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At least 721 records · Page 40

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)↗

Facet-dependent electron transfer induces distinct arsenic reallocations on hematite

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. In conclusion, these findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments.

54 ENVIRONMENTAL SCIENCES↗

Acid Etching‐Driven Self‐Assembly of Mn‐Shell Inducing Rock‐Salt Phase for Enhanced Single‐Crystal Ni‐Rich Cathodes

With the wide adoption of Li‐ion batteries, Ni‐rich cathode is considered as one of the most promising candidates of cathodes due to its high energy density and low cost. However, stability decreased with increasing Ni content in the Ni‐rich cathode. To solve this bottleneck, many strategies, such as coating, doping, surface modification, and special morphologies, have been developed. Herein, we introduce a groundbreaking approach for enhancing Ni‐rich cathode through an innovative acid etching process that promotes Mn shell self‐assembly, inducing a rock‐salt phase on the surface. This method not only simplifies the Ni‐rich cathode modification process, but also significantly improves the structural stability and electrochemical performance of Ni‐rich cathode. Our findings demonstrate that developed single‐crystal Ni‐rich cathode shows 3–34 % better stability compared to both commercial modified Ni‐rich cathode and unmodified counterparts. The unique Mn shell effectively mitigates reversible phase shifts during cycling, contributing to a remarkable enhancement in cycling stability. Additionally, this novel fabrication technique paves the way for cost‐effective production of high‐performance cathode materials, offering substantial benefits for lithium‐ion battery technology. And this study proves the potential of this method in advancing the design and development of durable, high‐capacity cathode materials for next‐generation batteries.

Ni-rich cathode↗

Atomically Dispersed Ru-doped Ti 4 O 7 Electrocatalysts for Chlorine Evolution Reaction with a Universal Activity

Chlorine has been supplied by the chlor-alkali process that deploys dimensionally stable anodes (DSAs) for the electrochemical chlorine evolution reaction (ClER). The paramount bottlenecks have been ascribed to an intensive usage of precious elements and inevitable competition with the oxygen evolution reaction. Herein, a unique case of Ru 2+ -O 4 active motifs anchored on Magnéli Ti 4 O 7 (Ru-Ti 4 O 7 ) via a straightforward wet impregnation and mild annealing is reported. The Ru-Ti 4 O 7 performs radically active ClER with minimal deployment of Ru (0.13 wt%), both in 5 m NaCl (pH 2.3) and 0.1 $\tiny{M}$ NaCl (pH 6.5) electrolytes. Scanning electrochemical microscopy demonstrates superior ClER selectivity on Ru-Ti 4 O 7 compared to the DSA. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a universally active ClER (over a wide range of pH and [Cl - ]), through a direct adsorption of Cl - on Ru 2+ -O 4 sites as the most plausible pathway, together with stabilized ClO* at low [Cl - ] and high pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic disproportionation on carbon superstructures enables long-life, high-loading Li–S batteries

Electrocatalysis has been widely explored as an effective strategy to accelerate polysulfide (PS) conversion and suppress the shuttle effect in lithium–sulfur (Li–S) batteries. However, the underlying mechanisms remain elusive, and electrocatalytic reactions are inactive during cell resting. In this work, we reveal and quantitatively analyze a previously unrecognized sulfur reduction route (SRR) driven by catalytic disproportionation at the carbon cathode surface—fundamentally distinct from conventional electrocatalysis. Unlike conventional stepwise pathways, this SRR enables high-order polysulfides (Sₓ²⁻, x = 5–8) to directly convert into S₈ and Li₂S₂, bypassing low-order intermediates. This sulfur-reduction shortcut is systematically elucidated through high-performance liquid chromatography, revealing the intrinsic catalytic contribution of carbon frameworks and the dynamic evolution of PS species. We demonstrate that carbon superstructures (CSS-0.5), assembled from nanosheet subunits with abundant N/O functionalities and interconnected charge-migration channels, synergistically promote this catalytic process. Benefiting from these features, CSS-0.5 delivers superior electrochemical performance under practical conditions, enabling high sulfur loading (6.0 mg cm⁻²) pouch cells with 80.5% capacity retention over 210 cycles. This study provides the first quantitative evidence of electrocatalytic disproportionation in Li–S batteries, offering mechanistic insights and design principles for advanced sulfur cathodes.

