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At least 469 records · Page 26

Restorable Neutralization of Poly(acrylic acid) Binders toward Balanced Processing Properties and Cycling Performance for Silicon Anodes in Lithium-Ion Batteries

Neutralization of poly(acrylic acid) (PAA)-based binders using lithium hydroxide is a common strategy for fabricating silicon anode laminates, which improves rheological properties of slurries toward high-quality electrode laminates. However, the significantly increased basicity causes degradation of Si particles while the irreversible conversion of carboxylic acid groups to lithium carboxylates undermines the binding strength, collectively leading to adverse cycling performance of the fabricated Si anodes. Herein, a novel neutralization process for PAA binders is developed. A weak base, ammonia (NH 3 ), was discovered as a neutralizing agent that still promotes rheological response of binder solutions but results in a reduced pH increase. Interestingly, the resulting ammonium carboxylate groups may cleave during the drying process to restore the neutralized PAA (PAA-NH 3 ) binders to their pristine states. The best-performing composition of 50% neutralization (PAA-50%NH 3 ) provides comparable rheological response as a PAA-Li binder as well as much improved cycling performance. Additionally, the half-cells using the PAA-50%NH 3 binder can deliver 60% capacity retention over 100 cycles at C/3 rate, affording a 23.8% increase compared to PAA-Li half-cells. This restorable neutralization process of PAA binders represents an innovative strategy of mitigating issues from slurry processing of Si particles to achieve concurrent improvements in high-quality lamination and cycling performance.

25 ENERGY STORAGE↗

An all-silicon single-wafer micro-g accelerometer with a combined surface and bulk micromachining process

This paper reports an all-silicon fully symmetrical z-axis micro-g accelerometer that is fabricated on a single-silicon wafer using a combined surface and bulk fabrication process. The microaccelerometer has high device sensitivity, low noise, and low/controllable damping that are the key factors for attaining micro g and sub-micro g resolution in capacitive accelerometers. The microfabrication process produces a large proof mass by using the whole wafer thickness and a large sense capacitance by utilizing a thin sacrificial layer. The sense/feedback electrodes are formed by a deposited 2-3 microns polysilicon film with embedded 25-35 microns-thick vertical stiffeners. These electrodes, while thin, are made very stiff by the thick embedded stiffeners so that force rebalancing of the proof mass becomes possible. The polysilicon electrodes are patterned to create damping holes. The microaccelerometers are batch-fabricated, packaged, and tested successfully. A device with a 2-mm x 1-mm proof mass and a full bridge support has a measured sensitivity of 2 pF/g. The measured sensitivity of a 4-mm x 1-mm accelerometer with a cantilever support is 19.4 pF/g. The calculated noise floor of these devices at atmosphere are 0.23 micro g/sqrt(Hz) and 0.16 micro g/sqrt(Hz), respectively.

Non-NASA Center↗

Energy conversion research and development with diminiodes

Diminiodes are variable-gap cesium diodes with plane miniature guarded electrodes. These converters allow thermionic evaluations of tiny pieces of rare solids. In addition to smallness, diminiode advantages comprise simplicity, precision, fabrication ease, parts interchangeability, cleanliness, full instrumentation, direct calibration, ruggedness, and economy. Diminiodes with computerized thermionic performance mapping make electrode screening programs practical.

