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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 361 records · Page 20

Superstructured NiMoO 4 @CoMoO 4 core-shell nanofibers for supercapacitors with ultrahigh areal capacitance

High areal capacitance for a practical supercapacitor electrode requires both large mass loading and high utilization efficiency of electroactive materials, which presents a great challenge. Herein, we demonstrated the unprecedented synthesis of superstructured NiMoO 4 @CoMoO 4 core-shell nanofiber arrays (NFAs) on a Mo-transition-layer-modified nickel foam (NF) current collector as a new material, achieving the synergistic combination of highly conductive CoMoO 4 and electrochemical active NiMoO 4 . Moreover, this superstructured material exhibited a large gravimetric capacitance of 1,282.2 F/g in 2 M KOH with a mass loading of 7.8 mg/cm 2 , leading to an ultrahigh areal capacitance of 10.0 F/cm 2 that is larger than any reported values of CoMoO 4 and NiMoO 4 electrodes. In conclusion, this work provides a strategic insight for rational design of electrodes with high areal capacitances for supercapacitors.

42 ENGINEERING↗

Investigating the effect of screen-printed structured graphite electrodes with low tortuosity for high-capacity and fast-charging lithium-ion batteries

A flexible screen-printed graphite electrode was fabricated as an anode for developing fast-charging lithium-ion batteries with low tortuosity. A homogenous anode ink was prepared by mixing graphite as the active material, carbon black (C45) as the conductive additive, and polyvinylidene fluoride (PVDF) as the binder in N-Methyl-2-pyrrolidone (NMP) solvent. The ink was deposited on a flexible copper foil via a stainless-steel screen consisting of an array of pores, that act as secondary pore networks (SPNs), using the screen-printing process. Lithium-ion battery half-cells were assembled using the printed graphite anode, lithium metal foil as the counter electrode, and 1.2 M lithium hexafluorophosphate (LiPF 6 ) in ethyl carbonate: ethyl methyl carbonate (EC: EMC = 3:7) as the electrolyte. The effect of SPNs on the cell performance was investigated by performing formation, rate and cycling tests on the assembled cells, at different C-rates. It was observed that the cells consisting of SPNs with a pore size of 100 μm and edge-to-edge distance of 100 μm between the pores exhibited significantly higher specific capacities of 168 and 129 mAh/g when compared to reference cells without SPNs, which had capacities of 120 and 85 mAh/g, at high C-rates of 4 C and 6 C, respectively. The cells with SPNs also demonstrated excellent cycling performance with ~ 95% capacity retention after 100 cycles at 2 C.

Fast charging lithium-ion battery↗

Facile in Situ Syntheses of Cathode Protective Electrolyte Additives for High Energy Density Li-Ion Cells

Increasing the energy densities of Li-ion batteries necessitates operation of layered lithiated oxide cathodes at potentials exceeding 4 V vs Li/Li + . When continually exposed to such high potentials, these materials gradually deteriorate unless protected by sacrificial agents called electrolyte additives. During the formation cycles, these electrolyte additives decompose on the electrodes forming thin protective layers of insoluble products impeding further deleterious reactions. Some of these electrolyte additives spontaneously react when introduced into the electrolyte to yield specific surface-modifying products that alone protect the cathode; in other words, the nominal additive is the precursor and the secondary product is the protective agent. Guided by this insight, we used molecular engineering to obtain such surface-active secondary products in situ with 100% yield. Two of these electrolyte additives proved exceptional in that they delay both the impedance rise and capacity fade in the Li-ion cells. We demonstrate this protective action and scrutinize the activation of these additives in the electrolyte. As a result, by “taming” spontaneous reactions and regaining full control over the chemical structure, new avenues open to targeted synthesis of electrolyte additives extending the operation of high voltage Li-ion batteries.

