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At least 811 records · Page 45

The LiAl/FeS2 battery power source for the future

Advanced high power density rechargeable batteries are currently under development. These batteries have the potential of greatly increasing the power and energy densities available for space applications. Depending on whether the system is optimized for high power or high energy, values up to 150 Wh/kg and 2100 W/kg (including hardware) are projected. This is due to the fact that the system uses a high conductivity molten salt electrolyte. The electrolyte also serves as a separator layer with unlimited freeze thaw capabilities. Life of 1000 cycles and ten calendar years is projected. The electrochemistry consists of a lithium aluminum alloy negative electrode, iron disulfide positive electrode, and magnesium oxide powder immobilized molten salt electrolyte. Processed powders are cold compacted into circular discs which are assembled into bipolar cell hardware with peripheral ceramic salts. The culmination of the work will be a high energy battery of 40 kWh and a high power battery of 28 kWh.

Briscoe, J. Douglass↗

Technology for Water Treatment

There are approximately 500,000 water cooling towers in the United States, all of which must be kept clear of "scale" and corrosion and free of pollutants and bacteria. Electron Pure, Ltd. manufactures a hydro cooling tower conditioner as well as an automatic pool sanitizer. The pool sanitizer consists of two copper/silver electrodes placed in a chamber mounted in the pool's recirculation system. The tower conditioner combines the ionization system with a water conditioner, pump, centrifugal solids separator and timer. The system saves water, eliminates algae and operates maintenance and chemical free. The company has over 100 distributors in the U.S. as well as others in 20 foreign countries. The buildup of scale and corrosion is the most costly maintenance problem in cooling tower operation. Jet Propulsion Laboratory successfully developed a non-chemical system that not only curbed scale and corrosion, but also offered advantages in water conservation, cost savings and the elimination of toxic chemical discharge. In the system, ozone is produced by an on-site generator and introduced to the cooling tower water. Organic impurities are oxidized, and the dissolved ozone removes bacteria and scale. National Water Management, a NASA licensee, has installed its ozone advantage systems at some 200 cooling towers. Customers have saved money and eliminated chemical storage and discharge.

Source record↗

Current Density Measurements of an Annular-Geometry Ion Engine

The concept of the annular-geometry ion engine, or AGI-Engine, has been shown to have many potential benefits when scaling electric propulsion technologies to higher power. However, the necessary asymmetric location of the discharge cathode away from thruster centerline could potentially lead to non-uniformities in the discharge not present in conventional geometry ion thrusters. In an effort to characterize the degree of this potential non-uniformity, a number of current density measurements were taken on a breadboard AGI-Engine. Fourteen button probes were used to measure the ion current density of the discharge along a perforated electrode that replaced the ion optics during conditions of simulated beam extraction. Three Faraday probes spaced apart in the vertical direction were also used in a separate test to interrogate the plume of the AGI-Engine during true beam extraction. It was determined that both the discharge and the plume of the AGI-Engine are highly uniform, with variations under most conditions limited to +/-10% of the average current density in the discharge and +/-5% of the average current density in the plume. Beam flatness parameter measured 30 mm from the ion optics ranged from 0.85 - 0.95, and overall uniformity was shown to generally increase with increasing discharge and beam currents. These measurements indicate that the plasma is highly uniform despite the asymmetric location of the discharge cathode.

Shastry, Rohit↗

Current Density Measurements of an Annular-Geometry Ion Engine

The concept of the annular-geometry ion engine, or AGI-Engine, has been shown to have many potential benefits when scaling electric propulsion technologies to higher power. However, the necessary asymmetric location of the discharge cathode away from thruster centerline could potentially lead to non-uniformities in the discharge not present in conventional geometry ion thrusters. In an effort to characterize the degree of this potential nonuniformity, a number of current density measurements were taken on a breadboard AGI-Engine. Fourteen button probes were used to measure the ion current density of the discharge along a perforated electrode that replaced the ion optics during conditions of simulated beam extraction. Three Faraday probes spaced apart in the vertical direction were also used in a separate test to interrogate the plume of the AGI-Engine during true beam extraction. It was determined that both the discharge and the plume of the AGI-Engine are highly uniform, with variations under most conditions limited to 10% of the average current density in the discharge and 5% of the average current density in the plume. Beam flatness parameter measured 30 mm from the ion optics ranged from 0.85 0.95, and overall uniformity was shown to generally increase with increasing discharge and beam currents. These measurements indicate that the plasma is highly uniform despite the asymmetric location of the discharge cathode.