Morris, J. F.↗

Flexible and Extensive Platinum Ion Gel Condensers for Programmable Catalysis

Catalytic condensers composed of ion gels separating a metal electrode from a platinum-on-carbon active layer were fabricated and characterized to achieve more powerful, high surface area dynamic heterogeneous catalyst surfaces. Ion gels comprised of poly(vinylidene difluoride)/1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide were spin coated as a 3.8 μm film on a Au surface, after which carbon sputtering of a 1.8 nm carbon film and electron-beam evaporation of 2 nm Pt clusters created an active surface exposed to reactant gases. Electronic characterization indicated that most charge condensed within the Pt nanoclusters upon application of a potential bias, with the condenser device achieving a capacitance of ∼20 μF/cm 2 at applied frequencies of up to 120 Hz. The maximum charge of ∼10 14 |e – | cm –2 was condensed under stable device conditions at 200 °C on catalytic films with ∼10 15 sites cm –2 . Grazing incidence infrared spectroscopy measured carbon monoxide adsorption isobars, indicating a change in the CO* binding energy of ∼19 kJ mol –1 over an applied potential bias of only 1.25 V. Condensers were also fabricated on flexible, large area Kapton substrates allowing stacked or tubular form factors that facilitate high volumetric active site densities, ultimately enabling a fast and powerful catalytic condenser that can be fabricated for programmable catalysis applications.

Catalysis↗

A study on sub-bandgap photoexcitation in nitrogen- and boron-doped diamond with interdigitated device structure

Diamond is an ultrawide-bandgap semiconductor suitable for high power devices that require high current carrying capacity, high blocking voltages, and smaller form factors. We investigated various diamond structures for extrinsic photoconductive semiconductor switches, including an insulating high-pressure high-temperature type Ib (highly nitrogen-doped) substrate, a chemical vapor deposited (CVD) type IIa (unintentionally doped) substrate, a CVD grown semiconducting boron-doped epilayer on a type IIa substrate, and boron-implanted type Ib and IIa substrates. Using these samples, we fabricated and characterized planar interdigitated photoconductive switches with 30 μm, electrode gaps. 532 and 1064 nm Nd:YAG laser pulses with energies up to 3.5 mJ/pulse were used to trigger the switches. Photoresponses were measured at bias voltages ranging from 10 to 100 V, corresponding to electric fields of 3.3–33 kV/cm. In this field range, the type Ib device exhibited the highest average on/off-state current ratio, on the order of 10 11 , when triggered with 0.8 mJ/pulse, 532 nm laser pulses. However, only the CVD grown boron-doped epilayer and boron implanted IIa devices showed decent sensitivity to 1064 nm.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Synthetic Metal Atomic Layer Deposition Tool (Final Report)

As part of the Cyclotron Road program, Laminera Inc. worked towards development of atomic layer deposition process customizations and tool modifications to produce synthetic metal films at commercial scale and improve the film quality. Today's state-of-the-art in atomic layer deposited synthetic metal technology is only possible at a research-scale because current tools have practical limitations for scaling industrially and generating high conductivity films. Ultrathin, conformal synthetic metal films have many possible applications such as high surface area nanoporous electrodes for supercapacitors and water desalination devices; protective electrode coatings for electrochemical devices; seed layers for semiconductor device fabrication; or metallic component stabilizing coatings that enable enhanced storage density in next generation hard disk drives. The best synthetic metal conductive and plasmonic properties have been demonstrated using sputtering, which relies on high temperature sputtering with substrate dependent and directional growth limiting usage. This work explored refining process and tool modifications to create ultrathin, conformal, synthetic metal films that can be deposited with high quality over complex three-dimensional surfaces.

36 MATERIALS SCIENCE↗

A Molten Salt Electrochemical Process for the Preparation of Cost-Effective p-Block (Coating) Materials

Solar energy applications rely heavily on p-block elements and transition metals. Silicon is, by far, the most commonly used material in photovoltaic cells and accounts for about 85% of modules sold presently. Of late, thin film photovoltaic cells have gained momentum because of their higher efficiencies. Most of these thin film devices are made out of just five elements, namely, cadmium, tellurium, selenium, indium, gallium and copper. The present manuscript describes an elegant and inexpensive molten salt-based electrolytic process for fabricating a tellurium-coated metallic substrate. A three-electrode set up was employed to coat iridium with tellurium from a molten bath containing lithium chloride, lithium oxide and tellurium tetrachloride (LiCl-Li 2 O-TeCl 4 ) at 650 °C for a duration ranging from 30 to 120 min under a galvanostatic mode. The tellurium coating was observed to be thick, uniform, smooth and homogeneous. Additionally, the deposited tellurium did not chemically react with the iridium substrate to form intermetallic compounds, which is a good feature from the standpoint of the device’s performance characteristics. The present process, being generic in nature, shows the potential for the manufacture of both the coated substates and high-purity elements not just for tellurium but also for other p-block elements.

