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At least 1,297 records · Page 72

Production of graphene-derivatives using organic molecules for supercapacitors and beyond

Graphene is rapidly expanding for applications ranging from nanoelectronics to space exploration. A material with such enormous potential requires a variety of synthesis methods. Here, we report a library of relatively sustainable redox-active organic molecules for the reduction of graphene oxide (GO) namely N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), 7,7,8,8-tetracyanoquinodimethane (TCNQ), ferrocene (Ferro), and decamethylferrocene (DFerro). Among them, the reduction of GO using TMPD starts even with simple hand-shaking for just a few minutes. By controlling the sonication time under ambient conditions, one can control the electronic properties of the reduced graphene oxide (rGO). The resulting free-standing films delivered a capacitance of 185 F/g when tested them as supercapacitor electrodes. We also demonstrated that TMPD can exfoliate graphite into few-layer graphene sheets with simple sonication. Here, we further show that under mild heating, these molecules can serve as dopants during the reduction process to produce nitrogen-doped graphene. Our results may guide researchers to explore sustainable organic molecules for the large-scale production of graphene-based materials for diverse applications.

36 MATERIALS SCIENCE↗

Probing the electrolyte/electrode interface with vibrational sum frequency generation spectroscopy: A review

Over the past decades, Lithium-ion batteries have seen extensive improvements, and as a result are now the primary choice in many applications for their power, energy, and durability. In recent years, battery cost has reduced by orders of magnitude through adoption of new materials and processes. Despite these advances, interfaces in these battery systems are yet to be fully understood. This is seen as a major limitation to further increase cycle life, calendar life, abuse tolerance, and performances. A major obstacle is a lack of comprehensive understanding of the complex dynamic chemical processes occurring at the electrolyte/electrode interface. In this context, vibrational sum frequency generation (vSFG) spectroscopy possesses the unique capability of probing a molecularly thin interfacial layer to obtain molecular-level information through nonlinear optical interaction. Probing the molecular level processes at the interfaces using such a versatile technique would be a game changer in the advancement of current battery research knowledge. This review article summarizes recent vSFG studies on the electrolyte/electrode interface of various electrode materials and nonaqueous electrolytes for LIBs and discusses future research perspectives. Finally, overall, this focused review highlights the advantages and versatility of vSFG that can be used to further advance present-day battery research.

25 ENERGY STORAGE↗

A Comparative Study of Electrical Double Layer Effects for CO Reduction Reaction Kinetics

Solvation models describe how the interactions between the solutes and solvents affect the reactivity and selectivity in electrochemical processes. In this study, we developed a framework for evaluating the effects of applied potential and electrical double layer on CO reduction (COR), comparing fully explicit, implicit, and hybrid solvation models at the standard hydrogen electrode (SHE) scale. We analyzed all crucial intermediates leading to the production of C 1 and C 2 products and found good agreement across these models. Some notable differences were observed in the implicit description of *C and *CO adsorption at higher overpotentials and overall trends in the adsorption energies within the hybrid model. Using this unified SHE framework, we built comparable microkinetic models for COR kinetics and rates. Despite small differences in thermodynamics, solvation-model-based microkinetic simulations showed good agreement for onset potentials against the benchmark experiment. Only qualitative difference was observed for C 1+ versus hydrogen evolution at high overpotentials for the implicit model. Finally, we constructed a generalized C 2 selectivity map in descriptor space (U SHE , ΔG electrolyte CO ), which highlights the limitations of a copper-based COR catalyst and guides the search for optimal descriptor parameters to maximize C 2 selectivity. In conclusion, these findings demonstrate the importance of considering electrical double layer effects in reduction reactions and offer a useful framework for comparing solvation models and predicting optimal electrochemical conditions for specific applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic/molecular layer deposition for energy storage and conversion