25 ENERGY STORAGE↗

Redox Behaviors in Li-Excess Cation-Disordered Mn-Nb-O-F Rocksalt Cathode

Lithium-excess cation-disordered rocksalt oxide (DRX) is a new choice of high energy Li-ion cathode materials. DRX cathode can deliver an exceptionally high capacity of >250 mAh/g, implying the participation of cationic transition metal and anionic oxygen redox in the electrochemistry. Understanding the explicit roles of both redox reactions in the newly developed cathode is of critical importance to further development of these materials. Herein, we synthesize a representative Mn-redox-based fluorinated DRX material, Li1.2Mn0.625Nb0.175O1.95F0.05 (LMNOF). Using a comprehensive suite of electroanalytical methods, we probe the cationic and anionic redox processes and their evolution upon cycling exclusively from the electrochemical point of view. This work sheds light on understanding of cationic and anionic redox and their roles in the capacity loss for high-capacity fluorinated DRX cathode, meanwhile, showcases an explicit approach to study the electrochemistry of novel electrode materials using such non-disruptive electroanalytical methods.

Li-ion battery, high-capacity cathode, Li-excess m↗

Understanding the Nature of Capacity Decay and Interface Properties in Li//LiNi 0.5 Mn 1.5 O 4 Cells by Cycling Aging and Titration Techniques

The spinel structure LiNi 0.5 Mn 1.5 O 4 (LNMO) is a propitious cathode material for next-generation lithium-ion batteries for fast charge–discharge applications, but its capacity decay mechanism and rate-limiting process are not yet well understood. In this work, electrochemical impedance spectroscopy (EIS) with galvanostatic intermittent titration (GITT) and cycling aging techniques were employed to investigate the nature of capacity decay in disordered-phase LNMO. Different resistive components were separated after every 10 cycles. Cell overvoltages (ΔVs) due to ohmic conduction, charge transfer (CT), and concentration polarization (CP) were individually determined. Results revealed that the cell exhibited a higher ΔV at a higher discharged state. However, the ΔV value for CP was higher at a higher state of charge (SOC), and the overall LNMO/electrolyte interface played a major role in the rate-determining step. Battery life was estimated based on the results. Battery calendar life was found to be more vulnerable than cycle life. Furthermore, results also indicated that the working SOC range could be optimized based on the resistance analysis by avoiding those SOCs that have the most detrimental impact (e.g., heat generation and fire hazard).

25 ENERGY STORAGE↗

Electro-chemo-mechanically Driven Ni Exsolution from (Pr,Ce,Ni)O 2−δ : Controlled Nucleation Density and Enhanced Electrode Kinetics

In situ exsolution of metal nanoparticles is a promising strategy to prepare electrocatalysts with enhanced activity and resistance to agglomeration for efficient chemical transformations and energy conversion. Achieving a high nucleation density of nanoparticles under mild conditions and understanding how to tailor the process is important for performance of these electrodes in electrochemical cells. In this work, we demonstrate facile exsolution of Ni nanoparticles using fluorite-structured (Pr,Ce)O 2−δ as the support oxide, driven by electrochemical potential and aided by the metastability of Ni in the solid solution (elastic driving force). We prepare single-phase oriented thin films of (Pr,Ce,Ni)O 2−δ (NPCO) on (Zr,Y)O 2−δ (YSZ) substrates by pulsed laser deposition. With the aid of a high-throughput electrochemical cell that provides a lateral gradient in Nernst voltage, we apply in situ near-ambient pressure synchrotron X-ray photoelectron spectroscopy and ex situ atomic force microscopy to investigate the impact of electrochemical potential on Ni nucleation density. We find that metallic Ni can be successfully exsolved at 550 °C upon cathodic biasing in 20 mTorr O 2 , and its nucleation density increases with increasing electrochemical driving force/decreasing oxygen chemical potential. We further evaluate the electrochemical performance under highly reducing (fuel electrode) conditions by electrochemical impedance spectroscopy. With the exsolved Ni nanoparticles, the surface exchange coefficient of the NPCO is found to be ∼4× higher than for PCO without exsolution. This work confirms mixed conducting fluorites as beneficial host lattices for facile transition-metal exsolution and suggests the possibility for constructing an all ceria-based electrochemical cell with PCO serving as both the cathode and the anode.

