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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Carbon decorated Li 3 V 2 (PO 4 ) 3 for high-rate lithium-ion batteries: Electrochemical performance and charge compensation mechanism

Fast charging and high-power delivering batteries are highly demanded in mobile electronics, electric vehicles and grid energy storage, but there are full of challenges. The star-material Li 3 V 2 (PO 4 ) 3 is demonstrated as a promising high-rate cathode material meeting the above requirements. Herein, we report the carbon decorated Li 3 V 2 (PO 4 ) 3 (LVP/C) cathode prepared via a facile method, which displays a remarkable high-rate capability and long-term cycling performance. Briefly, the prepared LVP/C delivers a high discharge capacity of 122 mAh g -1 (~93% of the theoretical capacity) at a high rate up to 20 C and a superior capacity retention of 87.1% after 1000 cycles. Importantly, by applying a combination of X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering, we clearly elucidate the structural and chemical evolutions of LVP upon various potentials and cycle numbers. Furthermore, we show unambiguous spectroscopic evidences that the evolution of the hybridization strength between V and O in LVP/C as a consequence of lithiation/delithiation is highly reversible both in the bulk and on the surface during the discharge-charge processes even over extended cycles, which should be responsible for the remarkable electrochemical performance of LVP/C. Our present study provides not only an effective synthesis strategy but also deeper insights into the surface and bulk electrochemical reaction mechanism of LVP, which should be beneficial for the further design of high-performance LVP electrode materials.

25 ENERGY STORAGE↗
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 OSTI2023

Structural and electrochemical evolution of alloy interfacial layers in anode-free solid-state batteries

“Anode-free” solid-state batteries feature high energy density since there is no anode active material. Although the beneficial effects of interfacial layers at the anode-solid electrolyte interface have been demonstrated, the mechanisms through which they influence lithium plating/stripping are unclear. Here, in this study, we reveal the evolution of 100-nm silver and gold interfacial layers during lithium plating/stripping using electrochemical methods, electron microscopy, X-ray microcomputed tomography, and modeling. The alloy layers improve Coulombic efficiency and resistance to short circuiting, even though the alloys form solute regions or particulates that detach from the current collector during plating. In situ electrochemical impedance spectroscopy shows that the alloys return to the interface and mitigate contact loss at the end of stripping, avoiding a critical vulnerability of anode-free cells. Contact retention is driven by even Li thickness that promotes spatially uniform stripping, as well as local alloy delithiation in response to current concentrations that homogenizes current and diminishes voiding.

25 ENERGY STORAGE↗
DOE OSTI2020

Correlative electron and ion beam analysis of the electrochemical performances of LiV 3 O 8 cathode films as a function of microstructures

Degradation mechanisms in LiV 3 O 8 cathode films (~500 nm) with different initial microstructures i.e., globular nanocrystals in amorphous matrix and needle-like nanocrystals, synthesized by annealing the cathodes at 150 °C and 300 °C for 6 h are studied by Transmission Electron Microscopy (TEM) and Auger Electron Spectroscopy (AES). In addition, a unique in-situ combination of TEM and Secondary Ion Mass Spectrometry (SIMS) imaging techniques, namely Parallel Ion and Electron beam Spectrometry (PIES) is carried out to measure the 3D distribution of V and Li with nanoscale resolution. These characterization studies focus on correlating the pre- and post-cycling microstructure to observed electrochemical performance. The LiV 3 O 8 cathode film with needle-like nanocrystals (300 °C) shows a higher initial capacity but it degrades rapidly compared to the film with globular nanocrystals embedded in amorphous matrix (150 °C). We observed that LiV 3 O 8 films with needle-like nanocrystals are more susceptible to cathode decohesion and vanadium dissolution than the films with globular nanocrystals embedded in amorphous matrix, explaining the differences in their electrochemical performance. The findings from this study have relevance to the development of thin film electrode microstructures for high capacity and cyclic stability.

