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At least 1,153 records · Page 64

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DOE OSTI2023

Microstructural Insights into Performance Loss of High-Voltage Spinel Cathodes for Lithium-ion Batteries

Spinel-structured LiNi x Mn 2-x O 4 (LNMO), with low-cost earth-abundant constituents, is a promising high-voltage cathode material for lithium-ion batteries. Even though extensive electrochemical investigations have been conducted on these materials, few studies have explored correlations between their loss in performance and associated changes in microstructure. Here, down to the atomic scale, the structural evolution of these materials is investigated upon the progressive cycling of lithium-ion cells. Transgranular cracking is revealed to be a key feature during cycling; this cracking is initiated at the particle surface and leads to the penetration of electrolytes along the crack path, thereby increasing particle exposure to the electrolyte. The lattice structure on the crack surface shows spatial variances, featuring a top layer of rock-salt, a sublayer of a Mn 3 O 4 -like arrangement, and then a mixed-cation region adjacent to the bulk lattice. The transgranular cracking, along with the emergence of local lattice distortion, becomes more evident with extended cycling. Further, phase transformation at primary particle surfaces and void formation through vacancy condensation is found in the cycled samples. All these features collectively contribute to the performance degradation of the battery cells during electrochemical cycling.

25 ENERGY STORAGE↗

DOE OSTI2025

Critical Insights into Solvent Choice for High-Voltage Organosulfur Electrolytes

Organosulfur electrolytes are promising candidates for enabling high-voltage cathodes due to their superior oxidative stability compared to conventional carbonate-based systems. However, their viscous nature and inability to passivate the anode necessitate the use of passivating agents and diluents to achieve meaningful charge/discharge rates. In this study, we investigate the use of cyclic fluorinated carbonates (CFCs) to form passivating interphases on electrode surfaces, aiming to optimize electrolyte performance in high-voltage systems. Electrolyte formulations containing 1.2 M LiPF 6 in a CFC:sulfone:1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) mixture (2/5/3 V/V/V) were assessed in full-cell configurations with a LiNi 0.8 Mn 0.1 Co 0.1 O 2 (FCG-NMC) cathode and a 4.5 V upper cutoff potential. The results reveal that 3-3-3-trifluoropropylene carbonate (TFPC) combined with ethyl methyl sulfone (EMS) optimizes electrolyte performance, resulting in lower resistance buildup and reduced capacity loss compared to commercial electrolytes. We also explore the failure mechanisms of several carbonate/sulfone mixtures and identify key considerations for electrolyte compatibility in high-voltage systems. TFPC enhances cycling stability and lowers overall cell resistance, while fluoroethylene carbonate (FEC) formulations, despite higher ionic conductivity, fail to form adequate passivation layers, leading to rapid capacity loss. Additionally, EMS provides superior physical properties that avoid common failure modes seen with other sulfone solvents like methyl isopropyl sulfone and tetramethylene sulfone. Furthermore, this study underscores the importance of carefully selecting passivating carbonates and sulfone solvents to improve electrolyte performance and expand the viability of high-voltage electrolyte systems.

LiNi0.8Mn0.1Co0.1O2 cathode↗

DOE OSTI2020

Stable bromine charge storage in porous carbon electrodes using tetraalkylammonium bromides for reversible solid complexation

Electrolytes for use in electric double-layer capacitors (EDLCs; often referred as supercapacitors or ultracapacitors) are disclosed. In one example, the electrolyte comprises viologen in both the anolyte and the catholyte (with bromide). In another example, the electrolyte comprises viologen (in the anolyte) and tetraalkylammonium with bromide (in the catholyte), wherein the tetraalkylammonium is used to achieve solid complexation of bromine in the activated carbon of the cathode. In a third example, a zinc bromine/tetraalkylammonium supercapacitor/battery hybrid is disclosed. Also disclosed is a corrosion resistant bipolar pouch cell that can be used with the electrolyte embodiments described herein.

25 ENERGY STORAGE↗

DOE OSTI2023

First-Principles Examination of Multiple Criteria of Organic Solvent Oxidative Stability in Batteries

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precursors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode–electrolyte interphase (CEI) film formation, transition-metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply density functional theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen-terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition-metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition-metal ions. Further, the structure–degradation relation complexity underscores the challenge of understanding the function of the CEI but also offers a guide to future degradation-mitigation strategies including facet engineering. Our predictions and models help establish a framework for future studies relevant to high-voltage conditions.

