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At least 91 records · Page 5

Mass Spectrometer Containing Multiple Fixed Collectors

A miniature mass spectrometer that incorporates features not typically found in prior mass spectrometers is undergoing development. This mass spectrometer is designed to simultaneously measure the relative concentrations of five gases (H2, He, N2, O2, and Ar) in air, over the relative-concentration range from 10(exp -6) to 1, during a sampling time as short as 1 second. It is intended to serve as a prototype of a product line of easy-to-use, portable, lightweight, highspeed, relatively inexpensive instruments for measuring concentrations of multiple chemical species in such diverse applications as detecting explosive or toxic chemicals in air, monitoring and controlling industrial processes, measuring concentrations of deliberately introduced isotopes in medical and biological investigations, and general environmental monitoring. The heart of this mass spectrometer is an integral combination of a circular cycloidal mass analyzer, multiple fixed ion collectors, and two mass-selective ion sources. By circular cycloidal mass analyzer is meant an analyzer that includes (1) two concentric circular cylindrical electrodes for applying a radial electric field and (2) a magnet arranged to impose a magnetic flux aligned predominantly along the cylindrical axis, so that ions, once accelerated into the annulus between the electrodes, move along circular cycloidal trajectories. As in other mass analyzers, trajectory of each ion is determined by its mass-to-charge ratio, and so ions of different species can be collected simultaneously by collectors (Faraday cups) at different locations intersected by the corresponding trajectories (see figure). Unlike in other mass analyzers, the installation of additional collectors to detect additional species does not necessitate increasing the overall size of the analyzer assembly.

Moskala, Robert↗

Apparatus for Pumping a Fluid

An electrochemically actuated pump and an electrochemical actuator for use with a pump. The pump includes one of various stroke volume multiplier configurations with the pressure of a pumping fluid assisting actuation of a driving fluid bellows. The electrochemical actuator has at least one electrode fluidically coupled to the driving fluid chamber of the first pump housing and at least one electrode fluidically coupled to the driving fluid chamber of the second pump housing. Accordingly, the electrochemical actuator selectively pressurizes hydrogen gas within a driving fluid chamber. The actuator may include a membrane electrode assembly including an ion exchange membrane with first and second catalyzed electrodes in contact with opposing sides of the membrane, and first and second hydrogen gas chambers in fluid communication with the first and second electrodes, respectively. A controller may reverse the polarity of a voltage source electrically coupled to the current collectors.

van Boeyen, Roger W.↗

Sodium-halogen secondary cell

An intermediate temperature sodium-halogen secondary cell that includes a negative electrode compartment housing a negative, molten sodium-based electrode and a positive electrode compartment housing a current collector disposed in a highly conductive molten positive electrolyte. A sodium halide (NaX) positive electrode is disposed in a molten positive electrolyte comprising one or more AlX3 salts, wherein X may be the same or different halogen selected from Cl, Br, and I, wherein the ratio of NaX to AlX3 is greater than or equal to one. A sodium ion conductive solid electrolyte membrane separates the molten sodium negative electrode from the molten positive electrolyte. The secondary cell operates at a temperature in the range from about 80° C. to 210° C.

Bhavaraju, Sai↗

Rational Selection of Sodium Layered Oxides for High Performance Na-Ion Batteries: P2 vs O3 vs P2-O3 Intergrowths

Sodium ion batteries (NIBs) are gaining importance as an energy storage technology complementary to the Li-ion batteries. In this regard, sodium-based layered oxides are recognized as one of the most suitable positive electrode candidate for NIBs, but vast variety of their chemical compositions and crystal structures complicates the selection of the best material. To shed light on different figures of merit that control the selection of layered oxide material for NIB applications, we compare here a P2, P2-O3 intergrowth and two O3 sodium layered oxides composed of the same transition metals (Ni, Mn, Ti and Zn) but in differing stoichiometries. The results show that the new P2-type Na 0.67 Ni 0.3 Zn 0.03 Mn 0.52 Ti 0.15 O 2 phase reported here combines most of the advantages, such as stability towards moisture, reduced surface reactivity, better thermal stability and high rate capability, which are essential for commercialization, except for a limited capacity (∼125 mAh g −1 ) compared to the O3 NaNi 0.45 Zn 0.05 Mn 0.4 Ti 0.1 O 2 phase (∼180 mAh g −1 ), reported by our group previously. Altogether, this work enlarges the family of attractive Na-based positive electrodes and teaches us that we should not solely be obsessed with the capacity of a material to decide of its applicability.