Energy storage and conversion systems, including batteries, supercapacitors, fuel cells, solar cells, and photoelectrochemical water splitting, have played vital roles in the reduction of fossil fuel usage, addressing environmental issues and the development of electric vehicles. The fabrication and surface/interface engineering of electrode materials with refined structures are indispensable for achieving optimal performances for the different energy-related devices. Atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques, the gas-phase thin film deposition processes with self-limiting and saturated surface reactions, have emerged as powerful techniques for surface and interface engineering in energy-related devices due to their exceptional capability of precise thickness control, excellent uniformity and conformity, tunable composition and relatively low deposition temperature. In the past few decades, ALD and MLD have been intensively studied for energy storage and conversion applications with remarkable progress. In this work, we give a comprehensive summary of the development and achievements of ALD and MLD and their applications for energy storage and conversion, including batteries, supercapacitors, fuel cells, solar cells, and photoelectrochemical water splitting. Moreover, the fundamental understanding of the mechanisms involved in different devices will be deeply reviewed. Furthermore, the large-scale potential of ALD and MLD techniques is discussed and predicted. Finally, we will provide insightful perspectives on future directions for new material design by ALD and MLD and untapped opportunities in energy storage and conversion.

25 ENERGY STORAGE↗

Advanced electrode manufacturing to enable low cost PEM electrolysis

A critical challenge for the implementation of proton exchange membrane (PEM)-based water electrolyzers for the H2@Scale vision is the capital cost, which is largely driven by related factors of overdesign and highly manual legacy manufacturing methods. Typical electrolyzer cells have an order of magnitude higher membrane thickness and catalyst loading vs. fuel cells, in part because the manufacturing methods being used are not capable of producing uniform and reliable electrodes on thin membranes with low loading. Advanced electrode manufacturing is therefore the key enabler to reduce the cost of the electrolyzer stack, particularly roll-to-roll (R2R) manufacturing of catalyst coated layers (CCLs) and catalyst coated membranes (CCMs). The electrolyzer manufacturing process still relies on traditional sheet-to-sheet (S2S) processes, which requires intensive labor to make parts to meet the specification requirements. This project leverages fuel cell expertise (GM) with Proton’s knowledge of electrolyzer components to develop the electrocatalyst ink formulations and coating processes using slot die (ORNL) and gravure (NREL) coatings, with proof of concept at the pilot-scale (Kodak).

08 HYDROGEN↗

Upcycling Low Linear Density Polyethylene Waste into Turbostratic Graphene for High Mass Loading Supercapacitors

In this work, LLDPE was upcycled into a high quality turbostratic graphene using a pre-treatment step to oxidatively crosslink the polymer with the assistance of solid additives (KCl and K2CO3) that improve crosslinking by increasing the effective surface area of the polymer melt during processing. After this pretreatment step, the crosslinked polymer could then be carbonized and catalytically graphenized between 400-950 °C without complete decomposition of the material. The LLDPE derived graphene (LLDPE-G) obtained from this process has a Brunauer–Emmett–Teller (BET) specific surface area, up to 1800 m2g-1 and average Raman ID/IG and I2D/IG ratios of 0.85 and 0.57, respectively, indicating high quality graphene. When used as an electrode material in symmetric supercapacitors, LLDPE-G possesses an outstanding specific capacitance up to 175 Fg-1 at a mass loading of 20 mgcm-2, which is two times the commercial requirement, yielding an excellent areal capacitance of 3.5 Fcm-2. Moreover, LLDPE-G exhibits exceptional cycling stability with a capacitance retention of 95.8% after 100,000 cycles at a current density of 4.0 Ag-1. Additionally, the KCl and K2CO3 were recycled and reused over 3 complete cycles to make new LLDPE-G with the material quality and electrocapacitive performance retained and verified after each cycle. Our approach creates new opportunities for upcycling not only waste LLDPE but also other varieties of PE to high value graphene materials.

Gao, Yuan [NETL Site Support Contractor, National ↗

Cell-free bioelectrocatalytic platform for carbon dioxide reduction (Final Technical Report)

