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At least 253 records · Page 14

Lithium-ion Battery Strain Gauge Monitoring and Depth of Discharge Estimation

Lithium-ion battery diagnostics and prognostics rely on measurements of electrical impedance, capacity, and voltage to infer the internal state of the battery. Mechanical changes to the cell structure represent an additional measure of the battery’s state because these changes are related to the overall battery health. As lithium-ion batteries are charged and discharged, lithium ions are inserted or removed from the anode and cathode, a process called intercalation and de-intercalation. As lithium ions intercalate and de-intercalate, they can cause changes to the lattice of the electrode particles, resulting in volumetric changes. These volumetric changes cause mechanical stresses and strains on the lithium-ion battery electrodes, and subsequently, the whole cell’s thickness varies as it is charged and discharged. This paper presents a study on the use of surface-mounted strain gauges for in-situ measurement of structural changes to lithium-ion batteries, along with a characterization of the unit-to-unit differences in strain response. A neural network modeling structure is then used to predict the battery’s depth of discharge under dynamic discharge conditions.

Lithium-ion batteries, depth of discharge, strain ↗

High Throughput Laser Processing for Enhanced Battery Performance and Manufacturing

For widespread adoption of electric vehicles, lithium-ion batteries (LiBs) need to achieve energy densities of >275 Wh/kg, cell costs less than $100/kWh, and charge to more than 80% capacity within 15 minutes. Recently, it has been shown that introducing a secondary pore network in thick battery electrodes enables higher extracted capacity without a severe reduction in charge/discharge rate performance. Secondary pore networks consisting of ordered arrays of microstructures reduce tortuosity of Li+-ion transport deep into the thick electrodes, diminishing detrimental concentration gradients within the cell. Ultrafast (femtosecond)-pulsed laser ablation is a promising method to introduce such micro pores or channels in thick battery electrodes as it allows for precise control of pattern geometries, results in minimal damage to the electrode, and can be introduced into existing roll-to-roll electrode manufacturing lines. We have explored laser patterning to create secondary pore networks in a variety of battery electrode materials for both anode and cathode applications and characterized the laser-material interaction parameters. In addition, advanced materials characterization techniques (SEM-EDS, XRD) were used to explore whether ultrafast laser ablation affects the remaining electrode materials' morphology and structure. Furthermore, we have translated lab-scale laser ablation to high-throughput roll-to-roll processing at industrially relevant scales. Finally, we worked with Argonne National Laboratory, developers of the battery cost-analysis package BatPac, to estimate the additional manufacturing costs (CapEx and OpEx) for incorporation of laser-ablation processing to current battery electrode manufacturing. We estimate that ultrafast laser processing will add only -$1kWh, which for considerable improvements in cell performance, creates a compelling case for industry adoption.

battery↗

Time-Resolved X-ray Operando Observations of Lithiation Gradients across the Cathode Matrix and Individual Oxide Particles during Fast Cycling of a Li-Ion Cell

Lithiated transition metal oxides serve as active materials in the positive electrode (cathode) of lithium-ion cells. During electrochemical cycling, lithium ions intercalate and deintercalate into these oxide particles. This behavior causes two types of lithiation gradients to emerge: (i) a bulk gradient across the depth of the cathode matrix (averaged over individual oxide particles) and (ii) a microscopic gradient across the particles themselves, which also depends on their location in the electrode. Here we show how both gradients can be studied using operando X-ray diffraction during 4C charge and 4C discharge. The oxide (de)lithiation is estimated from the unit cell parameters by indexing the X-ray diffraction spectra. By fitting the lithiation profiles with orthogonal polynomials, the bulk gradients across the electrode thickness are quantified. These gradients develop as the current flows through the cell and dissipate during open-circuit and potentiostatic-hold periods. Further details of lithiation dynamics can be obtained through shape analysis of the Bragg peaks. In particular, from electrochemical model simulations, we show that the width and skewness of the (003) peak track (de)lithiation fronts moving across the individual oxide particles.

