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At least 253 records · Page 14

Additive manufacturing of LiCoO 2 electrodes via vat photopolymerization for lithium ion batteries

Additive manufacturing has the potential to revolutionize the fabrication of lithium-ion batteries for a diversity of applications including in portable, biomedical, aerospace, and the transportation fields. Standard commercial batteries consist of stacked layers of various components (current collectors, cathode, anode, separator and electrolyte) in a two-dimensional manner. By leveraging the latest advances in additive manufacturing and computer-aided design, an improved geometric and electrochemical configuration of these batteries can maximize energy efficiency while allowing design optimization to reduce dead space for a given application. In this work, a composite UV photosensitive resin was prepared and used as feedstock in a vat photopolymerization system. The resin was loaded with LiCoO 2 acting as electrochemically active material for the cathode of a lithium-ion battery, and was further improved with the addition of conductivity-enhancing carbonaceous additives. Challenges to additive manufacturing arise from the opacity and high viscosity of the composite nature of these electrochemically-active resins, which cause light refraction during selective UV curing. Subsequently, items were printed and subjected to a thermal post-processing step to obtain an adequate compromise between electrochemical performance and mechanical integrity. Both sintered and green state 3D printed cathodes were assembled into half-cell lithium-ion batteries using lithium metal as a reference and counter electrode. Electrochemical cycling of these batteries yielded satisfactory results approaching commercial LiCoO 2 cathodes’ performance, with the potential advantages of additive manufacturing – high surface area anode–cathode configurations for power performance as well as shape conformability.

25 ENERGY STORAGE↗

Hydrogenated indium oxide window layers for high-efficiency Cu(In,Ga)Se{sub 2} solar cells

High mobility hydrogenated indium oxide is investigated as a transparent contact for thin film Cu(In,Ga)Se{sub 2} (CIGS) solar cells. Hydrogen doping of In{sub 2}O{sub 3} thin films is achieved by injection of H{sub 2}O water vapor or H{sub 2} gas during the sputter process. As-deposited amorphous In{sub 2}O{sub 3}:H films exhibit a high electron mobility of ∼50 cm{sup 2}/Vs at room temperature. A bulk hydrogen concentration of ∼4 at. % was measured for both optimized H{sub 2}O and H{sub 2}-processed films, although the H{sub 2}O-derived film exhibits a doping gradient as detected by elastic recoil detection analysis. Amorphous IOH films are implemented as front contacts in CIGS based solar cells, and their performance is compared with the reference ZnO:Al electrodes. The most significant feature of IOH containing devices is an enhanced open circuit voltage (V{sub OC}) of ∼20 mV regardless of the doping approach, whereas the short circuit current and fill factor remain the same for the H{sub 2}O case or slightly decrease for H{sub 2}. The overall power conversion efficiency is improved from 15.7% to 16.2% by substituting ZnO:Al with IOH (H{sub 2}O) as front contacts. Finally, stability tests of non-encapsulated solar cells in dry air at 80 °C and constant illumination for 500 h demonstrate a higher stability for IOH-containing devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Solvent Motion on Ion Transport in Electrolytes

We use concentrated solution theory to derive an equation governing solvent velocity in a binary electrolyte when a current passes through it. This equation, in combination with the material balance equation, enables the prediction of electrolyte concentration profiles and species velocities as a function of space and time. This framework is used to predict ion velocities in Li-Li symmetric cells containing a mixture of lithium bis(trifluoromethanesulfonyl)imide and poly(ethylene oxide) (LiTFSI/PEO), for which the cation transference number relative to the solvent velocity, ${t}_{+}^{0},$ can be either positive or negative, depending on salt concentration. Accounting for the solvent motion is increasingly important at higher concentrations. Especially for negative ${t}_{+}^{0},$ if solvent velocity is set to zero, the cation velocity, based on the electrode-electrolyte interface reference frame, is pointed opposite to the current flow. However, when solvent motion is taken into account, the cation velocity, based on the same reference frame, is in the same direction as the current. This analysis demonstrates the importance of accounting for solvent velocity rigorously in seemingly simple systems such as symmetric cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Latent Effects of Radiation on Li-ion Batteries in Robots