25 ENERGY STORAGE↗

Characterizing oxygen dynamics in multicellular tumor spheroids

In 2018, an estimated 1.7 million people in the United States will be diagnosed with cancer, and over one third of those people will die due to a lack of effective treatments and lack of a cure. To combat this issue, Lawrence Livermore National Laboratory (LLNL) is developing an ex vivo 3D tumor spheroid model that can be used to more efficiently and effectively conduct cancer research. Ultimately, the goal is for this model to become patient-derived as it would be a huge advancement in personalized medicine. To begin validating the biological relevance of these tumor spheroid models as in vivo surrogates, LLNL will use flexible microelectrode arrays (MEAs) to characterize their oxygen dynamics. LLNL MEAs were inserted into the tumor spheroids and amperometric oxygen detection was conducted using a 3-electrode system with 10 μm diameter platinum (Pt) working electrodes (WE), an Iridium Oxide (IrOx)-plated reference electrode (RE), and a platinum counter electrode (CE). Preliminary results suggest that real-time amperometric oxygen detection can feasibly be achieved in tumor spheroids using LLNL’s MEAs, however, the 10 μm diameter Pt WEs may lack both the sensitivity (-0.034 nA/% DO) and the limit of detection (LOD) (0.272 nA or 7.45% DO) needed to detect oxygen levels found in tumor spheroids in the 3.96-15.79% DO range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring electrode microstructure via ink content to enable improved rated power performance for platinum cobalt/high surface area carbon based polymer electrolyte fuel cells

Improvements in polymer electrolyte fuel cell (PEFC) electrode performance have primarily focused on catalyst and ionomer developments, marginalizing the importance of catalyst ink formulation. In this study, the effect of ink formulation is examined across a series of cathodes comprised of PtCo supported on high surface area carbon (PtCo/ HSC ) and Nafion ionomer using an array of in situ electrochemical and ex situ characterization techniques. In contrast to prior work on Pt/Vu systems, ink water content had little effect on the electrochemically determined ionomer coverage for the PtCo/HSC electrocatalyst examined here. Characterization using nano-scale resolution X-ray computed tomography (nano-CT) demonstrated that water-rich ink formulations lead to a reduction in aggregate size (ionomer + PtCo/HSC), improving local O 2 transport. This understanding, combined with the use of a commercially-available electrocatalyst was used to produced state-of-the-art membrane electrode assemblies with Pt loadings of 0.03/0.08 mg Pt /cm 2 on the anode and cathode respectively, having; i) > 1 A/mg Pt (0.9 V iR-free , 150 kPa, 80 °C, 100% RH, H 2 /O 2 ), ii) 320 mA/cm 2 at 0.8 V, 150 kPa, 80 ° C, 100% RH, H 2 /Air), and iii) > 1 W/cm 2 elec at rated power (0.67 V, 250 kPa, 94 °C, 65% RH, H 2 /Air) or < 0.11 g Pt /kW rated .

25 ENERGY STORAGE↗

A cylindrical quadrupole ion trap in combination with an electrospray ion source for gas-phase luminescence and absorption spectroscopy

A relatively simple setup for collection and detection of light emitted from isolated photo-excited molecular ions has been constructed. It benefits from a high collection efficiency of photons, which is accomplished by using a cylindrical ion trap where one end-cap electrode is a mesh grid combined with an aspheric condenser lens. The geometry permits nearly 10% of the emitted light to be collected and, after transmission losses, approximately 5% to be delivered to the entrance of a grating spectrometer equipped with a detector array. The high collection efficiency enables the use of pulsed tunable lasers with low repetition rates (e.g., 20 Hz) instead of continuous wave (cw) lasers or very high repetition rate (e.g., MHz) lasers that are typically used as light sources for gas-phase fluorescence experiments on molecular ions. A hole has been drilled in the cylinder electrode so that a light pulse can interact with the ion cloud in the center of the trap. Simulations indicate that these modifications to the trap do not significantly affect the storage capability and the overall shape of the ion cloud. The overlap between the ion cloud and the laser light is basically 100%, and experimentally >50% of negatively charged chromophore ions are routinely photodepleted. The performance of the setup is illustrated based on fluorescence spectra of several laser dyes, and the quality of these spectra is comparable to those reported by other groups. Finally, by replacing the optical system with a channeltron detector, we demonstrate that the setup can also be used for gas-phase action spectroscopy where either depletion or fragmentation is monitored to provide an indirect measurement on the absorption spectrum of the ion.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Rigid Biopolymer Nanocrystal Systems for Controlling Multicomponent Nanoparticle Assembly and Orientation in Thin Film Solar Cells. Final Report