Electrochemistry↗

Porin-Inspired Ionomers with sub-nm Gated Ion Channels for High Ion Conductivity and Selectivity (Final Project Report (2026))

The physiological functions of living systems heavily rely on biological ion channels, whose malfunction can lead to disease. These channels enable selective and regulated transport of water, ions, or small molecules across membranes. Analogously, ionomers used in energy conversion and storage technologies govern ion transport within membrane separators and catalyst binder layers. This DOE Office of Science Early CAREER project aimed to achieve molecular-level control over ionic conductivity and ion permselectivity by translating the functionalities of biological, gated ion channels into a novel class of ion-conducting polymers (ionomers) incorporating macrocyclic calix[4]arene-based repeat units. The overarching goal was to establish fundamental design principles and elucidate proton conduction mechanisms through strategic design of macrocyclic calix[4]arene-containing ionomers, with close relevance to energy conversion and storage devices, including proton exchange membrane fuel cells (PEMFCs). The project leveraged sub-nm-sized macrocyclic pores to facilitate exceptionally fast ion transport (beneficial to addressing sluggish ORR kinetics of PEMFC electrodes) and achieve functionalities of ionic diodes under applied electrochemical fields, beneficial for selective transport/separation.

59 BASIC BIOLOGICAL SCIENCES↗

Laser ablation for structuring Li-ion electrodes for fast charging and its impact on material properties, rate capability, Li plating, and wetting

Laser ablation is a scalable technique for decreasing the effective tortuosity of electrodes by selectively removing material with high precision. Applied to ≈ 110 um thick electrode coatings, this work focuses on understanding the impact of laser ablation on electrode material properties at the beginning of life and synergistic impacts of ablated channels on cell performance throughout their cycle life. Post laser ablation, local changes in chemistry, crystallography, and morphology of the laser-impacted electrode regions are investigated. It is shown that femtosecond pulsed laser ablation can achieve high-rate material removal with minor material damage locally at the interface of the impacted zones. The capacity achieved during a 6C (10 min) constant-current constant-voltage charge to 4.2 V improved from 1 mAh cm -2 for the non-ablated electrodes to almost 2 mAh cm -2 for the ablated electrodes. This benefit is attributed to a synergistic effect of enhanced wetting and decreased electrode tortuosity. The benefit was maintained for over 120 cycles, and upon disassembly decreased Li-plating on the graphite anode was observed. Finally, multi-physics modeling in conjunction with wetting analyses showed that laser ablating either one of the electrodes led to substantial improvements in wetting and rate capability, indicating that substantial performance benefits can be achieved by ablating only the graphite anode as apposed to both electrodes.

25 ENERGY STORAGE↗

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries

Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture, the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures. The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured, benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW), a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. Furthermore, while the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs, including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct and Sensitive Electrochemical Evaluation of Pramipexole Using Graphitic Carbon Nitride (gCN) Sensor