(003) peak↗

Plasma Potential and Langmuir Probe Measurements in the Near-Field Plume of the NASA-457Mv2 Hall Thruster

In order to further the design of future high-power Hall thrusters and provide experimental validation for ongoing modeling efforts, plasma potential and Langmuir probe measurements were performed on the 50-kW NASA-457Mv2. An electrostatic probe array comprised of a near-field Faraday probe, single Langmuir probe, and emissive probe was used to interrogate the near-field plume from approximately 0.1 ? 2.0 mean thruster diameters downstream of the thruster exit plane at the following operating conditions: 300 V, 400 V and 500 V at 30 kW and 500 V at 50 kW. Results have shown that the acceleration zone is limited to within 0.4 mean thruster diameters of the exit plane while the high-temperature region is limited to 0.25 mean thruster diameters from the exit plane at all four operating conditions. Maximum plasma potentials in the near-field at 300 and 400 V were approximately 50 V with respect to cathode potential, while maximum electron temperatures varied from 24 ? 32 eV, depending on operating condition. Isothermal lines at all operating conditions were found to strongly resemble the magnetic field topology in the high-temperature regions. This distribution was found to create regions of high temperature and low density near the magnetic poles, indicating strong, thick sheath formation along these surfaces. The data taken from this study are considered valuable for future design as well as modeling validation.

Shastry, Rohit↗

Plasma Potential and Langmuir Probe Measurements in the Near-field Plume of the NASA-457Mv2 Hall Thruster

In order to further the design of future high-power Hall thrusters and provide experimental validation for ongoing modeling efforts, plasma potential and Langmuir probe measurements were performed on the 50-kW NASA-457Mv2. An electrostatic probe array comprised of a near-field Faraday probe, single Langmuir probe, and emissive probe was used to interrogate the near-field plume from approximately 0.1 - 2.0 mean thruster diameters downstream of the thruster exit plane at the following operating conditions: 300 V, 400 V and 500 V at 30 kW and 500 V at 50 kW. Results have shown that the acceleration zone is limited to within 0.4 mean thruster diameters of the exit plane while the high-temperature region is limited to 0.25 mean thruster diameters from the exit plane at all four operating conditions. Maximum plasma potentials in the near-field at 300 and 400 V were approximately 50 V with respect to cathode potential, while maximum electron temperatures varied from 24 - 32 eV, depending on operating condition. Isothermal lines at all operating conditions were found to strongly resemble the magnetic field topology in the high-temperature regions. This distribution was found to create regions of high temperature and low density near the magnetic poles, indicating strong, thick sheath formation along these surfaces. The data taken from this study are considered valuable for future design as well as modeling validation.

Shastry, Rohit↗

Diamondlike carbon protective coatings for IR materials

Diamondlike carbon (DLC) films have the potential to protect optical windows in applications where it is important to maintain the integrity of the specular transmittance of these films on ZnS and ZnSe infrared transmitting windows. The films must be adherent and durable such that they protect the windows from rain and particle erosion as well as chemical attack. In order to optimize the performance of these films, 0.1 micro m thick diamondlike carbon films were deposited on fused silica and silicon wafers, using three different methods of ion beam deposition. One method was sputter deposition from a carbon target using an 8 cm ion source. The merits of hydrogen addition were experimentally evaluated in conjunction with this method. The second method used a 30 cm hollow cathode ion source with hydrocarbon/Argon gases to deposit diamondlike carbon films from the primary beam at 90 to 250 eV. The third method used a dual beam system employing a hydrocarbon/Argon 30 cm ion source and an 8 cm ion source. Films were evaluated for adherence, intrinsic stress, infrared transmittance between 2.5 and 50 micro m, and protection from particle erosion. An erosion test using a sandblaster was used to give quantitative values of the protection afforded to the fused silica by the diamondlike carbon films. The fused silica surfaces protected by diamondlike carbon films were exposed to 100 micro m diameter SiO particles at 60 mi/hr (26.8/sec) in the sandblaster.

Mirtich, M. J.↗

Electrochemical Synthesis of Zeolite Coatings with Controlled Crystal Polymorphism and Self-Regulating Growth

Zeolite coatings are studied as molecular sieves for membrane separation, membrane reactors, and chemical sensor applications. They are also studied as anticorrosive films for metals and alloys, antimicrobial and hydrophobic films for heating, ventilation, and air conditioning, and dielectrics for semiconductor applications. Zeolite coatings are synthesized by hydrothermal, ionothermal, and dry-gel conversion approaches, which require high process temperatures and lengthy times (ranging from hours to days). Here, we report the first zeolite coatings synthesized via electrochemical deposition on a cathodic electrode, with controlled crystal polymorphism achieved within subhourly duration. We demonstrate this approach by developing sodium zeolite (e.g., sodalite (SOD), NaA (LTA), and Linde Type N (LTN)) coatings on a titanium electrode and extending the synthesis method to porous stainless steel. The coating morphology and crystallinity depend on the temperature, time, and applied current. The coating thickness is independent of the applied current, showing the presence of a self-regulating mechanism to ensure a uniform coating thickness across the metal surface. The electrochemical zeolite growth mechanism was elucidated with high-resolution transmission electron microscopy, and applications of the resultant zeolite coatings for oil/water separation and ethanol/water pervaporation were exploited. Electrochemical synthesis represents a novel, simple, fast, and environmentally friendly approach to preparing zeolite coatings. It can potentially be generalized for developing zeolite materials with diverse framework structures, morphologies, and orientations for substrates with complicated geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of CO 2 -Regenerative Film Properties in Enhancing C 2+ Products Selectivity While Mitigating CO 2 Crossover