The rapid development of Li-ion batteries (LIBs) is due to their high energy-density storage capability, which makes them suitable for application in both vehicles (e.g., electrified car) and electronic devices (e.g., cell phone, laptop, etc.), which are currently ubiquitous. Another less common but important application of LIBs is the powering of equipment in extreme environments such as robots operating in a nuclear rescue mission, unmanned vehicles surveying environments exposed to radiation, or vehicles and probes for outer space exploration. In our previous study, coin cells with lithium metal serving as the reference and counter electrode were assembled with either an irradiated cathode or irradiated electrolyte. We have observed an increase in premature battery failure and degradation of capacity of the battery made from irradiated cathodes and battery made from the irradiated electrolyte. For the group with cathodes irradiated to a 9.8 Mrad cumulative dose, the resistance was 2-3 times higher than the control group. On the other hand, cells with irradiated electrolyte showed increased resistance even at very low dose levels. Most importantly, a significant color change to the irradiated electrolyte after a long-term storage in a glove box has been observed. However, the electrolyte did not show any noticeable change immediately after irradiation. We name this phenomenon latent effects, which is more significant than the damage received by batteries due to initial dose. Also, electrolyte irradiated to a medium dose (1.6 Mrad) showed a poorer performance (higher failure rate, higher resistance) than those cells which received high dose (5 Mrad). We attribute this to the latent effect because this group battery was unintentionally assembled 3 days after initial electrolyte irradiation. The existence of latent effects implies that in space missions or post-accident events, instruments equipped with LIBs may fail unpredictably at post-irradiation stages, even if they survive the initial dose or the performance tests conducted after the initial dose. These instruments may fail several days or even weeks after irradiation, depending on the initial cumulative dose and dosage rate. For comprehending the influence of latent effects on the entire battery instead of on the individual components, we performed an in-situ cycling of coin cells made in-house, where the batteries were cycled under irradiation and then cycled again to evaluate their overall capacity fade, cyclability, and cell resistance. Additionally we investigated the effects of battery fading due to radiation on the performance of a drone.

25 ENERGY STORAGE↗

SU-E-I-52: Validation of Multi-Frequency Electrical Impedance Tomography Using Computed Tomography

Purpose: Multi-frequency EIT has been reported to be a potential tool in distinguishing a tissue anomaly from background. In this study, we investigate the feasibility of acquiring functional information by comparing multi-frequency EIT images in reference to the structural information from the CT image through fusion. Methods: EIT data was acquired from a slice of winter melon using sixteen electrodes around the phantom, injecting a current of 0.4mA at 100, 66, 24.8 and 9.9 kHz. Differential EIT images were generated by considering different combinations of pair frequencies, one serving as reference data and the other as test data. The experiment was repeated after creating an anomaly in the form of an off-centered cavity of diameter 4.5 cm inside the melon. All EIT images were reconstructed using Electrical Impedance Tomography and Diffuse Optical Tomography Reconstruction Software (EIDORS) package in 2-D differential imaging mode using one-step Gaussian Newton minimization solver. CT image of the melon was obtained using a Phillips CT Scanner. A segmented binary mask image was generated based on the reference electrode position and the CT image to define the regions of interest. The region selected by the user was fused with the CT image through logical indexing. Results: Differential images based on the reference and test signal frequencies were reconstructed from EIT data. Result illustrated distinct structural inhomogeneity in seeded region compared to fruit flesh. The seeded region was seen as a higherimpedance region if the test frequency was lower than the base frequency in the differential EIT reconstruction. When the test frequency was higher than the base frequency, the signal experienced less electrical impedance in the seeded region during the EIT data acquisition. Conclusion: Frequency-based differential EIT imaging can be explored to provide additional functional information along with structural information from CT for identifying different tissues.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Electrically regenerated ion-exchange technology: Leveraging faradaic reactions and assessing the effect of co-ion sorption

Capacitive deionization (CDI) technologies have the potential to become cost-competitive alternatives to reverse osmosis for the treatment of brackish waters. In this study, we describe our findings on the effect of co-ion sorption and faradaic side reactions on our ion exchange resin functionalized desalination electrodes which passively capture salt and reject it upon charging. This system, which we previously reported on and refer to as electrically regenerated ion exchange (ERI), avoids the use of expensive ion exchange membranes in an effort to save costs. Surprisingly, we find that, compared to a reference CDI system, ERI electrodes capture salt most effectively at low applied voltages (0.5 mg/cm 3 at 0.8 V). Both CDI and ERI systems also seem to suffer from co-ion sorption effects which negatively impact salt adsorption. However, Faradaic side reactions at higher voltages (1 V and 1.2 V) which we track via pH measurements, serve as a detriment to CDI but seem to facilitate the functionality of ERI.