36 MATERIALS SCIENCE↗

Study of oxygen gas production phenomenon during stand and discharge in silver-zinc batteries

The effects of a number of cell process and performance variables upon the oxygen evolution rate of silver/silver oxide cathodes are studied to predict and measure the conditions which would result in the production of a minimum of oxygen. The following five tasks comprise the study: the design and fabrication of two pilot test cells to be used for electrode testing; the determination of the sensitivity and accuracy of the test cell; the determination of total volumes and rates of generation by cathodes of standard production procedures; the construction of a sequential test plan; and the construction of a series of positive formation cells in which formation process factors can be controlled.

Source record↗

Optically activated switch/modulator using a photoconductor and two channel waveguides

An optically activated switch was fabricated on LiNbO3 substrate by deposition of photoconductor-metal electrode structure on two channel waveguides obtained by the outdiffusion process. One waveguide was overcoated with a CdS film, and served as a light detector which converted the optical signal in that waveguide into an electric signal. Utilizing the electrooptic effect, this electric signal modulated the light propagating in the second waveguide by changing the refractive index, and the cutoff condition, of the waveguiding channel between two metal electrodes. The waveguides in the optically controlled switch can be either single or multimode. The length of the device can be short in comparison with other switching schemes. When binary optical signals are applied to the two waveguides, the switch can perform logic AND, NEGATION, OR and pseudo-amplification operations.

Goldberg, L.↗

The NASA GSFC MEMS Colloidal Thruster

A number of upcoming missions require different thrust levels on the same spacecraft. A highly scaleable and efficient propulsion system would allow substantial mass savings. One type of thruster that can throttle from high to low thrust while maintaining a high specific impulse is a Micro-Electro-Mechanical System (MEMS) colloidal thruster. The NASA GSFC MEMS colloidal thruster has solved the problem of electrical breakdown to permit the integration of the electrode on top of the emitter by a novel MEMS fabrication technique. Devices have been successfully fabricated and the insulation properties have been tested to show they can support the required electric field. A computational finite element model was created and used to verify the voltage required to successfully operate the thruster. An experimental setup has been prepared to test the devices with both optical and Time-Of-Flight diagnostics.

Cardiff, Eric H.↗

Directed Growth of Carbon Nanotubes Across Gaps

An experiment has shown that when single-walled carbon nanotubes (SWNTs) are grown by chemical vapor deposition in the presence of an electric field of suitable strength, the nanotubes become aligned along the electric field. In an important class of contemplated applications, one would exploit this finding in fabricating nanotube transistors; one would grow SWNTs across gaps between electrodes that would serve, subsequently, as source and drain contacts during operation of the transistors. In preparation for the experiment, a multilayer catalyst comprising a 20-nmthick underlayer of iridium (platinum group), a 1-nm-thick middle layer of iron, and a 0.2-nm-thick outer layer of molybdenum was ion-beam sputtered onto a quartz substrate. A 25 micrometers-diameter iron wire was used as a shadow mask during the sputtering to create a 25 micrometers gap in the catalyst. Then electrical leads were connected to the catalyst areas separated by the gap so that these catalyst areas would also serve as electrodes. The substrate as thus prepared was placed in a growth chamber that consisted of a quartz tube of 1-in. (2.54-cm) diameter enclosed in a furnace. SWNTs of acceptably high quantity and quality were grown in 10 minutes with methane at atmospheric pressure flowing through the chamber at a rate of 1,000 standard cubic centimeters per minute at a temperature of 900 C. To prevent oxidation of the SWNTs, the chamber was purged with 99.999-percent pure argon before and after growth, and the chamber was cooled to less than 300 C before opening it to the atmosphere after growth. When no voltage was applied across the gap, the SWNTs grew in random directions extending out from the edges of the catalyst at the gap. When a potential of 10 V was applied between the catalyst/electrode areas to create an electric field across the gap, the SWNTs grew across the gap, as shown in the figure.