Shastry, Rohit↗

Device and method to manipulate ions in multi level system

An apparatus includes multiple levels of ion transport channels, with successive levels coupled by elevator channels. Efficient three dimensional packing provides long path lengths in practical volumes for ion mobility separation with high resolving power. Disclosed elevator configurations provide efficient routing of ion transport channels across levels with low ion loss, enabling ion mobility separation over 100 levels or more. Elevator configurations include (i) opposed traveling waves meeting at an elevator entrance, (ii) external elevator with a wrap-around electrode bank, (iii) external elevator with electrode banks on parallel extension plates, or (iv) elevator operating in surfing mode, in various combinations. Manufacture is aided by printed wiring boards, with interchangeable boards. Assembly with motherboard, spacer block(s), and alignment pins provides efficient distribution of electrode excitations and accurate reproducible positioning.

Ibrahim, Yehia M.↗

Device and method to manipulate ions in multi-level system

An apparatus includes multiple levels of ion transport channels, with successive levels coupled by elevator channels. Efficient three dimensional packing provides long path lengths in practical volumes for ion mobility separation with high resolving power. Disclosed elevator configurations provide efficient routing of ion transport channels across levels with low ion loss, enabling ion mobility separation over 100 levels or more. Elevator configurations include (i) opposed traveling waves meeting at an elevator entrance, (ii) external elevator with a wrap-around electrode bank, (iii) external elevator with electrode banks on parallel extension plates, or (iv) elevator operating in surfing mode, in various combinations. Manufacture is aided by printed wiring boards, with interchangeable boards. Assembly with motherboard, spacer block(s), and alignment pins provides efficient distribution of electrode excitations and accurate reproducible positioning.

Ibrahim, Yehia M.↗

Dimensionally Controlled Lithiation of Chromium Oxide

Oxide conversion reactions are an alternative approach for high capacity lithium ion batteries but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. In particular, the morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. Here we use a model electrode with alternating layers of chromium and chromium oxide to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with X-ray reflectivity, XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials.

25 ENERGY STORAGE↗

Continuous-flow electrophoretic separator for biologicals

In the near absence of gravity, a continuous-flow type of electrophoretic separator can be operated with a much thicker separation chamber than is possible under 1 g conditions. This should permit either better resolution or shorter separation time per unit of sample. An apparatus to perform experiments on sounding rockets is under development and will be described. The electrophoresis cell is 5 mm thick by 5 cm wide with 10 cm long electrodes. It is supplied with buffer, sample, and coolant at about 4 C through the use of a passive refrigerant system. UV sample detection and provision for recovery and cold storage of up to 50 sample fractions are now being added to the basic unit. A wide range of operating conditions are electronically programmable into the unit, even up to a short time before flight, and a further range of some parameters can be achieved by exchanging power supplies and by changing gears in the motor drive units of the pump. The preliminary results of some separation studies on various biological products using a commercially available electrophoretic separator are also presented.