The focus of the proposed research is to direct the assembly of single or binary nanoparticles into meso- or macroscale three-dimensional crystals of any desired configuration and crystallographic orientation without using prohibitively expensive lithographic processes. The epitaxial nucleation of defect-free, surface-bound bulk single crystals will revolutionize technologies for energy to generate new types of solar cells that yield maximum conversion efficiencies. It has been proposed that having a nanostructured bulk hetero-interface will enable efficient charge-carrier separations, similar to organic based heterojunction cells but with potential improvements, including thermal and long-term stability, tunability of energy levels, large adsorption coefficients and carrier multiplication. However, engineering such devices requires nanoscale control and ordering in both 2- and 3-dimensions over macroscopic areas and this has yet to be achieved. In Nature, bulk organic and inorganic materials are arranged into precise and ordered programmed assemblies through the sequestration of raw materials into confined spaces and association through highly specific non-covalent interactions between biomolecules. Using similar strategies, the proposed research will focus on confining metal and semiconductor nanocrystals to pre-determined surface patterns and controlling their arrangement through tunable, orthogonal biomolecular binding. Once a perfect two-dimensional seed layer has been constructed, successive layers of single nanocrystals will be nucleated epitaxially with long-range order and tunable crystallographic orientations. The proposed research exploits the ability of biomolecules to bind specific targets in a tunable, orthogonal, multivalent, and reversible manner to the arrangements of DNA-nanoparticle conjugates on chemically defined surfaces. Through careful balance of the attractive and repulsive forces between the particles, the array, and the outside surface, it is envisioned that single or mixed nanoparticles can be packed to adopt uniform crystal orientation in two and three dimensions from simple mixing and annealing of biomolecule-nanoparticle conjugates with biomolecule-stamped surfaces. To control the crystallographic alignment of each particle with its neighbors, the nanoparticles will be assembled using a mixture of non-covalent biomolecular interactions. To create solar cells in which layers of donor and acceptor nanocrystals that are not only oriented normal to the top and bottom electrodes but are also arranged in a checkerboard pattern, multicomponent nanocrystals (e.g. CdSe, CdTe) will be conjugated with biochemical linkers such that only interactions between the CdTe and CdSe promote particle packing within the array. The proposed research will: (1) elucidate the role of single and binary cooperative particle-DNA interactions in influencing nanoparticle crystallographic orientation in two and three dimensions; (2) understand how confinement of nanoparticles on patterned arrays of biomolecules and modification of the surrounding substrate can nucleate long-range order over macroscopic areas via predefined grain boundaries; and (3) synthesize and characterize DNA conjugated semiconductor nanocrystals and assemble them into 2- and 3-D binary superlattice arrays for photovoltaics.

14 SOLAR ENERGY↗

Persistent and partially mobile oxygen vacancies in Li-rich layered oxides

Increasing the energy density of layered oxide battery electrodes is challenging as accessing high states of delithiation often triggers voltage degradation and oxygen release. Here we utilize transmission-based X-ray absorption spectromicroscopy and ptychography on mechanically cross-sectioned Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ electrodes to quantitatively profile the oxygen deficiency over cycling at the nanoscale. The oxygen deficiency penetrates into the bulk of individual primary particles (~200 nm) and is well-described by oxygen vacancy diffusion. Using an array of characterization techniques, we demonstrate that, surprisingly, bulk oxygen vacancies that persist within the native layered phase are indeed responsible for the observed spectroscopic changes. We additionally show that the arrangement of primary particles within secondary particles (~5 μm) causes considerable heterogeneity in the extent of oxygen release between primary particles. Finally, our work merges an ensemble of length-spanning characterization methods and informs promising approaches to mitigate the deleterious effects of oxygen release in lithium-ion battery electrodes.