25 ENERGY STORAGE↗
DOE OSTI2021

Multi-fidelity electrochemical modeling of thermally activated battery cells

Thermally activated batteries undergo a series of coupled physical changes during activation that influence battery performance. These processes include energetic material burning, heat transfer, electrolyte phase change, capillary-driven two-phase porous flow, ion transport, electrochemical reactions, and electrical transport. Several of these processes are strongly coupled and have a significant effect on battery performance, but others have minimal impact or may be suitably represented by reduced-order models. Additionally, assessing the relative importance of these phenomena must be based on comparisons to a high-fidelity model including all known processes. In this work, we first present and demonstrate a high-fidelity, multi-physics model of electrochemical performance. This novel multi-physics model enables predictions of how competing physical processes affect battery performance and provides unique insights into the difficult-to-measure processes that happen during battery activation. We introduce four categories of model fidelity that include different physical simplifications, assumptions, and reduced-order models to decouple or remove costly elements of the simulation. Using this approach, we show an order-of-magnitude reduction in computational cost while preserving all design-relevant quantities of interest within 5 percent. The validity of this approach and these model reductions is demonstrated by comparison between results from the full fidelity model and the different reduced models.

25 ENERGY STORAGE↗
DOE OSTI2025

Predicting Si-Anode Calendar Life Using Machine Learning: Correlating Electrolyte Properties and Electrochemical Signals

This study evaluates novel electrolytes tailored for Si-containing anodes to promote calendar-life. Drawing inspiration from advancements in electrolytes for Li-metal cells, the work investigates correlations between predicted electrolyte properties and measured electrochemical performance using several machine-learning models. By leveraging machine learning and advanced modeling techniques, this study aims to establish predictive frameworks that accelerate calendar-aging experiments and inform rational electrolyte design for Si-containing cells. In the present study, fifteen different electrolytes are evaluated in a Si-containing cell using an accelerated calendar-life protocol. For each electrolyte considered, 87 properties (features) from the Advanced Electrolyte Model were produced to identify key property/performance relationships. In this study, the best performing electrolytes were generally those formulations that included non-coordinating fluoroether solvents, and the most predictive features for long-term calendar-life were features related to salt concentration and electrolyte viscosity as well as early capacity, ionic conductivity, and Coulombic efficiency measurements. The framework developed in this study correlating electrolyte properties to measured electrochemical performance is expected to accelerate electrolyte design for Si-containing anodes and ultimately enable high-energy-density, long-life Li-ion batteries.

25 - ENERGY STORAGE↗
DOE OSTI2026

A structural and electrochemical study of perfluoropolyether-poly(ethylene oxide) solid polymer electrolytes

Solid polymer electrolytes offer attractive safety, processability, and interfacial adhesion for enabling high–energy solid-state lithium batteries, but they are often limited by narrow oxidative stability windows and low lithium-ion transference numbers. In an attempt to broaden the electrochemical stability window and increase lithium-ion transference number of poly(ethylene oxide) (PEO)-based solid polymer electrolytes, we produce an optically clear, crosslinked membrane of PEO and perfluoropolyether (PFPE) using a mixed solvent method and subsequently infuse the membrane with a lithium salt. Structural and thermal analyses reveal nanoscale phase separation between fluorocarbon and hydrocarbon domains with characteristic spacings of 7–8 nm and an elevated glass transition for the hydrocarbon phase. Consistent with this, PFPE-containing membranes exhibit substantially lower ionic conductivity than PEO analogs (dry and plasticized). The transference number and electrochemical stability are similar to pure PEO. These results demonstrate that fluorination implemented as segregated nanoscale domains does not deliver the anticipated transport or stability benefits; instead, phase separation increases tortuosity and suppresses hydrocarbon-phase dynamics. The work underscores the importance of fluorine placement and morphology control, guiding the design of partially fluorinated solid polymer electrolytes toward architectures that avoid detrimental nanoscale phase separation.