Mccreight, L. R.↗

WE-G-18A-01: JUNIOR INVESTIGATOR WINNER - Low-Dose C-Arm Cone-Beam CT with Model-Based Image Reconstruction for High-Quality Guidance of Neurosurgical Intervention

Purpose: To address the challenges of image quality, radiation dose, and reconstruction speed in intraoperative cone-beam CT (CBCT) for neurosurgery by combining model-based image reconstruction (MBIR) with accelerated algorithmic and computational methods. Methods: Preclinical studies involved a mobile C-arm for CBCT imaging of two anthropomorphic head phantoms that included simulated imaging targets (ventricles, soft-tissue structures/bleeds) and neurosurgical procedures (deep brain stimulation (DBS) electrode insertion) for assessment of image quality. The penalized likelihood (PL) framework was used for MBIR, incorporating a statistical model with image regularization via an edgepreserving penalty. To accelerate PL reconstruction, the ordered-subset, separable quadratic surrogates (OS-SQS) algorithm was modified to incorporate Nesterov's method and implemented on a multi-GPU system. A fair comparison of image quality between PL and conventional filtered backprojection (FBP) was performed by selecting reconstruction parameters that provided matched low-contrast spatial resolution. Results: CBCT images of the head phantoms demonstrated that PL reconstruction improved image quality (∼28% higher CNR) even at half the radiation dose (3.3 mGy) compared to FBP. A combination of Nesterov's method and fast projectors yielded a PL reconstruction run-time of 251 sec (cf., 5729 sec for OS-SQS, 13 sec for FBP). Insertion of a DBS electrode resulted in severe metal artifact streaks in FBP reconstructions, whereas PL was intrinsically robust against metal artifact. The combination of noise and artifact was reduced from 32.2 HU in FBP to 9.5 HU in PL, thereby providing better assessment of device placement and potential complications. Conclusion: The methods can be applied to intraoperative CBCT for guidance and verification of neurosurgical procedures (DBS electrode insertion, biopsy, tumor resection) and detection of complications (intracranial hemorrhage). Significant improvement in image quality, dose reduction, and reconstruction time of ∼4 min will enable practical deployment of low-dose C-arm CBCT within the operating room. AAPM Research Seed Funding (2013-2014); NIH Fellowship F32EB017571; Siemens Healthcare (XP Division)

60 APPLIED LIFE SCIENCES↗

Local structures in mixed Li{sub x}Fe{sub 1−y}M{sub y}PO{sub 4} (M=Co, Ni) electrode materials

We employ {sup 57}Fe Mössbauer spectroscopy as a local tool to probe electrical environments of Fe{sup 2+} and Fe{sup 3+} at different lithiation (x) and cation-substitution (y) levels in Li{sub x}Fe{sub 1−y}M{sub y}PO{sub 4}/C (M=Co, Ni) Li-ion battery electrode materials. Upon delithiation the local environment of Fe{sup 3+} remains unaffected for the parent y=0 system due to the LiFePO{sub 4}/FePO{sub 4} phase separation, whereas for y>0 changes in the electrical environment are seen for Fe{sup 3+}. When the Fe{sup 2+}/Fe{sup 3+} redox couple is partially-delithiated, a decreasing quadrupole splitting value is observed for Fe{sup 3+} with increasing y, implying a more symmetric electrical environment. The increasing concentration of the Co{sup 2+}/Ni{sup 2+} substituent introduces increasing amounts of Li atoms in the Fe{sup 3+}-containing phase, and these nearest-neighbor Li atoms are suspected to cause the changes seen in the local environment of Fe{sup 3+}. - Graphical abstract: Local environment of iron in Li{sub x}Fe{sub 1−y}(Co/Ni){sub y}PO{sub 4} is studied by {sup 57}Fe Mössbauer spectroscopy at different lithiation (x) and cation-substitution (y) levels. - Highlights: • Local Fe environment in Li{sub x}Fe{sub 1−y}(Co/Ni){sub y}PO{sub 4} is studied by {sup 57}Fe Mössbauer spectroscopy. • Co/Ni-for-Fe substitution results in a more symmetric electrical environment for Fe{sup 3+}. • Due to presence of Co{sup 2+}/Ni{sup 2+}, Li atoms are introduced into the Fe{sup 3+}-containing phase. • These nearest-neighbor Li atoms are suggested to change the local Fe{sup 3+} environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anomalous interfacial stress generation during sodium intercalation/extraction in MoS 2 thin-film anodes