25 ENERGY STORAGE↗

Bilayer Ion Trap Design for 2D Arrays

Junctions are fundamental elements that support qubit locomotion in two-dimensional ion trap arrays and enhance connectivity in emerging trapped-ion quantum computers. In surface ion traps they have typically been implemented by shaping radio frequency (RF) electrodes in a single plane to minimize the disturbance to the pseudopotential. However, this method introduces issues related to RF lead routing that can increase power dissipation and the likelihood of voltage breakdown. Here, we propose and simulate a novel two-layer junction design incorporating two perpendicularly rotoreflected (rotated, then reflected) linear ion traps. The traps are vertically separated, and create a trapping potential between their respective planes. The orthogonal orientation of the RF electrodes of each trap relative to the other provides perpendicular axes of confinement that can be used to realize transport in two dimensions. While this design introduces manufacturing and operating challenges, as now two separate structures have to be precisely positioned relative to each other in the vertical direction and optical access from the top is obscured, it obviates the need to route RF leads below the top surface of the trap and eliminates the pseudopotential bumps that occur in typical junctions. Here in this paper the stability of idealized ion transfer in the new configuration is demonstrated, both by solving the Mathieu equation analytically to identify the stable regions and by numerically modeling ion dynamics. Our novel junction layout has the potential to enhance the flexibility of microfabricated ion trap control to enable large-scale trapped-ion quantum computing.

42 ENGINEERING↗

Brine Availability Test in Salt (BATS) FY21 Update

This report summarizes the 2021 fiscal year (FY21) status of ongoing borehole heater tests in salt funded by the disposal research and development (R&D) program of the Office of Spent Fuel & Waste Science and Technology (SFWST) of the US Department of Energy’s Office of Nuclear Energy’s (DOE-NE) Office of Spent Fuel and Waste Disposition (SFWD). This report satisfies SFWST milestone M2SF- 21SN010303052 by summarizing test activities and data collected during FY21. The Brine Availability Test in Salt (BATS) is fielded in a pair of similar arrays of horizontal boreholes in an experimental area at the Waste Isolation Pilot Plant (WIPP). One array is heated, the other unheated. Each array consists of 14 boreholes, including a central borehole with gas circulation to measure water production, a cement seal exposure test, thermocouples to measure temperature, electrodes to infer resistivity, a packer-isolated borehole to add tracers, fiber optics to measure temperature and strain, and piezoelectric transducers to measure acoustic emissions. The key new data collected during FY21 include a series of gas tracer tests (BATS phase 1b), a pair of liquid tracer tests (BATS phase 1c), and data collected under ambient conditions (including a period with limited access due to the ongoing pandemic) since BATS phase 1a in 2020. A comparison of heated and unheated gas tracer test results clearly shows a decrease in permeability of the salt upon heating (i.e., thermal expansion closes fractures, which reduces permeability).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The organic redox transistor for neuromorphic computing

Inspired by the in-memory computing architectures of biological systems, neuromorphic computing using crossbar arrays of artificial synapses based on non-volatile memory (NVM) devices with variable conductances has emerged as a new paradigm to enable massively parallel and ultra-low power computing hardware for data centric applications. Although inference has been demonstrated successfully using crossbars based on a variety of NMV technologies, efficient learning and scaling to large arrays (>10 6 elements) remains a challenge due to the synaptic elements' non-ideal electrical characteristics which degrades ANN accuracy. A further challenge is that in the conductive state memristors draw large currents >μA resulting in significant voltage drops in the interconnect wires and increased probability of failure in scaled arrays. We suggest the organic polymer redox transistor (RT) is an alternate approach that could solve many of these challenges, enabling both inference and parallel outer product updates, as recently demonstrated by Fuller et al. An RT consists of redox-active channel and gate electrodes in contact with a liquid or solid electrolyte. lon insertion through the electrolyte controls the channel electronic conductivity, while electron transfer through an external circuit maintains overall charge neutrality. Unlike a rechargeable battery, in the RT the voltage built-up across the electrolyte is kept to a minimum (typically <100 mV) by using the same material for the gate and channel. Elimination of the voltage offset simplifies integration of the RT into programmable arrays by enabling the use of various selectors. RTs based on inorganic and organic materials have been recently demonstrated with conductance tuning occurring at potentials of just a few mV and hundreds to thousands of linearly and symmetrically programmable conductance states, enabling near ideal accuracy in neural network simulations. Introduced in the 1980's, redox transistors with metallic gate electrodes and organic channel materials, also known as organic electrochemical transistors (OECTs), have been explored for a variety of applications such as chem- and bio-sensing, neural interfaces, and low cost printed circuits. A typical channel material for OECTs is the conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS). PEDOT is a p-type semiconducting polymer with mobile positively charged polarons that hop chain-to-chain.