Zero-gap anion-exchange membrane electrode assembly (AEMEA) electrolyzers operating in alkaline media face challenges such as CO 2 crossover and salting-out. The bipolar membrane electrode assembly (BPMEA) electrolyzer, using DI water as the electrolyte, addresses both CO 2 crossover and salting-out issues. As cations, which are crucial in stabilizing the CO 2 R intermediates, are absent in the electrolyte, cations embedded in the AEM play an important role in dictating the CO 2 R selectivity and activity in BPMEA systems. So far, no systematic study has been conducted on the influence of cations embedded in AEMs on CO 2 selectivity and activity in BPMEA systems. Moreover, BPMEA systems impose an additional challenge: low stability due to delamination of the bipolar membrane caused by CO 2 regeneration at the membrane-membrane interface. To enhance the stability of the electrolyzer, a simple yet highly reproducible strategy for coating a porous CO 2 regenerative film on smooth Nafion 117 is demonstrated in this work, along with a systematic study of four different commercially available AEMs, composed of different cations and cation densities, for use in combination with Nafion 117 and copper catalyst at the cathode. We found that the PiperION membrane delivers selectivity and activity comparable to those of alkali-metal cations, owing to the enhanced local electric field resulting from the combined effects of a high positive charge on the N atom of the piperidinium cation and the high ion-exchange capacity. Further, we studied the influence of the thickness of the PiperION porous layer over Nafion 117 on CO 2 R selectivity and found that 70 μm is the minimum thickness to achieve maximum C 2+ products selectivity, reduced the CO 2 crossover to 5% from 25% at 4 SCCM and 150 mA cm –2 , and was stable for operation beyond 100 h. The selectivity of this system, compared with AEMEA, and stability outperformed both AEMEA and BPMEA. This study helps design more effective BPMs to inhibit CO 2 crossover while enabling stable and selective electrochemical CO 2 reduction to C 2+ hydrocarbons.

Cations↗

Development of sputtered techniques for thrust chambers

Procedures for closing out coolant passages in regeneratively cooled thrust chambers by triode sputtering, using post and hollow Cu-0.15 percent Zr cathodes are described. The effects of aluminum composite filler materials, substrate preparation, sputter cleaning, substrate bias current density and system geometry on closeout layer bond strength and structure are evaluated. High strength closeout layers were sputtered over aluminum fillers. The tensile strength and microstructure of continuously sputtered Cu-0.15 percent Zr deposits were determined. These continuous sputtered deposits were as thick as 0.75 cm. Tensile strengths were consistently twice as great as the strength of the material in wrought form.

Mullaly, J. R.↗

Manufacturing Aids

During a research program, MMTC/Textron invented a computer-aided automatic robotic system for spraying hot plasma onto a turbine blade. The need to control the thickness of the plasma deposit led to the development of advanced optical gaging techniques to monitor and control plasma spray build-up on blade surfaces. The techniques led to computerized optical gages for inspecting aircraft, industrial turbine blades, etc. MMTC offers 10 standard commercial robotic gages. The system also generates two dimensional profiles for assessing status and specifying repairs to the electromechanical cathodes used to make the parts. It is capable of accuracies to a ten-thousandth of an inch. An expanded product line is currently marketed. The gages offer multiple improvements in quality control and significant savings.