Although the generation of mechanical stress in the anode material is suggested as a possible reason for electrode degradation and fading of storage capacity in batteries, only limited knowledge of the electrode stress and its evolution is available at present. Here, we show real-time monitoring of the interfacial stress of a few-layer MoS 2 system under the sodiation/desodiation process using microcantilever electrodes. During the first sodiation with a voltage plateau of 1.0 to 0.85 V, the MoS 2 exhibits a compressive stress (2.1 Nm -1 ), which is substantially smaller than that measured (9.8 Nm -1 ) during subsequent plateaus at 0.85 to 0.4 V due to the differential volume expansion of the MoS 2 film. The conversion reaction to Mo below 0.1 V generates an anomalous compressive stress of 43 Nm -1 with detrimental effects. These results also suggest the existence of a separate discharge stage between 0.6 and 0.1 V, where the generated stress is only approximately one-third of that observed below 0.1 V. This approach can be adapted to help resolve the localized stress in a wide range of electrode materials, to gain additional insights into mechanical effects of charge storage, and for long-lifetime battery design.

36 MATERIALS SCIENCE↗

Advanced Electrochemical Separations of Actinide/Fission Products via the Control of Nucleation and Growth of Electrodeposits. Final Report

This is the final report to the NEUP regarding the “Advanced Electrochemical Separations of Actinide/Fission products via the Control of Nucleation and Growth of Electrodeposits” project. This report describes the project activities conducted during the period October 01, 2016 through September 30, 2019. The report includes a brief statement of the project objectives and approach, followed by the details of the performed research activities and suggestion for the future work. It is well known that according to current knowledge the pyroprocessing of spent nuclear fuels invariably leads to the dendritic form of electrodeposits, which from technological point of view is undesirable for many reasons. The aim of this research was to study and preclude the formation of electrodeposits with dendritic morphology (of essential importance to FC-1 Program). This project is characterized with four novel study categories: (1) exploring electrodeposit morphology control by controlling the electrochemical deposition reaction rate, (2) the use of rotating disk electrode technique to distinguish the electrodeposition control modes (reaction rate vs. diffusion), (3) morphology studies of lanthanides (La) and actinides (U) in characteristic stages of nucleation and growth, (4) exploring the need for separation of electrochemical cell in compartments for cathodic and anodic reactions. All these study categories were applied on two distinct electrolyte systems (a) high temperature ionic liquids, i.e. molten LiCl-KCl salts, and (b) room temperature ionic liquids (compounds exclusively made of organic cations, and organic/inorganic anions). Because the quality (dense and smooth) of electrodeposits is a direct function of the electrochemical reduction rate (slower the better), the major expectation was that addition of organic molecules would provide the desired slowing down of electroreduction effect, avoiding the undesired dependence on mass transfer. What was learned is summarized in seven key areas.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Ni/NiO Reference Electrode Potential Measurements in Molten CaCl 2 –CaO

A direct oxide reduction (DOR) process is used to reduce PuO 2 to Pu metal via Ca metal. Molten CaCl 2 is commonly used as the electrolyte for this reaction. As the DOR reaction proceeds, CaO accumulates in the salt and must be measured in real-time to know when the reaction has gone to completion. Open circuit potential (OCP) was measured in this report between a reference electrode consisting of Ni/NiO contained in a MgO tube and a tungsten working electrode. Two methods of CaO additions were performed over several experiments, and both methods correlated to a 0.11 to 0.23 V decrease in OCP up to 14.4 wt% CaO. CaO concentrations were separately measured via sampling and acid-base titration. A plot of OCP versus concentration of CaO fits the Nernst equation with the CaO powder additions up to 5.2 wt% and also at the higher end of the CaO pellet concentration range. While the MgO tubes were observed to be structurally stable in the molten salt, scanning electron microscopy and energy dispersive X-ray spectroscopy showed that Mg in the tubes had been partially replaced with Ca.