36 MATERIALS SCIENCE↗

Electro-chemo-mechanical evolution of sulfide solid electrolyte/Li metal interfaces: operando analysis and ALD interlayer effects

Sulfide solid electrolytes (SE) show promise for high-performance solid-state batteries because of their high ionic conductivity and ease of processing. However, sulfide electrolytes have suffered from chemical and electrochemical instability against Li metal anodes. In this paper, we use a suite of in situ/operando microscopy and spectroscopy techniques to demonstrate that Al 2 O 3 interlayers deposited using atomic layer deposition (ALD) delay degradation at the Li/LGPS interface by modifying the solid electrolyte interphase (SEI) chemistry and morphology. Optical and scanning electron microscopy are used to rationalize the electrochemical response of the system, which is attributed to a delayed onset of mechanical degradation at the interface when ALD interlayers are used. Operando X-ray photoelectron spectroscopy demonstrates that the dynamic evolution of SEI chemistry is impacted by the presence of the ALD interlayer. In situ Auger spectroscopy and operando optical microscopy provide visual evidence of spatial heterogeneity of Li plating, which is attributed to the chemo-mechanical degradation of the ALD interphase. The implications of these observations provide valuable insights toward the development of robust interlayers for solid-state batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Interconversion of Ammonia and Dinitrogen at Base Metals

Best known as a fertilizer, ammonia is also a carbon-free fuel that produces only benign byproducts, nitrogen and water. Moreover, the synthesis of ammonia from water and nitrogen in the air can be used to store energy from renewable, yet intermittent power sources such as solar and wind. This work develops new molecular electrocatalysts to efficiently extract electrical energy from ammonia, a process which currently is underdeveloped. These studies inspire complementary electrochemical approaches for the synthesis of ammonia from nitrogen by coupling it with the protons ultimately to be derived from acidified water. Careful mechanistic studies that outline the molecular steps involved in these chemical transformations will inform the design of new classes efficient catalysts that interconvert ammonia and nitrogen. Importantly, this study targets molecular electrocatalysts with inexpensive, Earth abundant metals such as iron and copper, consistent with the sustainable use and synthesis of ammonia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes the PE for high-temperature processing. After removing the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using a Fe-based low-temperature (<1500 °C) catalytic process. The PE-derived graphite powder showed excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs) with a capacity of up to 302 mAh/g at 0.5 discharge/charge cycles per hour (0.5 C) and capacity retention of 100% after 415 cycles.

Huynh, Ngoc Tien↗

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes the PE for high-temperature processing. After removing the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using a Fe-based low-temperature (<1500 °C) catalytic process. The PE-derived graphite powder showed excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs) with a capacity of up to 302 mAh/g at 0.5 discharge/charge cycles per hour (0.5 C) and capacity retention of 100% after 415 cycles. This method illustrates there are opportunities for upcycling large quantities of PE waste to produce graphite powders.

Huynh, Ngoc Tien [NETL Site Support Contractor, Na↗

Electrochemical Deburring

Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

Burley, R. K.↗

Metals production

Existing procedures for design of electrochemical plants can be used for design of lunar processes taking into consideration the differences in environmental conditions. These differences include: 1/6 Earth gravity, high vacuum, solar electrical and heat source, space radiation heat sink, long days and nights, and different availability and economics of materials, energy, and labor. Techniques have already been developed for operation of relatively small scale hydrogen-oxygen fuel cell systems used in the U.S. lunar landing program. Design and operation of lunar aqueous electrolytic process plants appears to be within the state-of-the-art. Finding or developing compatible materials for construction and designing of fused-magma metal winning cells will present a real engineering challenge.

Beck, Theodore S.↗

NASA Tech Briefs, May 2007

Topics include: Noise-Canceling Helmet Audio System; Program Analyzes Spacecraft/Ground Radio Links; Two-Way Communication Using RFID Equipment and Techniques; Six-Message Electromechanical Display System; Scanning Terahertz Heterodyne Imaging Systems; Master Clock and Time-Signal-Distribution System; Synchronous Phase-Resolving Flash Range Imaging; Integrated Radial Probe Transition From MMIC to Waveguide; Bar-Code System for a Microbiological Laboratory; MMIC Amplifier Produces Gain of 10 dB at 235 GHz; Mapping Nearby Terrain in 3D by Use of a Grid of Laser Spots; Digital Beam Deflectors Based Partly on Liquid Crystals; Narrow-Band WGM Optical Filters With Tunable FSRs; Better Finite-Element Analysis of Composite Shell Structures; Computing Spacecraft-Pointing Vectors for Limb Tracking; Enhanced Master Controller Unit Tester; Rover Graphical Simulator; Increasing Durability of Flame-Sprayed Strain Gauges; Multifunctional, High-Temperature Nanocomposites; Multilayer Impregnated Fibrous Thermal Insulation Tiles; Radiation-Shielding Polymer/Soil Composites; Film/Adhesive Processing Module for Fiber-Placement Processing of Composites; Fabrication of Submillimeter Axisymmetric Optical Components; Electrochemical Disposal of Hydrazines in Water; Statistical Model of Evaporating Multicomponent Fuel Drops; Resistively Heated SiC Nozzle for Generating Molecular Beams; Compact Packaging of Photonic Millimeter-Wave Receiver; Diffractive Combiner of Single-Mode Pump Laser-Diode Beams; Wide-Band, High-Quantum-Efficiency Photodetector; A Robustly Stabilizing Model Predictive Control Algorithm; Modeling Evaporation of Drops of Different Kerosenes; Development of Vapor-Phase Catalytic Ammonia Removal System; Several Developments in Space Tethers; Design Concept for a Nuclear Reactor-Powered Mars Rover; Formation-Initialization Algorithm for N Spacecraft; and DNSs of Multicomponent Gaseous and Drop-Laden Mixing Layers Achieving Transition to Turbulence.