The University of Minnesota (UMN) EcoSynBio Team aimed to develop a cell-free, enzyme-based platform for the electro- biocatalytic conversion of CO2 into formate as a platform chemical for further upgrading. This type of bio electrocatalytic process delivers a clean product stream without the need for extensive separation from the electrolyte as in electrochemical synthesis and microbial processes. The reduction reaction is catalyzed by metal-dependent formate dehydrogenases (mFDHs) that are capable of efficient electrocatalytic CO2 reduction without the need of costly co-factors. The development of an efficient, scalable electrobiocatalytic process with high total turnover numbers and viable space time yields, however, was not without its challenges. The UM team has developed a protein-based scaffolding system that facilitates enzyme stabilization and attachment to electrodes along with electron transfer. Yet, although FDHs are highly promising enzymes for cell-free, electrobiochemical CO2 reduction, they are also greatly understudied and especially for applications in electrocatalysis. The UM team used the best described mFDH from Clostridium as its benchmark system and spent significant time and effort in attempting to replicate published data and finally, redesigned a recombinant production system for proper metal co-factor incorporation. The UM team has also identified a small set of new enzyme homologs from extreme microorganisms with superior stabilities that have yielded initial structural data for further engineering. In addition, a new bioelectrocatalytic reactor system has been developed that can be 3D printed and used for enzyme attachment to electrodes. In summary the project has generated critical basic information for the further development of this class of enzymes for the electricity driven reduction of CO2 into formate as platform chemical for upgrading into various other chemicals, including fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable Diacid Coordinated Quaternary Ammonium Polymers for 80-230 °C Fuel Cells

Current automotive fuel cells that use sulfonated polymer-based proton exchange membranes are challenging to operate at > 100 °C without humidification. In this project, we developed polymer electrolyte fuel cells that run at > 100 °C without humidification using a novel class of proton exchange membranes made from thermos-oxidatively stable acid-coordinated quaternary ammonium polymers. These fuel cells remove the external humidifiers/demisters and reduce the size of radiators, thus vastly simplifying fuel cell integration, which increases tolerance to impurities and improves electrode kinetics of catalysts. Operating fuel cells without hydration has a significant benefit on fuel cell cost and economic feasibility was investigated by comparing existing fuel cell systems. This project bridges the scale-up process to manufacture the fuel cell component through the U.S. DOE L’Innovator project sponsored by the U.S. DOE Hydrogen and Fuel Cell Technologies Office (HFTO).

30 DIRECT ENERGY CONVERSION↗

Roadmap for Assessing Fuel Reprocessing in Fluoride-Based Salts

This joint report assesses the pyroprocessing of used nuclear fuel from molten fluoride salts being conducted between Idaho National Laboratory and Argonne National Laboratory. The goal of this report is to identify the research and development gaps needed to reduce the technical risks of extending pyroprocessing technologies and unit operations to molten fluoride salts used in molten salt reactors (MSRs). Assessing and performing the tasks outlined in this report will help mitigate the technical risks and design appropriate flowsheets for reprocessing fuel and coolant salts. These suggested tasks will provide necessary data to implement the development of unit operations. Sections are highlighted to identify processes that need to be assessed and unit operations that may be used in fluoride-based chemistries. Research and development needs are listed and discussed including re-fluorination methods, electrowinning for separations, reference electrode development, materials compatibility, salt purification/re-fluorination, and waste disposition. This report will examine the technical challenges associated with pyroprocessing in molten fluoride-based salt and outline approaches to increase the technical readiness level of pyroprocessing in molten fluoride salts.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The effect of microstructure and strength on the fracture toughness of an 18 Ni, 300 grade maraging steel

A 300 grade maraging steel was chosen as a vehicle by which to understand the inverse relationship between strength and toughness in high strength alloys such as the 18 Ni maraging steels. The 18 Ni, 300 grade maraging material was a commercial grade consumable-electrode, vacuum arc remelted heat obtained in the form of forged and annealed plate. The matrix contained a population of second-phase impurity inclusions which was a product of the casting and hot working processes. These inclusions did not change with subsequent precipitation hardening. Changes in microstructure resulting in strength increases were brought about by variations in aging temperature and time. Maximum strength was attained in the 300 grade maraging steel by aging at 427 C (800 F) for 100 hours. Tensile, fatigue precracked Charpy impact, and plane-strain fracture toughness tests were performed at room temperature, 20 C (68 F). With increasing strength the fracture toughness decreases as smaller and smaller inclusions act as sites for void initiation.

Psioda, J. A.↗

Time delay and integration array (TDI) using charge transfer device technology. Phase 2, volume 1: Technical

The 20x9 TDI array was developed to meet the LANDSAT Thematic Mapper Requirements. This array is based upon a self-aligned, transparent gate, buried channel process. The process features: (1) buried channel, four phase, overlapping gate CCD's for high transfer efficiency without fat zero; (2) self-aligned transistors to minimize clock feedthrough and parasitic capacitance; and (3) transparent tin oxide electrode for high quantum efficiency with front surface irradiation. The requirements placed on the array and the performance achieved are summarized. This data is the result of flat field measurements only, no imaging or dynamic target measurements were made during this program. Measurements were performed with two different test stands. The bench test equipment fabricated for this program operated at the 8 micro sec line time and employed simple sampling of the gated MOSFET output video signal. The second stand employed Correlated Doubled Sampling (CDS) and operated at 79.2 micro sec line time.

