improving the long-term durability of the SOFC cathodes to develop better performing impurity-tolerant cathode materials. We first examined the agreement between the simulation approach and the experimental observations at various atmospheric and temperature conditions to confirm the reliability of CALPHAD for poisoning simulations in these cathodes. Then, using this approach, we investigated the accelerated testing protocol, which has become the standard method for conducting impurity poisoning experiments involving these cathode materials. We found our simulation approach is able to predict in which systems, i.e., cathode material and treatment environment, the accelerated testing protocols reflect actual operating conditions. Finally, in-depth simulations were done for these three candidate cathodes under different experimental conditions and suggested directions toward alternative cathode materials that have superior impurity tolerance.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures

Abstract The key component in lithium solid‐state batteries (SSBs) is the solid electrolyte composed of lithium superionic conductors (SICs). Lithium oxide SICs offer improved electrochemical and chemical stability compared with sulfides, and their recent advancements have largely been achieved using materials in the garnet‐ and NASICON (sodium superionic conductor)‐ structured families. In this work, using the ion‐conduction mechanisms in garnet and NASICON as inspiration, a common pattern of an “activated diffusion network” and three structural features that are beneficial for superionic conduction: a 3D percolation Li diffusion network, short distances between occupied Li sites, and the “homogeneity” of the transport path are identified. A high‐throughput computational screening is performed to search for new lithium oxide SICs that share these features. From this search, seven candidates are proposed exhibiting high room‐temperature ionic conductivity evaluated using ab initio molecular dynamics simulations. Their structural frameworks including spinel, oxy‐argyrodite, sodalite, and LiM(SeO 3 ) 2 present new opportunities for enriching the structural families of lithium oxide SICs.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Interfacial Connections between Organic Perovskite/n + Silicon/Catalyst that Allow Integration of Solar Cell and Catalyst for Hydrogen Evolution from Water

Abstract The rapidly increasing solar conversion efficiency (PCE) of hybrid organic–inorganic perovskite (HOIP) thin‐film semiconductors has triggered interest in their use for direct solar‐driven water splitting to produce hydrogen. However, application of these low‐cost, electronic‐structure‐tunable HOIP tandem photoabsorbers has been hindered by the instability of the photovoltaic‐catalyst‐electrolyte (PV+E) interfaces. Here, photolytic water splitting is demonstrated using an integrated configuration consisting of an HOIP/n + silicon single junction photoabsorber and a platinum (Pt) thin film catalyst. An extended electrochemical (EC) lifetime in alkaline media is achieved using titanium nitride on both sides of the Si support to eliminate formation of insulating silicon oxide, and as an effective diffusion barrier to allow high‐temperature annealing of the catalyst/TiO 2 ‐protected‐n + silicon interface necessary to retard electrolytic corrosion. Halide composition is examined in the (FA 1‐x Cs x )PbI 3 system with a bandgap suitable for tandem operation. A fill factor of 72.5% is achieved using a Spiro‐OMeTAD‐hole‐transport‐layer (HTL)‐based HOIP/n + Si solar cell, and a high photocurrent density of −15.9 mA cm −2 (at 0 V vs reversible hydrogen electrode) is attained for the HOIP/n + Si/Pt photocathode in 1 m NaOH under simulated 1‐sun illumination. While this thin‐film design creates stable interfaces, the intrinsic photo‐ and electro‐degradation of the HOIP photoabsorber remains the main obstacle for future HOIP/Si tandem PEC devices.

08 HYDROGEN↗

DOE OSTI2023

Electronic signatures of Lorentzian dynamics and charge fluctuations in lithiated graphite structures

Lithium graphite intercalation compounds (Li-GICs) are essential materials for modern day portable electronics and obtaining insights into their atomic structure and thermodynamics is of fundamental interest. Here we explore the electronic and atomic states of Li-GICs at varying degrees of Lithium loading (i.e., “staging”) by means of ab-initio molecular dynamics simulations and simulated X-ray adsorption spectroscopy (XAS). We analyze the atomic correlation functions and shows that the enhancements of the Li-ion entropy with increased staging result from Lorentzian lithium-ion dynamics and charge fluctuations, which activate low-energy phonon modes. The associated electronic signatures are modulations of the unoccupied π*/σ* orbital energy levels and unambiguous fingerprints in Carbon K-edge XAS spectra. Thus, we extend the canonical view of XAS, establishing that these “static” measurements in fact encode the signature of the thermodynamic response and relaxation dynamics of the system. This causal link between atomic structure, spectroscopy, thermodynamics, and information theory can be generally exploited to better understand stability in solid-state electrochemical systems.

25 ENERGY STORAGE↗

DOE OSTI2021

Irradiation effects in tungsten—From surface effects to bulk mechanical properties

Advanced materials such as tungsten fibre-reinforced composites allow to overcome severe weaknesses of the baseline materials for plasma-facing components — copper and tungsten. The effect of the fusion environment on the mechanical properties of these materials, e.g. the embrittlement by neutron irradiation, plays a key role for the development of future fusion reactors. To simulate this effect, high-energy ions are used as a substitute for the displacement damage by neutrons. We propose the use of very fine tungsten wire as a possibility of studying the influence of irradiation damage on the mechanical properties. This is possible as they allow full-depth irradiation of almost the entire volume despite the limited penetration depth of ions. Geometrical size effects are mitigated due to the nanoscale microstructure of the wire. In addition, similar wire is used in tungsten fibre-reinforced composites. Thus, the investigation of irradiated wire can directly be used for the prediction of the bulk composite properties. For the proof of this concept tungsten wire with a diameter of 16 μm was electrochemically thinned to 5 μm and irradiated with 20.5 MeV W 6+ ions. The mechanical properties were subsequently determined by macroscopic tensile testing. Irradiation to 0.3, 1 and 9 dpa did not lead to a change of the mechanical behaviour. Both strength and ductility, the latter indicated by the reduction of area, were similar to the as-fabricated state.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent

Deep eutectic solvents (DESs) are emerging as promising electrolytes for electrochemical energy storage applications. Electroactive nitroxide-radical-containing organics can be dissolved in DESs to facilitate redox reactions; however, mechanistic know-how of their charge transfer kinetics at the electrode surface is rather limited. Here, we investigate the mechanism underlying the electrochemical oxidation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (4-hydroxy-TEMPO). Using polarization measurements on a platinum rotating disk electrode and micro-electrode, we show that the anodic charge transfer coefficient (a) for one-electron transfer oxidations of TEMPO and4-hydroxy-TEMPO approaches 0.9 in DES as well as in aqueous electrolytes, i.e., a significant deviation fromα≈0.5 expected for symmetric redox behavior. To explain this observation, a two-step oxidation mechanism is proposed wherein the nitroxide-containing species undergo fast charge transfer at an electrode surface followed by slow rate-limiting desorption of the adsorbed oxidized species. Numerical simulations are reported to characterize how the proposed two-step mechanism manifests intransient cyclic voltammetry behavior of the 4-hydroxy-TEMPO oxidation reaction, and good agreement with experiments is noted.

25 ENERGY STORAGE↗