42 ENGINEERING↗

Carbon Electrode with Sputtered Au Coating for Efficient and Stable Perovskite Solar Cells

Halide perovskite solar cells (PSCs) represent a low-cost and high-efficiency solar technology. However, most of the highly efficient PSCs need a noble electrode, such as Au, through thermal evaporation. Here it is reported that a sputtered Au electrode on a PSC could damage the organic hole transport layer (HTL) and the perovskite layer. Here, we report a simple, yet effective sputtered gold nanoparticle decorated carbon electrode to fabricate efficient and stable planar PSCs. The sputtered Au layer on the doctor-bladed coated carbon electrode can be directly applied to the perovskite semicells by mechanical stacking. By optimizing the gold thickness, a power conversion efficiency (PCE) of 16.87% was obtained for the composite electrode-based PSC, while the reference device recorded a PCE of 12.38%. The composite electrode-based device demonstrated 96% performance retention after being stored under humid conditions (50-60%) without encapsulation for ~100 h. This demonstrates a promising pathway toward the commercialization of large-scale manufacturable sputtered electrodes for the PSC solar module.

14 SOLAR ENERGY↗

Electrode size and boundary condition independent measurement of the effective piezoelectric coefficient of thin films

The determination of the piezoelectric coefficient of thin films using interferometry is hindered by bending contributions. Using finite element analysis (FEA) simulations, we show that the Lefki and Dormans approximations using either single or double-beam measurements cannot be used with finite top electrode sizes. We introduce a novel method for characterising piezoelectric thin films which uses a differential measurement over the discontinuity at the electrode edge as an internal reference, thereby eliminating bending contributions. This step height is shown to be electrode size and boundary condition independent. An analytical expression is derived which gives good agreement with FEA predictions of the step height.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Failure Analysis of Pinch Weld Electrodes

We present that Savannah River Site uses brazed copper/tungsten electrodes for a specialized weld referred to as a pinch weld. An alternative method to produce the pinch weld electrodes was sought to improve quality and to reduce the manufacturing steps. Backcasting of pinch weld electrodes was selected as such a process. During preliminary testing, deformation of the electrodes was observed. A failure analysis assessment was conducted and the strength of the electrodes was found to be significantly less than required to enable welding of the tubes. This assessment includes compression testing metallographic analysis. The pinch weld electrodes fabricated by backcasting do not meet the requirements with respect to strength. Additionally, a minimum strength requirement for conventionally prepared electrodes is recommended.

36 MATERIALS SCIENCE↗

Resonant anomalous X-ray reflectivity for revealing ion distributions near electrodes

Energy storage devices–batteries, for example–consist of an electrolyte sandwiched between two charged electrodes through which current can pass. The metal ion organization at the electrode–electrolyte interface, commonly referred to as the electric double layer, determines the efficiency and stability of the device. There are two major challenges with experimentally characterizing the metal ion distribution at the interface.

42 ENGINEERING↗

Fabrication of Enhanced Pinch Weld Electrodes

Savannah River Site uses brazed copper / tungsten electrodes for a specialized weld referred to as a pinch weld. As part of an internally funded PDRD program, an alternative method to produce the pinch weld electrodes was sought to improve quality and to reduce the manufacturing steps. Back casting of pinch weld electrodes was selected as such a process. During preliminary testing, deformation of the electrodes was observed. A failure analysis was conducted, and the strength of the electrodes was found to be significantly less than required to enable welding of the tubes. This assessment includes compression testing metallographic analysis. The pinch weld electrodes fabricated by back casting do not meet the requirements with respect to strength. In addition, a minimum strength requirement for conventionally prepared electrodes is recommended.