Source record↗

Welding arc and plasma studies using real time, multipass holographic interferometry

Flow visualization of the plasma process in a welding arc is being studied with a multipass Argon ion interferometer. High speed movies at 10,000 frames per/sec are taken. The multipass interferometer and several interferograms of the plasma near the electrode of the welding are given. Digitization of the fringes is currently done by hand.

Deason, Vance↗

Freeze Tape Casting of Functionally Graded Porous Ceramics

Freeze tape casting is a means of making preforms of ceramic sheets that, upon subsequent completion of fabrication processing, can have anisotropic and/or functionally graded properties that notably include aligned and graded porosity. Freeze tape casting was developed to enable optimization of the microstructures of porous ceramic components for use as solid oxide electrodes in fuel cells: Through alignment and grading of pores, one can tailor surface areas and diffusion channels for flows of gas and liquid species involved in fuel-cell reactions. Freeze tape casting offers similar benefits for fabrication of optimally porous ceramics for use as catalysts, gas sensors, and filters.

Sofie, Stephen W.↗

In-Line Capacitance Sensor for Real-Time Water Absorption Measurements

A capacitance/dielectric sensor was designed, constructed, and used to measure in real time the in-situ water concentration in a desiccant water bed. Measurements were carried out with two experimental setups: (1) passing nitrogen through a humidity generator and allowing the gas stream to become saturated at a measured temperature and pressure, and (2) injecting water via a syringe pump into a nitrogen stream. Both water vapor generating devices were attached to a downstream vertically-mounted water capture bed filled with 19.5 g of Moisture Gone desiccant. The sensor consisted of two electrodes: (1) a 1/8" dia stainless steel rod placed in the middle of the bed and (2) the outer shell of the stainless steel bed concentric with the rod. All phases of the water capture process (background, heating, absorption, desorption, and cooling) were monitored with capacitance. The measured capacitance was found to vary linearly with the water content in the bed at frequencies above 100 kHz indicating dipolar motion dominated the signal; below this frequency, ionic motion caused nonlinearities in the water concentration/capacitance relationship. The desiccant exhibited a dielectric relaxation whose activation energy was lowered upon addition of water indicating either a less hindered rotational motion or crystal reorientation.

Nurge, Mark A.↗

Identifying electrochemical processes by distribution of relaxation times in proton exchange membrane electrolyzers

Distribution of relaxation time (DRT) is used to interpret electrochemical impedance spectroscopy (EIS) for proton exchange membrane (PEM) water electrolyzers, with an attempt to separate overlapped relaxation processes in Nyquist plots. By varying operating conditions and catalyst loadings, four main relaxation peaks arising from EIS can be identified and successfully separated from low to high frequencies as (P1) mass transport, (P2) oxygen evolution reaction kinetics, (P3) reaction kinetics (with faster time constant than P2), and (P4) ionic transport. Here, the shape, height, and frequency of the DRT peaks change with different membrane electrode assembly (MEA) configurations. Electron microscopy reveals distinct features from the cross-sectioned MEAs which verify critical DRT results in that increasing the iridium (Ir)-anode loading from 0.2 mgIr/cm 2 to 1.5 mgIr/cm 2 reduces kinetic losses due to higher site-access; a thick and compacted anode, however, also triggers higher ohmic resistances from membrane/catalyst layer hydration and increases transport losses due to longer ionomer pathways. DRT provides higher resolution to EIS for deconvoluting processes with different relaxation times and the quantification of DRT peaks improves the accounting of total losses from each process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Si-based materials for lithium-ion batteries VI. 15% surface-modified Si/C-graphite/carbon black/lithiated polyacrylic acid electrode

X-ray photoelectron spectroscopy was used to analyze a 15%Si/C-graphite/carbon black/lithiated polyacrylic acid electrode fabricated at the Cell Analysis, Modeling, and Prototyping Facility (CAMP), Argonne National Laboratory. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.83 401 nm). An initial survey spectrum together with O 1s, C 1s, and Si 2p are presented. A final survey spectrum was collected to ascertain the amount of beam-induced damage, which appears to be minimal. The spectra indicate the principal core level photoelectron and Auger electron signals with only minor nitrogen and lithium signals and show the expected silicon-carbon species related to the surface modification process in addition to oxidized carbon and silicon due to atmospheric exposure as well contributions related to the binder material.