Carden, Peyton [ORNL] (ORCID:0000000162296538)↗
DOE OSTI2022

Energy-Efficient Microbial Electrochemical Lignin and Alkaline Hydroxide Recovery from DMR Black Liquor

Black liquor is a complex waste stream generated from the fast-expanding biorefinery industry, and the high management cost has been known as a major development barrier. In this work, we demonstrated a rationally designed 4-chamber microbial electrolysis process that was capable of recovering the value-added lignin, NaOH, and H2 products while removing waste organics from the Deacetylation and Mechanical Refining (DMR) black liquor, which could potentially reduce the disposal cost by up to 40%. The lab-scale MEC achieved 52% organic removal from a highly concentrated feedstock (28,960 ± 212 mg/L COD) and recovered 83.2 mM NaOH under a small voltage application (1.2 V). Lignin recovery was observed to be as high as 13.98 +/- 0.28 g/L, and 0.35 L/L/day H2 was produced with a faradaic efficiency of 93.5%. This work provided a good example on how complex liquid waste stream can be valorized via multi-functional microbial electrochemical technology, and how the traditionally unfavored pH gradient in an electrochemical reactor can be manipulated for lignin precipitation and alkaline recovery at the same time. The versatility and good performance in concurrent contaminants removal, lignin precipitation, H2 production and NaOH recovery demonstrate a good potential for microbial electrolysis in black liquor treatment.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2022

Spectroscopic investigation of the electronic and excited state properties of para-substituted tetraphenyl porphyrins and their electrochemically generated ions

Porphyrins play pivotal roles in many crucial biological processes including photosynthesis. However, there is still a knowledge gap in understanding electronic and excited state implications associated with functionalization of the porphyrin ring system. These effects can have electrochemical and spectroscopic signatures that reveal the complex nature of these somewhat minor substitutions, beyond simple inductive or electronic effect correlations. To obtain a deeper insight into the influences of porphyrin functionalization, four free-base, meso-substituted porphyrins: tetraphenyl porphyrin (TPP), tetra(4-hydroxyphenyl) porphyrin (THPP), tetra(4-carboxyphenyl) porphyrin (TCPP), and tetra(4-nitrophenyl) porphyrin (TNPP), were synthesized, characterized, and investigated. The influence of various substituents, (-hydroxy,-carboxy, and -nitro) in the para position of the meso-substituted phenyl moieties were evaluated by spectroelectrochemical techniques (absorption and fluorescence), femtosecond transient absorption spectroscopy, cyclic and differential pulse voltammetry, ultraviolet photoelectron spectroscopy (UPS), and time-dependent density functional theory (TD-DFT). Spectral features were evaluated for the neutral porphyrins and differences observed among the various porphyrins were further explained using rendered frontier molecular orbitals pertaining to the relevant transitions. Electrochemically generated anionic and cationic porphyrin species indicate similar absorbance spectroscopic signatures attributed to a red-shift in the Soret band. Emissive behavior reveals the emergence of one new fluorescence decay pathway for the ionic porphyrin, distinct from the neutral macrocycle. Femtosecond transient absorption spectroscopy analysis provided further analysis of the implications on the excited-state as a function of the para substituent of the free-base meso-substituted tetraphenyl porphyrins. Herein, we provide an in-depth and comprehensive analysis of the electronic and excited state effects associated with systematically varying the induced dipole at the methine bridge of the free-base porphyrin macrocycle and the spectroscopic signatures related to the neutral, anionic, and cationic species of these porphyrins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Conspectus (Photo)electrochemical energy conversion is important in the development of a carbon-neutral energy economy because it can provide a pathway for mitigating the intermittency of renewable energy sources such as wind and solar. In order to operate efficiently, these technologies, which include photoelectrochemical cells, water and CO 2 electrolyzers, fuel cells, and redox flow batteries, require fast charge transfer kinetics at the electrode/electrolyte interface as well as robust ion management in the electrolyte. In conventional electrolyzers and fuel cells, the electrolyte is strongly acidic or basic and ionic current is carried by H + or OH – ions. In contrast, photoelectrodes and electrocatalysts for water splitting are often studied in buffered solutions. The question of ion balance in these systems led us to analyze the polarization losses due to ion concentration gradients in cells that employed various buffer–membrane combinations. Continuously driving the buffer ions across an ionomer membrane not only lowers the buffer capacity of an aqueous electrolyte but also introduces pH gradients that result in significant energy losses. To address the problem, we and other groups have studied the use of reverse-biased bipolar membranes (BPMs) in (photo)electrolytic cells. BPMs consist of an anion exchange layer (AEL) laminated with a cation exchange layer (CEL) and are usually equipped with a catalytic layer in between to accelerate the water dissociation reaction. At the AEL/CEL interface, water dissociates into protons and hydroxide ions, which replenish those consumed at the cathode and anode. Compared to conventional water electrolyzers with proton/anion exchange membranes (PEM/AEM), BPM electrolyzers provide the unique advantage of continuously operating the cathode and anode under different pH conditions, which is desirable when the two electrode reactions have different pH requirements. BPMs also enable the use of buffered electrolytes at pH values that are optimized for electrode stability and product selectivity in applications such as CO 2 electrolysis. Product crossover losses and CO 2 pumping can be dramatically reduced in BPM-based CO 2 electrolyzers, relative to conventional alkaline membranes, by electrostatic repulsion (of anionic products) and electroosmotic drag (for neutral products). BPM-based gas fed CO 2 electrolyzers can achieve high current density, but they suffer from low Faradaic efficiency (FE) due to the acidic local environment of the CEL. This problem can be mitigated by adding an aqueous buffering layer or by creating a weak acid cation exchange film on the CEL face of the membrane. The use of BPMs in fuel cells and redox flow batteries offers some interesting advantages. Configurations with both reverse and forward bias have been studied, but forward bias has been favored due to material compatibility, reaction kinetics, and thermodynamic considerations. The net reaction at the AEL/CEL interface is the acid–base neutralization reaction, which has a high inherent reaction rate constant, but in the BPM is limited to a nanometric space-charge layer and requires efficient catalysis to achieve high current density. Understanding the mechanism of the acid–base neutralization and the opposite process, the water dissociation reaction, will be essential for improving the performance of forward-biased BPMs. In conclusion, this Account reviews our current understanding of the working mechanisms of BPMs and discusses how we can use them to effectively manage ions for various (photo)electrochemical applications.