42 ENGINEERING↗

Regenerative Performance of the NASA Symmetrical Solid Oxide Fuel Cell Design

The NASA Glenn Research Center is developing both a novel cell design (BSC) and a novel ceramic fabrication technique to produce fuel cells predicted to exceed a specific power density of 1.0 kW/kg. The NASA Glenn cell design has taken a completely different approach among planar designs by removing the metal interconnect and returning to the use of a thin, doped LaCrO3 interconnect. The cell is structurally symmetrical. Both electrodes support the thin electrolyte and contain micro-channels for gas flow-- a geometry referred to as a bi-electrode supported cell or BSC. The cell characteristics have been demonstrated under both SOFC and SOE conditions. Electrolysis tests verify that this cell design operates at very high electrochemical voltage efficiencies (EVE) and high H2O conversion percentages, even at the low flow rates predicted for closed loop systems encountered in unmanned aerial vehicle (UAV) applications. For UAVs the volume, weight and the efficiency are critical as they determine the size of the water tank, the solar panel size, and other system requirements. For UAVs, regenerative solid oxide fuel cell stacks (RSOFC) use solar panels during daylight to generate power for electrolysis and then operate in fuel cell mode during the night to power the UAV and electronics. Recent studies, performed by NASA for a more electric commercial aircraft, evaluated SOFCs for auxiliary power units (APUs). System studies were also conducted for regenerative RSOFC systems. One common requirement for aerospace SOFCs and RSOFCs, determined independently in each application study, was the need for high specific power density and volume density, on the order of 1.0 kW/kg and greater than 1.0 kW/L. Until recently the best reported performance for SOFCs was 0.2 kW/kg or less for stacks. NASA Glenn is working to prototype the light weight, low volume BSC design for such high specific power aerospace applications.

Cable, Thomas L.↗

Direct Measurement of Cl − Activity in Metal Chloride Molten Salts using a Cl 2 /Cl − Electrode

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. The activity of the chloride ion in the salt has a large influence on the redox characteristics of the corresponding molten salt. There exists a knowledge gap for the direct measurement of chlorobasicity (Lewis basicity) in molten-salt mixtures. Here, the focus of this work was to develop a Cl 2 /Cl − electrode for the direct measurement of chloride activity in molten metal-chloride salt mixtures. The LiCl–KCl eutectic system was utilized as the reference melt to determine the change in chloride ion activity as increasing concentrations of MgCl 2 are added to the LiCl–KCl eutectic working electrode. The results of the measurements indicated a reduction in chloride ion activity as the concentration of magnesium chloride increased, consistent with the complexation of free chlorides by Lewis acidic magnesium cationic species. The Temkin model was used to estimate the thermodynamic properties of MgCl 4 2− complex.

Chloride↗

Printed Potentiometric Ammonium Sensors for Agriculture Applications

Ammonium (NH 4 + ) concentration is critical to both nutrient availability and nitrogen (N) loss in soil ecosystems but can be highly variable across spatial and temporal scales. For this reason, effectively informing agricultural practices such as fertilizer management and understanding of mechanisms of soil N loss require sensor technologies to monitor ammonium concentrations in real time. Our work investigates the performance of fully printed ammonium ion-selective sensors used in diverse soil environments. Ammonium sensors consisting of a printed ammonium ion-selective electrode and a printed Ag/AgCl reference were fabricated and characterized in aqueous solutions and three different soil types (sand, peat, and clay) under the range of ion concentrations likely to be present in soil (0.01–100 mM). The response of ammonium sensors was further evaluated under variable gravimetric moisture content in the soil to reflect their reliability under field conditions. Ammonium sensors demonstrated a sensitivity of 53.6 ± 5.1 mV/decade when tested in aqueous solution, and a sensitivity of 55.7 ± 11 mV/dec, 57.5 ± 4.1 mV/dec, and 43.7 ± 4 mV/dec was measured in sand, clay, and peat soils, respectively.