Pramipexole (PMXL) belongs to the benzothiazole class of aromatic compounds and is used in treating Parkinson’s disease; however, overdosage leads to some abnormal effects that could trigger severe side effects. Therefore, it demands a sensitive analytical tool for trace level detection. In this work, we successfully developed an electrochemical sensor for the trace level detection of PMXL, using the voltammetric method. For the analysis, graphitic carbon nitride (gCN) was opted and synthesized by using a high-temperature thermal condensation method. The synthesized nanoparticles were employed for surface characterization, using transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic force microscopy (AFM) techniques. The electrochemical characterization of the material was evaluated by using the electrochemical impedance spectroscopy (EIS) technique to evaluate the solution–electrode interface property. The cyclic voltammetry (CV) behavior of PMXL displayed an anodic peak in the forward scan, indicating that PMXL underwent electrooxidation, and an enhanced detection peak with lower detection potential was achieved for gCN-modified carbon paste electrode (gCN·CPE). The influence of different parameters on the electrochemical behavior was analyzed, revealing the diffusion governing the electrode process with an equal number of hydronium ions and electron involvement. For the fabricated gCN·CPE, good linearity range was noticed from 0.05 to 500 µM, and a lower detection limit (L D ) of 0.012 µM was achieved for the selected concentration range (0.5 to 30 µM). Selectivity of the electrode in PMXL detection was investigated by conducting an interference study, while the tablet sample analysis demonstrates the sensitive and real-time application of the electrode. The good recovery values for the analysis illustrate the efficiency of the electrode for PMXL analysis.

36 MATERIALS SCIENCE↗

Water-coupled monovalent and divalent ion transport in polyviologen networks

Redox-active polymers (RAPs) are of interest as environmentally friendly and earth-abundant energy storage materials. Polyviologens are promising RAPs, but they tend to dissolve during operation. Further, the two-electron redox reaction for polyviologens in various electrolytes is not always reversible, highlighting the need for a deeper understanding of the redox mechanism. Here, the energy storage mechanism for a cross-linked viologen (PTPM) is demonstrated using electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D), comparing NaCl and Na2SO4 aqueous electrolytes. E-QCMD reveals that the ion-electron transport mechanism is strongly dependent on the valency of the anion. More sudden and dramatic changes in the electrode's mass were observed for the divalent sulfate ion as compared to the smooth mass transitions associated with the monovalent chloride ion. Meanwhile, there was marked hysteresis in the mass transfer profile for NaCl, but little hysteresis for Na2SO4. Our results demonstrate that electrolyte design, and specifically ion valency, will have a large impact on the nature of mass transport in polymer-based electrodes. This work enables electrolyte selection for the next generation polymer batteries with improved performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-iron oxide hybrid films for controlling electrokinetic properties

Electrokinetic phenomena at polymer-water interfaces are central to technologies for water purification, ion separations, and energy conversion, yet the ability to systematically control polymer surface charge and associated electrokinetic processes remains limited. Here, we demonstrate a simple liquid-phase infiltration (LPI) method to synthesize polymer–metal oxide hybrid films with controllable interfacial properties. Hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) brushes grafted to silicon substrates were infiltrated with iron nitrate from ethanolic solution, followed by low-temperature thermal treatment to convert the infiltrated precursor into iron oxide. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis confirmed oxide incorporation and hybrid film formation without polymer degradation. Electrokinetic measurements reveal that the hybrid films acquire the electrokinetic properties of the infiltrated oxide, with concentration-dependent streaming potentials and surface conductivities closely matching those of pure iron oxide films. These results establish metal oxide infiltration as a scalable and low-cost strategy for controlling interfacial charge in polymer surfaces. The approach introduces new materials and design parameters for tailoring ion selectivity, transport, and energy conversion, with broad implications for the development of advanced membranes, electrokinetic harvesting devices, and polymer-supported oxide electrodes.