17 WIND ENERGY↗

Laser Optogalvanic Spectroscopy pf Neon and Argon in a Discharge Plasma and its Significance for Microgravity Combustion

A detailed study of combustion mechanisms in flames, employing laser-based diagnostics, has provided good knowledge and understanding of the physical phenomena, and led to better characterization of the dynamical and chemical combustion processes, both under low-gravity (in space) and normal gravity (in ground based facilities, e.g. drop towers). Laser induced fluorescence (LIF), laser-induced incandescence (LII) and LIF thermometry have been widely used to perform nonintrusive measurements and to better understand combustion phenomena. Laser optogalvanic (LOG) spectroscopy has well-established applications in ion mobility measurements, atomic and molecular spectroscopy, ionization rates, recombination rates, velocity measurements and as a combustion probe for trace element detection. Absorption spectra of atomic and molecular species in flames can be obtained via LOG spectroscopy by measuring the voltage and current changes induced by laser irradiation. There are different kinds of processes that contribute to a discharge current, namely: (1) electron impact ionization, (2) collisions among the excited atoms of the discharge species and (3) Penning ionization. In general, at higher discharge currents, the mechanism of electron impact ionization dominates over Penning ionization, whereby the latter is hardly noticeable. In a plasma, whenever the wavelength of a laser coincides with the absorption of an atomic or molecular species, the rate of ionization of the species momentarily increases or decreases due to laser-assisted acceleration of collisional ionization. Such a rate of change in the ionization is monitored as a variation in the transient current by inserting a high voltage electrode into the plasma. Optogalvanic spectroscopy in discharges has been useful for characterizing laser line-widths and for providing convenient calibration lines for tunable dye lasers in the ultraviolet, visible and infrared wavelength regions. Different kinds of quantitative information, such as the electron collisional ionization rate, can be extracted from the complex processes occurring within the discharge. In the optogalvanic effect (OGE), there is no problem of overlap from background emissions, and hence even weak signals can be detected with a high signal-to-noise ratio, which makes the optogalvanic effect sensitive enough to resolve vibrational changes in molecular bonds and differences in energy levels brought about by different electron spins. For calibration purposes, neon and argon gaseous discharges have been employed most extensively, because these gases are commonly used as buffer gases within hollow-cathode lamps and provide an acceptable density of calibration lines. In the present work, our main aim has been to understand the dominant physical processes responsible for the production of the OGE signal, based on the extensive time resolved optogalvanic waveforms recorded, and also to extract quantitative information on the rates of excited state collisional processes.

Misra, Prabhakar↗

On the irreversible sodiation of tin disulfide

Tin disulfide is considered as a promising electrode material for sodium-ion batteries because of its two-dimensional layered structural characteristics allowing the intercalation of Na ions. Understanding the underlying reaction mechanisms and the decisive step of the reaction reversibility is critical for its applications. Herein, we investigate the sodiation and desodiation processes of SnS 2 by employing in situ transmission electron microscopy (TEM). After the initial intercalation reaction, a rock-salt Na y SnS 2 phase with disordering Na and Sn cations is observed, followed with a conversion reaction and an alloying reaction. Additionally, the disordering reaction occurs along <1-10> direction of pristine SnS 2 phase which is correlated with local bonding rearrangements induced by the exchange of Sn and Na cations. In-situ TEM studies and first-principles calculations indicate that the original 2D SnS 2 structure could not be recovered during desodiation. Instead, the disordered Na y SnS 2 phase is finally formed, which indicates that the irreversible disordering transition is the determining step of irreversible cycling. This work probes the structural evolution of sodiation, providing a fundamental understanding of the electrochemical properties of metal sulfides and inspiring rational designs of high performance electrodes for sodium-ion batteries.

25 ENERGY STORAGE↗