Yan, Zhifei↗
DOE OSTI2020

Electrochemical Detection of Oxycodone and Its Main Metabolites with Nafion-Coated Single-Walled Carbon Nanotube Electrodes

Oxycodone is a strong opioid frequently used as an analgesic. Although proven efficacious in the management of moderate to severe acute pain and cancer pain, use of oxycodone imposes a risk of adverse effects such as addiction, overdose, and death. Fast and accurate determination of oxycodone blood concentration would enable personalized dosing and monitoring of the analgesic as well as quick diagnostics of possible overdose in emergency care. However, in addition to the parent drug, several metabolites are always present in the blood after a dose of oxycodone, and to date, there is no electrochemical data available on any of these metabolites. In this paper, a single-walled carbon nanotube (SWCNT) electrode and a Nafion-coated SWCNT electrode were used, for the first time, to study the electrochemical behavior of oxycodone and its two main metabolites, noroxycodone and oxymorphone. Both electrode types could selectively detect oxycodone in the presence of noroxycodone and oxymorphone. However, we have previously shown that addition of a Nafion coating on top of the SWCNT electrode is essential for direct measurements in complex biological matrices. Therefore, in this work, the Nafion/SWCNT electrode was further characterized and used for measuring clinically relevant concentrations of oxycodone in buffer solution. The limit of detection for oxycodone with the Nafion/SWCNT sensor was 85 nM, and the linear range was 0.5–10 μM in buffer solution. Furthermore, this study shows that the fabricated Nafion/SWCNT sensor has potential to be applied in clinical concentration measurements.