Source record↗

Freeze Casting of LAGP for 3D Textured Solid-State Structural Electrolytes

In this study, all-solid-state structural lithium-ion batteries, a type of load bearing electrochemical energy storage that provides systems-level weight savings is being pursued for the realization of inherently safe next generation hybrid-electric and all-electric green aerospace propulsion systems. Currently investigated all-solid-state batteries do not meet the requirements for specific power and mechanical stability. To address these issues, freeze casting of lithium aluminum germanium phosphate (LAGP) electrolyte material has been explored for the creation of a textured 3D electrolyte scaffold with large interfacial surface area for high power discharge and hierarchical porosity for accommodation of active material volume changes during electrochemical cycling. We report the effects of freeze casting processing parameters on the microstructural development and mechanical performance of the scaffolds, characterized through scanning electron microscopy and ring-on-ring mechanical testing. Slurry composition and casting parameters such as solids loading, casting speed, tape angle, and temperature gradients have been modified to determine the impact on density, lamellar morphology, and final load-bearing performance.

ceramics↗

Automated Redox Titrations via Interdigitated Electrode Arrays: Application to the Mediated Electron Transfer Interrogation of Charge and Rate on Electrodeposited Polymers

Mediated electron transfer (MET) plays a crucial role in energy storage and conversion technologies such as redox targeting flow batteries (RTFBs), yet its experimental investigation often requires labor-intensive and low-throughput setups. To address this, we developed a microfabricated interdigitated electrode array (IDA) platform that enables automated, high-throughput electrochemical redox titration measurement to be performed to study the MET process. Our redox titration method enables simultaneous measurement of the charge capacity and rate of MET processes on a material or surface. Automated redox titration (ART) facilitates systematic investigation of the MET process across a broad parameter space, exemplified through the study of polypyrrole (PPy) and a pyrene-4,5,9,10-tetrone azo group-based polymer (PTAP), both redox-active polymers relevant to various energy storage applications. Using PPy as a model material, 500 redox titration measurements were conducted within 50 h, varying the electrode gap widths, polymer charging potentials, voltammetric scan rates, and electrolyte concentrations. Finite-element simulations confirmed the electrochemical responses and elucidated the kinetics of the MET reactions. Our automated methodology was further tested with PTAP, revealing a surprising charging potential dependence on the rate of MET. The automation, flexibility, and scalability of our redox titration platform pave the way not only for advanced studies of MET processes relevant to RTFBs, but also with implications in the understanding of next-generation energy storage materials, molecular electrocatalysis, and biosensing.

electrochemical analysis↗

Bipolar Membrane Capacitive Deionization for pH-Assisted Ionic Separations

Selective ionic separations represent an increasingly important technical area for the strategic interests of the U.S. economy–for example, securing critical minerals and materials and circular economy aspirations that include recovering organic acids from processed biomass. This work disseminates bipolar membrane (BPM) capacitive deionization for selective ionic separations from multicomponent, ionic species mixtures. The selective separations are guided by the Pourbaix diagram and acid–base equilibria principles. BPM capacitive deionization was demonstrated to generate alkaline or acidic process streams depending upon the location of the BPM in the electrochemical cell. The role of system operating parameters, such as the cell voltage, residence time, and feed concentration on effluent stream pH was studied. It was observed that the pH adjustment in BPM-CDI/MCDI (MCDI, membrane capacitive deionization) was more sensitive to the cell voltage when compared to the process stream residence time and salt feed concentration. The BPM-MCDI gave over 6 times higher percentage of copper(II) removal when compared to sodium ion removal from brine mixtures. Lastly, BPM-MCDI demonstrated over 40% greater removal for copper ions from brine mixtures and fivefold higher removal for itaconic acid from brine mixtures when benchmarked against a traditional flow-by-MCDI setup.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