60 APPLIED LIFE SCIENCES↗

Improved open-circuit voltage in Cu(In,Ga)Se{sub 2} solar cells with high work function transparent electrodes

Hydrogenated indium oxide (IOH) is implemented as transparent front contact in Cu(In,Ga)Se{sub 2} (CIGS) solar cells, leading to an open circuit voltage V{sub OC} enhanced by ∼20 mV as compared to reference devices with ZnO:Al (AZO) electrodes. This effect is reproducible in a wide range of contact sheet resistances corresponding to various IOH thicknesses. We present the detailed electrical characterization of glass/Mo/CIGS/CdS/intrinsic ZnO (i-ZnO)/transparent conductive oxide (TCO) with different IOH/AZO ratios in the front TCO contact in order to identify possible reasons for the enhanced V{sub OC}. Temperature and illumination intensity-dependent current-voltage measurements indicate that the dominant recombination path does not change when AZO is replaced by IOH, and it is mainly limited to recombination in the space charge region and at the junction interface of the solar cell. The main finding is that the introduction of even a 5 nm-thin IOH layer at the i-ZnO/TCO interface already results in a step-like increase in V{sub OC}. Two possible explanations are proposed and verified by one-dimensional simulations using the SCAPS software. First, a higher work function of IOH as compared to AZO is simulated to yield an V{sub OC} increase by 21 mV. Second, a lower defect density in the i-ZnO layer as a result of the reduced sputter damage during milder sputter-deposition of IOH can also add to a maximum enhanced V{sub OC} of 25 mV. Our results demonstrate that the proper choice of the front TCO contact can reduce the parasitic recombination and boost the efficiency of CIGS cells with improved corrosion stability.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

MRT 7365: Power flow physics and key physics phenomena

The Z accelerator at Sandia National Laboratories conducts z-pinch experiments at 26 MA in support of DOE missions in stockpile stewardship, dynamic materials, fusion, and other basic sciences. Increasing the current delivered to the z-pinch would extend our reach in each of these disciplines. To achieve increases in current and accelerator efficiency, a fraction of Z’s shots are set aside for research into transmission-line power flow. These shots, with supporting simulations and theory, are incorporated into this Advanced Diagnostics milestone report. The efficiency of Z is reduced as some portion of the total current is shunted across the transmission-line gaps prior to the load. This is referred to as “current loss”. Electrode plasmas have long been implicated in this process, so the bulk of dedicated power-flow experiments are designed to measure the plasma environment. The experimental analyses are enhanced by simulations conducted using realistic hardware and Z voltage pulses. In the same way that diagnostics are continually being improved for sensitivity and resolution, the modeling capability is continually being improved to provide faster and more realistic simulations. The specifics of the experimental hardware, diagnostics, simulations, and algorithm developments are provided in this report. The combined analysis of simulation and data confirms that electrode plasmas have the most detrimental impact on current delivery. Experiments over the last three years have tested the theoretical current-loss mechanisms of enhanced ion current, plasma gap closure, and Hall-related current. These mechanisms are not mutually exclusive and may be coincident in the final feed as well as in upstream transmission lines. The final-feed geometries tested here, however, observe lower-density plasmas without dominant ion currents which is consistent with a Hall-related current. The picture of plasma formation and transport formed from experiment and simulation is informing hardware designs being fielded on Z now and being proposed for the Next-Generation Pulsed Power (NGPP) facility. In this picture, the strong magnetic fields that heat the electrodes above particle emission thresholds also confine the charged particles near the surface. Some portion of the plasmas thus formed is transported into the transmission-line gap under the force of the electric field, with aid from plasma instabilities. The gap plasmas are then transported towards the load by a cross-field drift, where they accumulate and contribute to a likely Hall-related cross-gap current. The achievements in experimental execution, model validation, and physical analysis presented in this report set the stage for continued progress in power flow and load diagnostics on Z. The planned shot schedule for Z and Mykonos will provide data for extrapolation to higher current to ensure the predicted performance and efficiency of a NGPP facility.

43 PARTICLE ACCELERATORS↗

Pitting of titanium. I - Titanium-foil experiments. II - One-dimensional pit experiments.

Pitting experiments were conducted with strips of titanium foil in beakers containing chloride, bromide, or iodide solutions. The potentials were determined in reference to the saturated calomel electrode. Corrosion occurred at the edge of a foil specimen when it was maintained at a potential between the steady-state pitting potential of about 0.9 V and a potential of about 1.4 V in neutral bromide solution. A model is discussed to account for the complex relationships observed in the experiments. Conclusions based on experiments conducted with one-dimensional pits at the ends of insulated titanium pencils in the anode-facing-up position are also presented.

Beck, T. R.↗