25 ENERGY STORAGE↗

NASA NTRS1989

Numerical modeling of a vortex stabilized arcjet thruster

A numerical method to solve the equations governing a vortex stabilized arcjet thruster is being developed. The model will allow the effects of swirling flow and geometry on arcjet thruster performance to be determined. The propellant flow equations, i.e., the axisymmetric, thin layer, Navier-Stokes equations, are solved using a Gauss-Siedel line-relaxation procedure. An implicit FTCS method is used to solve the electromagnetic field equations. A grid generation scheme was developed for an arbitrary arcjet geometry. The model will allow the radial and axial components of velocity and current distributions to be determined from a region upstream of the cathode, through the constrictor, to the exit plane of the nozzle.

Keith, Theo G., Jr.↗

NASA NTRS2005

Nanostructured and layered lithium manganese oxide and method of manufacturing the same

Nanostructured and layered lithium manganese oxide powders and methods of producing same. The powders are represented by the chemical formula, LixMn1-yMyO2, where 0.5<x<1.33, 0?y?0.5 and have an average primary particle diameter from 5 nm to 300 nm, preferably between 5 and 100 nm, and M is at least one cation dopant. The powders can be formed into active cathode materials in Li-ion and Li rechargeable batteries.

Singhal, Amit↗

DOE OSTI2026

Influence of CO 2 -Regenerative Film Properties in Enhancing C 2+ Products Selectivity While Mitigating CO 2 Crossover

Zero-gap anion-exchange membrane electrode assembly (AEMEA) electrolyzers operating in alkaline media face challenges such as CO 2 crossover and salting-out. The bipolar membrane electrode assembly (BPMEA) electrolyzer, using DI water as the electrolyte, addresses both CO 2 crossover and salting-out issues. As cations, which are crucial in stabilizing the CO 2 R intermediates, are absent in the electrolyte, cations embedded in the AEM play an important role in dictating the CO 2 R selectivity and activity in BPMEA systems. So far, no systematic study has been conducted on the influence of cations embedded in AEMs on CO 2 selectivity and activity in BPMEA systems. Moreover, BPMEA systems impose an additional challenge: low stability due to delamination of the bipolar membrane caused by CO 2 regeneration at the membrane-membrane interface. To enhance the stability of the electrolyzer, a simple yet highly reproducible strategy for coating a porous CO 2 regenerative film on smooth Nafion 117 is demonstrated in this work, along with a systematic study of four different commercially available AEMs, composed of different cations and cation densities, for use in combination with Nafion 117 and copper catalyst at the cathode. We found that the PiperION membrane delivers selectivity and activity comparable to those of alkali-metal cations, owing to the enhanced local electric field resulting from the combined effects of a high positive charge on the N atom of the piperidinium cation and the high ion-exchange capacity. Further, we studied the influence of the thickness of the PiperION porous layer over Nafion 117 on CO 2 R selectivity and found that 70 μm is the minimum thickness to achieve maximum C 2+ products selectivity, reduced the CO 2 crossover to 5% from 25% at 4 SCCM and 150 mA cm –2 , and was stable for operation beyond 100 h. The selectivity of this system, compared with AEMEA, and stability outperformed both AEMEA and BPMEA. This study helps design more effective BPMs to inhibit CO 2 crossover while enabling stable and selective electrochemical CO 2 reduction to C 2+ hydrocarbons.

Cations↗

NASA NTRS1980

Catalyst surfaces for the chromous/chromic redox couple

An electricity producing cell of the reduction-oxidation (REDOX) type is described. The cell is divided into two compartments by a membrane, each compartment containing a solid inert electrode. A ferrous/ferric couple in a chloride solution serves as a cathode fluid which is circulated through one of the compartments to produce a positive electric potential disposed therein. A chromic/chromous couple in a chloride solution serves as an anode fluid which is circulated through the second compartment to produce a negative potential on an electrode disposed therein. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which was added to the anode fluid. If the REDOX cell is then discharged, the current flows between the electrodes causing the lead to deplate from the negative electrode and the metal coating on the electrode will act as a catalyst to cause increased current density.