36 MATERIALS SCIENCE↗

Electrochemically-assisted removal of cadmium ions by redox active Cu-based metal-organic framework

An electrochemically-assisted wastewater treatment using Faradaic materials offers a promising technique for the selective removal of hazardous substances. Here, we demonstrate the reversible capture and release of cadmium ions in aqueous solutions, using a redox-active metal-organic framework (MOF) electrode. As-synthesized copper-based MOF (Cu-MOF-74; copper 2,5-dihydroxyterephthalate) is a highly attractive candidate for Faradaic electrosorption due to its large surface area, water stability, and redox-active metal nodes. Our work demonstrates the reversible capture and release of Cd 2+ ions assisted by the electrochemical redox reaction of Cu 2+ /Cu + within the MOF structure. Combined material characterization and electrosorption tests were carried out to determine the operational conditions for maximizing adsorption capacity, energy efficiency, and material stability, thus leading to excellent electrosorption (>100 mg g -1 ) and regeneration efficiency (>90%). This study demonstrates the feasibility of leveraging MOFs containing redox-active metal nodes for the selective separation of toxic cations, and paves the way for promising future applications of these 3-D porous structures for wastewater treatment and environmental remediation.

42 ENGINEERING↗

NASA Redox Storage System Development Project

The Redox Storage System Technology Project was jointly supported by the U.S. Department of Energy and NASA. The objectives of the project were to develop the Redox flow battery concept and to probe its technical and economic viability. The iron and chromium redox couples were selected as the reactants. Membranes and electrodes were developed for the original mode of operating at 25 C with the reactants separated by an ion-exchange membrane. Analytical capabilities and system-level operating concepts were developed and verified in a 1-kW, 13-kWh preprototype system. A subsequent change was made in operating mode, going to 65 C and using mixed reactants. New membranes and a new electrode catalyst were developed, resulting in single cell operation as high as 80 mA/sq cm with energy efficiencies greater than 80 percent. Studies indicate a likely system cost of about $75/kWh. Standard Oil of Ohio (Sohio) has undertaken further development of the Redox system. An exclusive patent license was obtained from NASA by Sohio. Transfer of Redox technology to Sohio is supported by the NASA Technology Utilization Office.

Hagedorn, N. H.↗

Structure and Stability of the Ionic Liquid Clusters [EMIM]n[BF4]n+1- (n = 1 – 9): Implications for Electrochemical Separations

Precise functionalization of electrodes with size-selected ionic liquid (IL) clusters may improve the application of ILs in electrochemical separations. Herein, we report our combined experimental and theoretical investigation of the IL clusters [EMIM]????[BF4]????+1- (n = 1 – 9) and demonstrate their selectivity and efficiency towards targeted adsorption of molecules from solution. The structures and energies of the IL clusters, predicted with global optimization, agree with and help interpret the ion abundances and stabilities measured by high mass resolution electrospray ionization mass spectrometry and collision induced dissociation experiments. The [EMIM][BF4]2- cluster, which was identified as the most stable IL cluster, was selectively soft landed onto a working electrode. Electrochemical impedance spectroscopy revealed a lower charge transfer resistance on the soft-landed electrode containing [EMIM] [BF_4 ]_2^- compared to an electrode prepared by drop casting of IL solution, which contains the full range of IL clusters. Our findings indicate that specific IL clusters may be used to increase the efficiency of electrochemical separations by lowering the overpotentials involved.

Zhang, Jun↗

Transient current interruption mechanism in a magnetically delayed vacuum switch

The capacity of a magnetically delayed vacuum switch to conduct current depends on the density of plasma injected into the switch. Exceeding the current capacity results in the switch entering a lossy mode of operation characterized by a transient interruption of the main current (opening behavior) and a rapid increase of voltage across the vacuum gap. Streak and framing photographs of the discharge indicate that a decrease of luminosity near the middle of the gap preceeds the transition to the opening phase. The zone of low luminosity propagates toward the cathode. This evidence suggests that the mechanism causing the opening phase is erosion of the background plasma in a manner similar to that in a plasma-opening switch. The resulting ion depletion forces a space-charge-limited conduction mode. The switch inductance maintains a high discharge current even during the space-charge-limited conduction phase, thus producing high internal fields. The high accelerating voltage, in turn, produces electron and ion beams that heat the electrode surfaces. As a result of the heating, jets of electrode vapor issue from the electrodes, either cathode or anode, depending on the selection of electrode materials.