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

Scanning Electrochemical Microscopy for Kinetic Investigations in Viscous Deep Eutectic Solvents: Identifying Practical Approach Curves and Deviations from Electron Transfer Models

Determining heterogeneous electrochemical electron transfer (ET) kinetics in electrolytes with a wide range of physical properties is of great interest for achieving high-performance redox flow batteries. Among such electrolytes, concentrated hydrogen-bonded electrolytes (CoHBEs), including deep eutectic solvents (DESs), have recently garnered significant attention. Unfortunately, traditional Tafel analysis using macroelectrodes often encounters issues with mass transfer limitations in CoHBEs with high viscosities, thereby restricting kinetic analysis to a narrow potential window. Here, in this work, we introduce a methodology for evaluating ET kinetics in viscous DES using the scanning electrochemical microscopy (SECM). We first determined practical solutions to SECM tip positioning in ethaline DES, which yield pseudopositive feedback responses. Lattice Boltzmann method (LBM) simulations helped us rationalize the impact of the fluid and concentration fields, as well as tip geometry, tip approach velocity v, and the solvent viscosity ηs, on the shape of the approach curves. In addition to successfully recreating approach curves over a variety of conditions, we found that approaching a conductor ensured a practical point where the normalized tip response (Ni T = 2) converged at L = 0.7 within ∼10% error regardless of tip velocity. With positioning capabilities at hand, we investigated the kinetics of Fe 3+ /Fe 2+ redox couple in aqueous and the ethaline media. The experimental kinetic results were interpreted using the Butler–Volmer (BV) and Marcus–Hush–Chidsey (MHC) models. For ethaline, a nonideal kinetic behavior was observed, potentially attributed to solvent dynamics within DESs or to the interplay of chloride anions in the charge transfer process.

electrodes↗
DOE OSTI2020

Production of C 2 /C 3 Oxygenates from Planar Copper Nitride-Derived Mesoporous Copper via Electrochemical Reduction of CO 2

Electrochemical reduction of CO 2 provides an opportunity to produce fuels and chemicals in a carbon-neutral manner, assuming that CO 2 can be captured from the atmosphere. To do so requires efficient, selective, and stable catalysts. In this study, we report a highly mesoporous metallic Cu catalyst prepared by electrochemical reduction of thermally nitrided Cu foil. Under aqueous saturated CO 2 reduction conditions, the Cu 3 N-derived Cu electrocatalyst produces virtually no CH 4 , very little CO, and exhibits a faradaic efficiency of 68% in C 2+ products (C 2 H 4 , C 2 H 5 OH, and C 3 H 7 OH) at a current density of ~18.5 mA cm –2 and a cathode potential of -1.0 V versus the reversible hydrogen electrode. Under these conditions, the catalyst produces more oxygenated products than hydrocarbons. We show that surface roughness is a good descriptor of catalytic performance. The roughest surface reached 98% CO utilization efficiency for C 2+ product formation from CO 2 reduction and the ratio of oxygenated to hydrocarbon products correlates with the degree of surface roughness. These effects of surface roughness are attributed to the high population of undercoordinated sites as well as a high pH environment within the mesopores and adjacent to the surface of the catalyst.

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

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

The electrochemical lithiation and delithiation of the layered oxysulfide Sr 2 MnO 2 Cu 4-δ S 3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and 7 Li NMR spectroscopy, together with a range of electrochemical experiments. Sr 2 MnO 2 Cu 4-δ S 3 consists of [Sr 2 MnO 2 ] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu 4-δ S 3 ] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li 4 S 3 slabs and Cu + is reduced and extruded as metallic particles. For the initial 2-3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn 2.5+ is reduced to Mn 2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn 2+ to Mn 2.5+ . However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

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

Structure and Electrochemical Properties of Bronze Phase Materials Containing Two Transition Metals

Bronze phase transition-metal oxides have recently attracted attention as high-rate lithium-ion battery anode materials. Their crystal structures are distinguished by large tunnels and an open framework, facilitating lithium-ion diffusion and high-rate charge–discharge properties. The presence of two transition metals also offers a route to achieve high energy density from multielectron redox. In this paper, we report the chemistry, structure, and electrochemical properties of two different bronze phase compositions having the same stoichiometry: W 3 Nb 2 O 14 and Mo 3 Nb 2 O 14 . These materials provide insight into how the transition metals affect the electrochemical behavior and structural stability of bronze phase materials. Mo 3 Nb 2 O 14 exhibits greater than 1 electron redox per transition metal leading to lithium capacities above 200 mAh g –1 at C/2 but is unable to maintain this high capacity at high rates due to incomplete Mo redox reactions. In contrast, W 3 Nb 2 O14 exhibits reversible redox reactions and retains its open structure on cycling. This study highlights the potential of bronze phase materials containing two transition metals to exhibit fast charging properties with a high energy density.