Talin, Albert Alec↗

Grid indentation analysis of mechanical properties of composite electrodes in Li-ion batteries

We report that electrodes in commercial rechargeable batteries are microscopically heterogeneous materials. The constituent components, including active materials, polymeric binders, and porous conductive matrix, often have large variation in their mechanical properties, making the mechanical characterization of composite electrodes a challenging task. In a model system of LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathode, we employ the instrumented grid indentation to determine the elastic modulus and hardness of the constituent phases. The approach relies on a large array of nanoindentation experiments and statistical analysis of the resulting data provided that the maximum indentation depth is carefully chosen. The statistically extracted properties of the active particles and the surrounding medium are in good agreement with the tests of targeted indentation at selected sites. Lastly, the combinatory technique of grid indentation and statistical deconvolution represents a fast and reliable route to quantify the mechanical properties of composite electrodes that feed the parametric input for the mechanics models.

25 ENERGY STORAGE↗

The digital mirror Langmuir probe: Field programmable gate array implementation of real-time Langmuir probe biasing

High bandwidth, high spatial resolution measurements of electron temperature, density, and plasma potential are valuable for resolving turbulence in the boundary plasma of tokamaks. While conventional Langmuir probes can provide such measurements, either their temporal or spatial resolution is limited: the former by the sweep rate necessary for obtaining I-V characteristics and the latter by the need to use multiple electrodes, as is the case in triple and double probe configurations. The Mirror Langmuir Probe (MLP) bias technique overcomes these limitations by rapidly switching the voltage on a single electrode cycling between three bias states, each dynamically optimized for the local plasma conditions. The MLP system on Alcator C-Mod used analog circuitry to perform this function, measuring Te, VF, and Isat at 1.1 MSPS. Recently, a new prototype digital MLP controller has been implemented on a Red Pitaya Field Programmable Gate Array (FPGA) board which reproduces the functionality of the original controller and performs all data acquisition. There is also the potential to provide the plasma parameters externally for use with feedback control systems. The use of FPGA technology means the system is readily customizable at a fraction of the development time and implementation cost. A second Red Pitaya was used to test the MLP by simulating the current response of a physical probe using C-Mod experimental measurements. This project is available as a git repository to facilitate extensibility (e.g., real-time control outputs and more voltage states) and scalability through collaboration.

47 OTHER INSTRUMENTATION↗

The Digital Mirror Langmuir Probe: Field Programmable Gate Array Implementation of Real-Time Langmuir Probe Biasing

High bandwidth, high spatial resolution measurements of electron temperature, density and plasma potential are valuable for resolving turbulence in the boundary plasma of tokamaks. While conventional Langmuir probes can provide such measurements either their temporal or spatial resolution is limited: the former by the sweep rate necessary for obtaining I-V characteristics and the latter by the need to use multiple electrodes, as is the case in triple and double probe configurations. The Mirror Langmuir Probe (MLP) bias technique overcomes these limitations by rapidly switching the voltage on a single electrode cycling between three bias states, each dynamically optimised for the local plasma conditions. The MLP system on Alcator C-Mod used analog circuitry to perform this function, measuring Te, VF, and Isat at 1.1 MSPS. Recently, a new prototype digital MLP controller has been implemented on a Red Pitaya Field Programmable Gate Array (FPGA) board which reproduces the functionality of the original controller and performs all data acquisition. There is also the potential to provide the plasma parameters externally for use with feedback control systems. The use of FPGA technology means the system is readily customisable at a fraction of the development time and implementation cost. A second Red Pitaya was used to test the MLP by simulating the current response of a physical probe using C-Mod experimental measurements. This project is available as a git repository to facilitate extensibility (e.g. real-time control outputs, more voltage states) and scalability through collaboration.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