Source record↗

Electrochemistry-Induced Direct Deposition of Nanoscale Thin Zeolitic Imidazolate Framework-8 Films on Insulator Substrates

Electrochemical approaches have been explored as controlled means to prepare thin films of metal–organic frameworks (MOFs) on electrodes but have rarely been used to form insulator films on insulator surfaces. Herein, we report an electrochemistry-based approach to direct deposition of a thin film of zeolitic imidazolate framework-8 (ZIF-8) onto an insulator surface. The film deposition was induced by a cathodic reaction at an electrode that was placed above the insulator with a separation of ≈100 μm in a methanol solution containing ZnCl 2 and 2-methylimidizole. The effects of the electrode and insulator material, applied potential, electrode–substrate distance, deposition time, and the number of deposition cycles were systematically investigated to gain insight into the deposition mechanism. The results of these measurements were consistent with a hypothesized mechanism involving cathodic base generation at the working electrode for ligand deprotonation, formation of intermediate species, their diffusion toward the substrate, and the formation of ZIF-8 on the substrate. Interestingly, the size, shape, and position of the film on the substrate replicated those of the working electrode, showing the applicability of this approach to the patterned deposition of a ZIF-8 film. In addition, film thickness could be easily controlled in the range of tens to hundreds of nanometers by adjusting the potential application conditions. Furthermore, this electrochemistry-induced method will provide a simple means for the patterned formation of a MOF film of controlled thickness on an insulator without metal precoating and thus will open the possibility of designing unique devices for various applications including chemical sensing and separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

OES CO 2 Pipeline FEED Project Design Basis Memorandum

The OES CO₂ Pipeline project will move captured carbon dioxide from two ethanol facilities near Gibson City, Illinois, roughly 7.8 miles southeast to three injection wells outside Anchor, where it will be permanently stored underground. The system is designed to handle up to 4.5 million metric tonnes per year of dense-phase CO₂ at pressures up to 2,500 psig, using 16-inch mainline pipe and 10.750-inch laterals made from API 5L X-60 and X-65 steel. Wall thicknesses vary depending on location, with thinner pipe in open country, heavier wall at road crossings, and the heaviest where the pipe passes under highways or railroads via horizontal directional drill. The pipe gets a fusion-bonded epoxy coating, with an added abrasion-resistant layer wherever it's bored or drilled. Major water crossings will use HDD rather than open trenching. The pipeline will be cathodically protected, equipped with SCADA-compatible pressure and temperature instrumentation, and monitored for leaks using a computational pipeline monitoring system per API RP 1130. Hydrostatic testing will be performed at 1.25 times design pressure, and an ILI caliper run will follow to catch any construction defects. Several items, including fracture toughness requirements, specific NDE methods, and ILI tool selection, are left for the detailed design phase. The whole system falls under 49 CFR Part 195 and ASME B31.4, and Gulf Interstate Engineering prepared this document as the FEED-level design basis under the CarbonSAFE Phase III program.

09 BIOMASS FUELS↗

Performance Restoration of Iron Electrodes by Polarity Reversal after Long-Term Surface Fouling in Wastewater Electrocoagulation

Iron electrocoagulation (Fe-EC) performance often declines with time, producing lower contaminant removal efficiencies and higher energy requirements due to formation of a fouling layer on the electrodes. Here, we investigate the formation of the fouling layer and the effectiveness of polarity reversal to restore the Fe-EC performance. A thin, porous iron oxide layer initially forms on the anode, thickening into a dense, over 150-μm thick crystalline layer after extended operation. This fouling layer restricts dissolution and diffusion of Fe ions into the bulk solution, thus increasing the anode potential required to maintain a desired electrical current and decreasing Faradaic efficiency. Polarity reversal applied when performance decline is observed effectively removes the fouling layer, thereby restoring Faradaic and contaminant removal efficiencies and decreasing energy consumption. Our findings suggest that gas generation at the cathode surface after polarity reversal causes removal of the fouling layer. This study enhances the current understanding of fouling-layer formation in Fe-EC and offers a practical approach, involving polarity reversal, to maintain electrode reactivity and optimal Fe-EC performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

The biggest obstacle to the widespread implementation of polymer electrolyte membrane fuel cells (PEMFCs) is their cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited on a rotating disk electrode (RDE) is rarely realized in a membrane electrode assembly (MEA), which is a long-standing challenge for PEMFCs and a cause of low catalyst utilization. To translate the high RDE performance of a catalyst into a MEA, the design of an ideal ionomer/catalyst interface is proposed: a thin, conformal ionomer film covers the maximum surface of a Pt nanoparticle and thus simultaneously maximizes catalyst utilization, (i.e., high mass activity and electrochemically active surface area) and O 2 diffusion rate (i.e., high current density performance) without compromising proton conduction. Building such an interface is a long-standing challenge due to the lack of interaction between the ionomer and catalyst particles, resulting in large ionomer agglomerates and inhomogeneous ionomer coverage over the catalyst nanoparticle, with consequent poor fuel cell performance. In this work, this ionomer/catalyst interface has been engineered, utilizing the electrostatic attraction between positively charged catalyst and negatively charged ionomer particles in a catalyst ink and preserved in a solid catalyst layer. As a result, this interface leads to previously unachieved proton exchange membrane fuel cell performance in terms of both catalyst utilization (75% vs. 45%) and peak/rated power density (i.e., 1.430/0.930 W cm -2 , H 2 /air, cathode Pt loading: 0.1 mgPt cm -2 ) for pure Pt catalysts, even better than those of Pt alloy catalysts. This work demonstrates the formation of an interface in the liquid phase (using ultra-small-angle X-ray scattering in combination with cryo-TEM, isothermal–titration–calorimetry) and the preservation of the interface in the solid catalyst layer (using TEM) and estimates the effective coverage and thickness of the ionomer film (using limiting current density, RDE and fuel cell performance).