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

Understanding the Beneficial Role of Transition-Metal Layer Na + Substitution on the Structure and Electrochemical Properties of the P2-Layered Cathode Na 2+ x Ni 2– x /2 TeO 6

Layered Na x MO 2 sodium oxide positive electrode materials have experienced renewed interest owing to the current commercial attention on sodium-ion batteries. Although there are many attractive qualities of these materials, they suffer from serious shortcomings owing to Na + ordering and transition-metal layer gliding that cause a plethora of voltage plateaus during cycling. The P2-layered Na 2+x Ni 2–x/2 TeO 6 (0 ≤ x ≤ 0.5) system provides a framework for investigating the effect of dual Na + substitution into the sodium layer and the transition-metal layer of the structure and its effects on the electrochemical properties of the materials. A careful investigation into the synthesis and properties of these materials reveals that the sodium content used during material preparation has a drastic effect on the composition and electrochemical profile of these materials. The sodium substitution disrupts ordering within the transition-metal layer, thereby disrupting Na + ordering in the adjacent sodium layers. Beyond a critical sodium concentration, the layer stacking shifts, and all voltage plateaus of the P2-Na 2 Ni 2 TeO 6 material are no longer observed at 4.4 V versus Na + /Na. These results also question the common belief that additional sodium precursor is required when preparing layered sodium oxide cathodes, providing new guidelines for material synthesis and characterization.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic configurations, from the extremes of classical molecular dynamics of a complete interface with point-charge atoms to correlated electronic structure methods of a single electrode configuration with no dynamics or electrolyte. Here, we review the spectrum of simulation techniques suitable for electrochemistry, focusing on the key approximations and accuracy considerations for each technique. Additionally, we discuss promising approaches, such as enhanced sampling techniques for atomic configurations and computationally efficient beyond density functional theory (DFT) electronic methods, that will push electrochemical simulations beyond the present frontier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electrochemical Recovery of Rare-Earth Elements from Coal Fly Ash Using Ionic Liquids as both Extractant and Electrolyte

Rare-earth elements (REEs) are critical for medical technologies, electronics, and clean energy. Coal fly ash (CFA), a byproduct of coal combustion, offers a promising alternative REE source. However, efficient extraction and separation of REEs from CFA remain challenging due to the complex composition of CFA. This study introduces a sustainable method for REE recovery using a recyclable ionic liquid, betainium bis(trifluoromethylsulfonyl)imide ([Hbet]- [Tf 2 N]), which serves both as the extractant from CFA and as the electrolyte in electrodeposition. In the first stage, [Hbet][Tf 2 N] preferentially extracts REEs from CFA through leaching. In the second stage, the REE-enriched ionic liquid undergoes electrochemical deposition using amperometry techniques, where REEs are reduced and deposited onto the electrode. The deposition experiments were conducted from −0.5 to −2.0 V vs a Pt quasireference electrode in a three-electrode setup comprising titanium as the working electrode and platinum as both the reference and counter electrodes. Varying the applied potential enabled potential-dependent preferential REE deposition. At −0.5 V, neodymium (Nd) showed preferential recovery, reaching 25% with a separation factor of 37 over other REEs. In contrast, applying a more negative potential increased overall deposition, yielding ∼50% Nd recovery and 10−20% recovery for the remaining REEs. After recovery, the ionic liquid was regenerated and reused for a subsequent electrochemical recovery cycle. Overall, this study demonstrates a feasible approach for REE recovery from CFA waste, with potential to enhance resource utilization within the REE supply chain.

coal fly ash↗