Giner, J. D.↗

NASA NTRS1990

Plasma contactor research, 1989

The characteristics of double layers observed by researchers investigating magnetospheric phenomena are contrasted to those observed in plasma contacting experiments. Experiments in the electron collection mode of the plasma contacting process were performed and the results confirm a simple model of this process for current levels ranging to 3 A. Experimental results were also obtained in a study of the process of electron emission from a hollow cathode plasma contactor. High energy ions are observed coming from the cathode in addition to the electrons and a phenomenological model that suggests a mechanism by which this could occur is presented. Experimental results showing the effects of the design parameters of the ambient plasma simulator on the plasma potential, electron temperature, electron density and plasma noise levels induced in plasma contacting experiments are presented. A preferred simulator design is selected on the basis of these results.

Williams, John D.↗

DOE OSTI2025

Reciprocal Ternary Molten Salts Enable the Direct Upcycling of Spent Lithium‐Nickel‐Manganese‐Cobalt Oxide (NMC) Mixtures to Make NMC 622

Cathode active material is the most valuable component of spent lithium‐ion batteries, accounting for ≈30% of their overall value. Direct recycling of cathode materials involves recovering, regenerating, and reusing them without breaking down their chemical structure. This approach maximizes the added value of the cathode compound and reduces manufacturing costs by avoiding the need for virgin material production. However, one key challenge in scaling direct recycling from lab to industry is the requirement for highly purified cathode materials, contrasting with the low purity of black mass generated from battery shredding. No efficient separation process currently exists to isolate different lithium‐nickel‐manganese‐cobalt oxides (NMCs) from each other. Thus, direct recycling technologies that can operate with mixtures of multiple NMC stoichiometries will be best‐suited for industrial adoption. This study explores the direct recycling of NMC mixtures into NMC 622 using a “reciprocal ternary molten salts (RTMS)” system. Ionothermal relithiation and upcycling within the RTMS system successfully restore the layered structure, lithium content, and electrochemical performance of degraded NMCs, yielding results comparable to pristine NMC 622 (P‐NMC 622).

25 ENERGY STORAGE↗

DOE OSTI2025

Mechanism of Mesoscale Woodpile Development via Photoelectrochemical Deposition of Se–Te

A combination of experiments and optical modeling provided insight into the mechanism of mesoscale woodpile formation in response to an orthogonal shift in polarization during photoelectrochemical deposition of Se–Te. Cathodic deposition of semiconducting Se–Te using spatially uniform, linearly polarized illumination produced arrays of lamellae that were aligned parallel to the optical E-field oscillation. Continued deposition in conjunction with an orthogonal shift in the polarization direction then produced aligned bridging features that spanned the void space between, and were orthogonal to, the preexisting lamellae. The height and pitch, respectively, in each layer of the woodpile were a function of the charge density and illumination wavelength during deposition. A Monte Carlo model, in which material addition was scaled by the absorption magnitude obtained from electromagnetic simulations, produced morphologies that were nominally identical to those observed experimentally. Here, the formation of mesoscale woodpiles is consistent with a mechanism that involves a series of spontaneously initiated, concerted light–matter interactions during the photoelectrochemical deposition process.

absorption↗

DOE OSTI2020

Thin Cation-Exchange Layers Enable High-Current-Density Bipolar Membrane Electrolyzers via Improved Water Transport

With suitable water dissociation (WD) catalysts, bipolar membranes (BPMs) can efficiently dissociate water into H + and OH – at the junction between anion- and cation-exchange layers (AEL and CEL, respectively). First, however, water must be transported through the AEL or CEL and thus against the outward flow of hydrated H + and OH – . This is a challenge intrinsic to the BPM architecture and limits operation to current densities typically less than ~0.5 A·cm –2 . Here we explore how water transport affects durability and performance in reference alkaline and acidic membrane electrolyzers, and we use the insight gained to design BPMs with improved water transport. We demonstrate a thin-CEL BPM (2-μm Nafion CEL|~200 nm TiO 2 |~200 nm NiO + ionomer|50 μm Sustainion AEL) which maintains a pH difference of ~14 units between the anode and cathode for current densities of up to 3.4 A·cm –2 with a total water electrolysis voltage of ~4 V and an estimated WD overpotential of ~1.5 V. Finally, such high-current-density operation is crucial for key emerging BPM applications, including in water and carbon-dioxide electrolyzers and in (regenerative) fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Designing lithium halide solid electrolytes

All-solid-state lithium batteries have attracted widespread attention for next-generation energy storage, potentially providing enhanced safety and cycling stability. The performance of such batteries relies on solid electrolyte materials; hence many structures/phases are being investigated with increasing compositional complexity. Among the various solid electrolytes, lithium halides show promising ionic conductivity and cathode compatibility, however, there are no effective guidelines when moving toward complex compositions that go beyond ab -initio modeling. Here, we show that ionic potential, the ratio of charge number and ion radius, can effectively capture the key interactions within halide materials, making it possible to guide the design of the representative crystal structures. This is demonstrated by the preparation of a family of complex layered halides that combine an enhanced conductivity with a favorable isometric morphology, induced by the high configurational entropy. This work provides insights into the characteristics of complex halide phases and presents a methodology for designing solid materials.