25 ENERGY STORAGE↗

Protection layers for metal anodes

A protection layer is formed on a highly-reactive substantially-pure metal anode to a thickness of between 1 nm and 200 nm, inclusive, using atomic layer deposition (ALD). The ALD protection layer allows the conduction of ions of the metal of the anode therethrough but suppresses electron transport therethrough. The ALD protection layer may also be effective to inhibit passage of air and/or water therethrough. The ALD protection layer can allow more relaxed purity requirements for subsequent battery assembly, electrolyte specifications, and/or cathode gas purity. Fabrication methods for the protection layers, protected metal anodes, and systems and devices incorporating such protected metal anodes are also disclosed herein.

Kozen, Alexander C.↗

Self-Stabilized LiNi 0.8 Mn 0.1 Co 0.1 O 2 in thiophosphate-based all-solid-state batteries through extra LiOH

Nickle-rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC 811) cathode material exhibits engaging properties in high energy density and low cost, making it great potential for the next generation high-energy all-solid-state lithium batteries (ASSLBs). However, NMC 811 suffers from severe surface electrochemical, chemical, and voltage incompatibility towards solid-state electrolytes (SSE), especially thiophosphate-based electrolytes like Li 6 PS 5 Cl. Although diverse coating methods have been made to overcome this issue, they are typically cumbersome and expensive. A coating strategy that satisfied all the requirements of cost-efficiency, stability, uniformity, scalability, and easy-achieving is still challenging. Here, we developed a LiOH-based surface stabilization strategy that provides a ~10 nm stable permeable layer on NMC 811. After one-step sintering of NMC 811 precursor mixed with LiOH, which is commonly used for NMC 811 lithiation process, excessive LiOH simultaneously distributes on NMC 811 particles. Unlike other reported methods, this coating method can be easily controlled and fabricated without additional complicated processes. By simply controlling the thickness of LiOH layer, which protects the Li 6 PS 5 Cl solid electrolyte materials from being oxidized, optimized cycling stability can be obtained for 600 cycles with capacity of 130 mAh g – 1 on average at a wide electrochemical window of 2.50–4.20 V (vs. Li-In).

25 ENERGY STORAGE↗

Electrodeposited Zinc-based Films as Anodes for Aqueous Zinc Batteries

Zinc-based batteries have attracted extensive attention in recent years, due to high safety, high capacities, environmental friendliness, and low cost compared to lithium ion batteries. However, the zinc anode suffers primarily from dendrite formation as a mode of failure in the mildly acidic system. Herein, we report on electrochemically deposited zinc (ED Zn) and copper-zinc (brass) alloy anodes, which are critically compared with a standard commercial zinc foil. The film electrodes are of commercially relevant thicknesses (21 and 25µM). The electrodeposited zinc-based anodes exhibit low electrode polarization (~0.025V) and stable cycling performance in 50 cycle consecutive experiments from 0.26-10 mA cm-2 compared to commercial Zn foil. Coulombic efficiencies at 1 mA cm-2 were over 98% for the electrodeposited zinc-based materials and were maintained for over 100 cycles. Furthermore, full cells with an electrodeposited Zn/brass anode, EMD MnO2 cathode, in 1M ZnSO4 + 0.1M MnSO4 delivered capacities of 96.3, and 163 mAh g-1, respectively, at a 100 mA g-1 compared to 92.1 mAh g-1 for commercial Zn. The zinc-based anodes also show better rate capability, delivering full cell capacities of 35.9 and 47.5 mAh g-1 at high current of up to 3 A g-1. Lastly, the electrodeposited zinc-based anodes show enhanced capacity for up to 100 cycles at 100 mA g-1, making them viable anodes for commercial use.

Fayette, Matthew R.↗