Delzeit, Lance↗

Number Codes Readable by Magnetic-Field-Response Recorders

A method of encoding and reading numbers incorporates some of the features of conventional optical bar coding and radio-frequency identification (RFID) tagging, but overcomes some of the disadvantages of both: (1) Unlike in conventional optical bar coding, numbers can be read without having a line of sight to a tag; and (2) the tag circuitry is simpler than the circuitry used in conventional RFID. The method is based largely on the principles described in Magnetic-Field-Response Measurement-Acquisition System (LAR-16908), NASA Tech Briefs, Vol. 30, No. 6 (June 2006) page 28. To recapitulate: A noncontact system includes a monitoring unit that acquires measurements from sensors at distances of the order of several meters. Each sensor is a passive radio-frequency (RF) resonant circuit in the form of one or more inductor(s) and capacitor(s). The monitoring unit a handheld unit denoted a magnetic field response recorder (MFRR) generates an RF magnetic field that excites oscillations in the resonant circuits resulting in the sensors responding with their own radiated magnetic field. The resonance frequency of each sensor is made to differ significantly from that of the other sensors to facilitate distinction among the responses of different sensors. The MFRR measures selected aspects of the sensor responses: in a typical application, the sensors are designed so that their resonance frequencies vary somewhat with the sensed physical quantities and, accordingly, the MFRR measures the resonance frequencies and variations thereof as indications of those quantities. In the present method, the resonance circuits are not used as sensors. Instead, the circuits are made to resonate at fixed frequencies that correspond to digits to be encoded. The number-encoding scheme is best explained by means of examples in which each resonant circuit consists of a spiral trace inductor electrically connected to a set of parallel-connected capacitors in the form of interdigitated electrode pairs (see figure). The inductor and capacitor(s) in each resonant circuit can be fabricated as a patterned thin metal film by means of established metal-deposition and -patterning techniques. The capacitance and, hence, the resonance frequency, depends on the number of interdigitated electrodes connected to the inductor. In a similar manner, sets of electrodes could be used.

Woodard, Stanley E.↗

The Role of Metal Oxides in Li-S Batteries: A High-Areal-Capacity Sulfur Composite Cathode Investigation

Compared to lithium-ion batteries (LIB), lithium-sulfur (Li-S) batteries have low cost and high theoretical specific energy (2510 Wh/kg or about 10 times of the LIB). However, Li-S batteries have several challenges, including large volume expansion, poor utilization of the end products, sluggish kinetics of polysulfides, and crossover, so-called the "shuttle effect". To address these issues, we have introduced metal oxides to the Li-S electrode to develop a metal-oxide-sulfur composite electrode. We aim to use metal oxides to assist the Li-S formation (dissociation) during discharge (charge) cycles. We elect to focus on LIB-based metal oxides to ensure that the added material can contribute storage capacity to the battery. Our cathodes are fabricated by both the conventional slurry casting and air-controlled electrospray. LIB electrode materials, such as Li(Ni 0.6 Mn 0.6 Co 0.2 )O 2 , LiMn 2 O 4 , Li 2 TiO 3 , etc, were incorporated with the sulfur-carbon composite and their charge-discharge performances are compared. We found that the presence of metal oxides increased sulfur utilization with stable cycling performance, even in cells with high areal capacities. To unveil the interactions between lithium metal oxides and sulfur, the cathodes were analyzed by various characterization techniques, including scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and electrochemistry. The analysis of the role of the oxides will be presented along with the reaction mechanism.

25 ENERGY STORAGE↗

Self-Forming Thin Interphases and Electrodes Enabling 3-D Structured High Energy Density Batteries

An electrolytically in-situ formed fluoride/lithium based battery has been developed to offer a pathway to scalable reconfigurable solid state batteries of high energy density. Research into the development of novel in-situ formed chemistries encompassing the negative and positive reactive current collectors, and the bi-ion glass conductor along with electrode structure was accomplished with a focused attention on transport. The solid state in-situ batteries were fabricated with a maskless scalable patterning technique to offer a pathway to high throughput, low material loss and fabrication of complex architectures. Such development and integration enabled to achieve the 12 V bipolar batteries at > 1000 Wh/L energy density based on electrode pairs and current collectors.