36 MATERIALS SCIENCE↗

Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength

Ion permselectivity can lead to accumulation in zero-dimensional nanopores, producing a significant increase in ion concentration, an effect which may be combined with unscreened ion migration to improve sensitivity in electrochemical measurements, as demonstrated by the enormous current amplification (~2000-fold) previously observed in nanopore electrode arrays (NEA) in the absence of supporting electrolyte. Ionic strength is a key experimental factor that governs the magnitude of the additional current amplification (AF ad ) beyond simple redox cycling through both ion accumulation and ion migration effects. Here, separate contributions from ion accumulation and ion migration to the overall AF ad were identified by studying NEAs with varying geometries, with larger AF ad values being achieved in NEAs with smaller pores. In addition, larger AF ad values were observed for Ru(NH 3 ) 6 3/2+ than for ferrocenium/ferrocene (Fc + /Fc) in aqueous solution, indicating that coupling efficiency in redox cycling can significantly affect AF ad . While charged species are required to observe migration effects or ion accumulation, poising the top electrode at an oxidizing potential converts neutral species to cations, which can then exhibit current amplification similar to starting with the cation. The electrical double layer effect was also demonstrated for Fc/Fc + in acetonitrile and 1,2-dichloroethane, producing AF ad up to 100× at low ionic strength. The pronounced AF ad effects demonstrate the advantage of coupling redox cycling with ion accumulation and migration effects for ultrasensitive electrochemical measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling a High-Temperature Electrochemically Driven Water-Gas-Shift Process Using a Mixed-Conducting Membrane without External Electrical Power

This paper develops a model to predict and interpret the performance of an elevated-temperature, electrochemical, membrane-assisted, water-gas-shift process. The process uses separated feed streams of H 2 O and CO to produce separated streams of H 2 and CO 2 , without an external electrical power source. The dense ceramic membrane is mixed ionic-electronic-conducting (MIEC) gadolinium-doped ceria (GDC) and the porous composite electrodes are Ni-YSZ. At elevated temperature, GDC conducts both oxygen ions and small polarons. The present process uses chemical potential to drive the process. Electrochemical oxidation of CO proceeds within the composite anode and H 2 O reduction proceeds within the composite cathode. At high temperature (e.g., T > 700 °C), GDC has significant electronic leakage in the form of a reduced-cerium small polaron, which supports the charge-transfer reactions. In a typical electrolyzer or fuel cell, this leakage is significantly problematic. However, the present process depends on the leakage current to complete the electrochemical circuit. Model development and validation is based on measured material properties and reactor performance. Potential applications include using CO-rich blast-furnace off gases in steel processing, producing separated streams of H 2 and CO 2 .

Zhu, Huayang↗

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Hooker, M. W.↗

Stabilizing the Garnet Solid-Electrolyte/Polysulfide Interface in Li–S Batteries

Chemical and physical short circuits are the main challenges faced by lithium batteries which compromise battery performance and safety. At the cathode, solvation of active cathode materials and shuttling of unwanted chemical species in the liquid electrolyte result in “chemical short circuits”, which deteriorate the Li metal electrode and limit the deployment of new cathode materials, such as high voltage cathodes, sulfur, and air/O 2 . In Li–S batteries, the repeated shuttling of polysulfides between electrodes constantly corrodes the Li metal anode and the loss of active material will result in low Coulombic efficiency. At the anode, Li dendrite penetration through the separator causes internal electronic, or “physical”, short circuits. Finally, several strategies have been reported to prevent chemical and physical short circuits by using a cathode host, small sulfur molecules, modified separators, or electrolyte additives to alleviate sulfur materials diffusion and shuttling, and finding ways to delay, confine, or block Li dendrites to extend the cycling lifetime and avoid thermal runaway in lithium metal batteries.

25 ENERGY STORAGE↗