25 ENERGY STORAGE↗

DOE OSTI2026

Photovoltage behaviour of p-Sb 2 S 3 photocathodes for hydrogen evolution: effect of n-In 2 S 3 passivation layers

The 1.76 eV band gap of antimony(iii) sulphide (Sb 2 S 3 ) makes this semiconductor material a promising light absorber for photoelectrochemical water splitting, but scalable fabrication approaches to efficient devices are still lacking. Here we show that compact Sb 2 S 3 films on FTO can be obtained by electrochemical growth from aqueous colloidal sulphur and antimony trichloride solutions, followed by mild annealing. These films can be converted into hydrogen evolution photocathodes after coating with In 2 S 3 passivation layers and the addition of Pt proton reduction co-catalysts. For the first time, vibrating Kelvin probe surface photovoltage (VKP-SPV) spectroscopy is used to observe the carrier dynamics in such photoelectrodes. While the bare Sb 2 S 3 films suffer from high surface recombination rates and poor electron extraction, the In 2 S 3 overlayer is found to raise the photovoltage and cathodic photocurrent density, due to passivation of surface defects and formation of a p–n heterojunction. In thick In 2 S 3 films, these benefits are offset by shading and slow electron transfer. Also, we find that O 2 strongly affects the band bending in the Sb 2 S 3 –air and In 2 S 3 –air junctions and their photovoltage. The optimised devices evolve H 2 at 77.5% Faradaic efficiency and with 0.084% applied bias photon-to-current efficiency (ABPE) at 0.12 V vs. RHE. The low ABPE value is attributed to Sb 2 S 3 sub-bandgap defects visible in SPV spectra, the random orientation of Sb 2 S 3 crystallites in the films, which inhibits charge transport, the absence of crystal facets of Sb 2 S 3 , and a detrimental Schottky junction at the FTO|Sb 2 S 3 interface.

de Araújo, Moisés A. [University of California, Da↗

DOE OSTI2020

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗

DOE OSTI2021

Spatially-resolved lithiation dynamics from operando X-ray diffraction and electrochemical modeling of lithium-ion cells

In this study, energy dispersive X-ray diffraction is used to profile the time evolution of ordered Li x C 6 phases in solid electrodes of lithium-ion cells charged at rates between 0.2 and 4.7C (where 1C corresponds to full discharge in 1 h). The methods for quantifying lithium concentration in these phases from the acquired diffraction patterns are described. Compact expressions for time-dependent concentration gradients in the solid electrodes using orthogonal polynomial expansions are presented. Experimentally, these gradients persisted in lithiated graphite electrodes even after the cells rested at open-circuit for over 9 h. A multiphase electrochemical model of graphite intercalation captured many of the observed behaviors, including the progression of phase transitions and the persistent gradients at zero current. However, the magnitude of concentration gradients in both the oxide cathode and graphite anode is underestimated by the model, even at moderate currents.

25 ENERGY STORAGE↗

DOE OSTI2022

Developing an In-situ Formed Dynamic Protection Layer to Mitigate Lithium Interface Shifting: Preventing Dendrite Formation on Metallic Lithium Surface to Facilitate Long Cycle Life of Lithium Solid-State Batteries

After extensive research on various system, a fully lithiated Si anode material (Li 3.75 Si) was synthesized. The high energy density, long cycle life anode demonstrated no apparent dendrite growth in an all-solid-state Li battery. A flexible solid-state electrolyte film with a thickness less than 50 μm was developed. All-solid-state Li full batteries were built and tested with NMC811, organic, organosulfide and sulfur cathode. Energy density of 1140 Wh/Kg at material level and 376 Wh/Kg at electrode level were demonstrated for over 500 cycles and with no apparent dendrite formation on the Li anode.

25 ENERGY STORAGE↗

DOE OSTI2025

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↗