Morris, Gibson, Jr.↗

Impact of Electrolyte Additives on the Lifetime of High Voltage NMC Lithium-Ion Pouch Cells

This work involves improving the lifetime of lithium-ion cells during high voltage cycling using electrolyte additives. Three generations of electrolyte additives were investigated and screened in NMC442/graphite pouch cells using a 24 h voltage-hold protocol at 40 degrees C to accelerate oxidative reactions occurring at 4.4 V. Once promising additives and combinations were identified, they were then tested in cobalt-free NMC640/graphite cells for long-term cycling to upper cutoff voltages of 4.3, 4.4, and 4.5 V at temperatures of 20, 40, and 55 degrees C. Degradation mechanisms were probed using dV/dQ analysis, micro-X-ray fluorescence spectroscopy, and electrochemical impedance spectroscopy. The primary failure mode of cells held at high voltages is due to increase in cell impedance, which is correlated to the dissolution of transition metals, specifically manganese, originating from the positive electrode. We believe this dissolution is presumably due to the formation of a high impedance rock salt surface layer on the NMC positive electrode particles. Such deleterious outcomes can be limited by selecting an appropriate electrolyte additive package. It is hoped that this paper can provide a starting point for developing NMC Li-ion cells that can operate to voltages as high as 4.4 V and still display long lifetimes.

Azam, Saad↗

Battery Separator Characterization and Evaluation Procedures for NASA's Advanced Lithium-Ion Batteries

To address the future performance and safety requirements for the electrical energy storage technologies that will enhance and enable future NASA manned aerospace missions, advanced rechargeable, lithium-ion battery technology development is being pursued within the scope of the NASA Exploration Technology Development Program s (ETDP's) Energy Storage Project. A critical cell-level component of a lithium-ion battery which significantly impacts both overall electrochemical performance and safety is the porous separator that is sandwiched between the two active cell electrodes. To support the selection of the optimal cell separator material(s) for the advanced battery technology and chemistries under development, laboratory characterization and screening procedures were established to assess and compare separator material-level attributes and associated separator performance characteristics.

Baldwin, Richard S.↗

Assessing the coating implications of slurry formulations in NCMA and LFMP blend cathodes for lithium-ion batteries

This paper investigates the implications of slurry formulations and electrode processing on the performance of lithium-ion battery (LIB) cathodes, focusing on Nickel Cobalt Manganese Aluminum (NCMA) and Lithium Ferro Manganese Phosphate (LFMP) blends. Through a comprehensive examination of electrode processing steps, from material selection to coating application, we elucidate the critical role of processing parameters in shaping electrode morphology and electrochemical behavior. Rheological studies reveal the influence of slurry composition on viscosity and flow behavior, highlighting the importance of achieving optimal rheological properties for uniform coating deposition. Electrochemical characterization, including cyclic voltammetry and rate capability tests, unveils the electrochemical behavior of NCMA, LFMP, and their blend, showcasing the synergistic effects of material blending on battery performance. In conclusion, our findings underscore the intricate relationship between slurry formulation, electrode processing, and LIB performance, offering valuable insights for the design and optimization of high-performance electrode materials for next-generation batteries.

25 ENERGY STORAGE↗

High energy density secondary lithium batteries

A lithium ion battery includes a positive electrode comprising carbon fibers, a binder composition with conductive carbon, and a lithium rich composition. The lithium rich composition comprises at least one selected from the group consisting of Li 1+x (My Mz II Mw III )O 2 where x+y+z+w = 1, and where M, M II and M III are interchangeably manganese, nickel and cobalt, and LiM* 2-x M x * II O 4 , where M* and M* II are manganese and nickel, respectively, with x = 0.5. A negative electrode comprises carbon fibers having bound thereto silicon nanoparticles, and a mesophase pitch derived carbon binder between the silicon nanoparticles and the carbon fibers. An electrolyte is interposed between the positive electrode and the negative electrode. Methods of making positive and negative electrodes are also disclosed.

Nanda, Jagjit↗