25 ENERGY STORAGE↗

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↗

Scalable Solution-Processed Electrolyte Membranes with Optimized Microstructure for High-Performance Protonic Ceramic Electrochemical Cells

Proton-conducting electrochemical cells (PCECs) are promising for efficient hydrogen production, but achieving dense, uniform, thin electrolyte layers remains a key challenge, particularly for scalable fabrication. Here, we present a solution-processed deposition approach with a mechanistically optimized slurry for uniform electrolyte formation. By tailoring particle size distribution, solid loading, and solvent/additive balance, we regulated wetting behavior and evaporation kinetics of the electrolyte slurry to promote homogeneous electrolyte particle packing. These features facilitate tight grain boundary contact and early stage neck growth during sintering, eliminating residual porosity, and improving mechanical integrity. The resulting ∼15 μm thick electrolyte shows high density, strong electrode adhesion, and stable interfaces outperforming the previously reported spray-based fabricated electrolyte by about 31% at 600 °C in FC mode. Single cells deliver 0.962 W cm –2 at 600 °C in fuel cell mode and 1.31 A cm –2 at 1.3 V in electrolysis mode, maintaining robust performance over 100 h with negligible degradation (≤0.02% h –1 ) in each mode. Scale-up to 2.5 cm diameter substrates confirmed reproducible densification and geometric stability. This work demonstrates a cost-effective, scalable route where control over particle-fluid interactions and drying dynamics enables a superior electrolyte microstructure and high PCEC performance.

dense microstructure↗

Single Component Dye-Sensitized Solar Cells Enabled by Copper Chemistry: Introduction of the Retro Cell

The possibility of utilizing a single molecule to act as both a chromophore and a redox shuttle in a new configuration of a dye-sensitized solar cell (DSSC) is investigated. This design, termed a retro cell, exploits the copper chromophore, [Cu(dsbtmp) 2 ] + (dsbtmp = bis(2,9-di(sec-butyl)-3,4,7,8- tetramethyl-1,10-phenanthroline), which has been shown to have excited state lifetimes in excess of a microsecond, enabling sensitization of TiO 2 while dissolved in solution. The oxidized chromophore can then diffuse to the counter electrode to be regenerated. This concept simplifies the device components and fabrication and eliminates a charge transfer step compared to that of traditional DSSCs. Initial investigations show the concept is viable; however, the performance is suboptimal. We have found the addition of 4-tertbutylpyridine (TBP) to the electrolyte plays a crucial role in enabling solar energy conversion. Evidence of TBP displacing one of the dsbtmp ligands in the oxidized [Cu(dsbtmp) 2 ] 2+ complex has been presented, which likely plays an important role in reducing recombination and enabling charge collection. The performance-limiting steps and routes to improved performance and viability of a retro cell are further discussed.

14 SOLAR ENERGY↗

Fabrication and testing of silver-hydrogen cells

The development and life testing of single electrode and multi electrode stacks to optimize the individual components and characterize the performance of a silver hydrogen battery system are described. A NASA-developed inorganic separator material was used as the main separator within the cells. Single electrode test cells were cycled at 75% of nominal capacity out through approximately 1,000 cycles in a number of cases where deterioration in performance was observed. This deterioration appears to be a decay in usable capacity of the silver electrode; but the exact mechanism is still unidentified. Twenty ampere-hour boilerplate test cells consisting of a stack of ten silver electrodes and twenty hydrogen electrodes were cycled also at 75% depth of discharge. The oldest stack achieved 522 stable cycles to the end of the program. Weight analysis of light-weight cells showed that 50 ampere-hour cells with improved components could be capable of as much as 40 watt hours per pound.

Klein, M. G.↗