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At least 667 records · Page 37

Effect of Substrate Temperature on the Electrochemical and Supercapacitance Properties of Pulsed Laser-Deposited Titanium Oxynitride Thin Films

Electrocatalytically active titanium oxynitride (TiNO) thin films were fabricated on commercially available titanium metal plates using a pulsed laser deposition method for energy storage applications. The elemental composition and nature of bonding were analyzed using X-ray photoelectron spectroscopy (XPS) to reveal the reacting species and active sites responsible for the enhanced electrochemical performance of the TiNO electrodes. Symmetric supercapacitor devices were fabricated using two TiNO working electrodes separated by an ion-transporting layer to analyze their real-time performance. The galvanostatic charge–discharge studies on the symmetric cell have indicated that TiNO films deposited on the polycrystalline titanium plates at lower temperatures are superior to TiNO films deposited at higher temperatures in terms of storage characteristics. For example, TiNO films deposited at 300 °C exhibited the highest specific capacity of 69 mF/cm 2 at 0.125 mA/cm 2 with an energy density of 7.5 Wh/cm 2 . The performance of this supercapacitor (300 °C TiNO) device is also found to be ~22% better compared to that of a 500 °C TiNO supercapacitor with a capacitance retention ability of 90% after 1000 cycles. Furthermore, the difference in the electrochemical storage and capacitance properties is attributed to the reduced leaching away of oxygen from the TiNO films by the Ti plate at lower deposition temperatures, leading to higher oxygen content in the TiNO films and, consequently, a high redox activity at the electrode/electrolyte interface.

30 DIRECT ENERGY CONVERSION↗

Galvanostatic Intermittent Titration Technique Reinvented: Part I. A Critical Review

The galvanostatic intermittent titration technique (GITT), introduced in 1977 by Weppner and Huggins, provided a readily accessible means to measuring the chemical diffusion coefficient of electrochemical electrode materials. The method continues to be widely used today, but the reported diffusivity values are highly inconsistent, ranging as much as four orders of magnitude for some Li layered oxide compositions. Even qualitative trends of diffusivity are inconsistent, suggesting significant flaws in the implementation of the method. Other variants of the GITT method also suffer from similar inconsistency problems. Here we identify numerous sources of significant error including composition-dependent reaction overpotentials, mathematical flaws in the relaxation analysis methods, finite-size and non-planar geometry effects, inter-particle inhomogeneity issues, early transient effects, and surface area uncertainties. We propose a simple relaxation analysis scheme using the time variable t relax + τ - t relax , where t relax is relaxation time and τ is the galvanostatic pulse duration. We also propose to use dense diffusion-limited samples to isolate the bulk-diffusion process in the time domain. Chemical diffusivity can be extracted much more reliably with this improved implementation of the GITT method.

25 ENERGY STORAGE↗

Potentiodynamic Polarization of Pure Metals and Alloys in Molten LiF-NaF-KF (FLiNaK) Using the K/K + Dynamic Reference Electrode

The potentiodynamic polarization method using the K/K + dynamic reference electrode was used to understand the corrosion behavior of Ni, Fe, Cr, the Ni-20Cr binary alloy, and 316L stainless steel in molten 46.5LiF-11.5NaF-42KF (FLiNaK, composition in mol %) salt at 700 °C. Exposure of the materials without an applied potential revealed that Ni and Fe were stable in FLiNaK, but Cr was dissolved rapidly. The apparent redox potentials of each material with respect to the K/K + redox couple are compared to gain insight into how the applied potential relates to the dominant corrosion mechanism for each alloy. Furthermore, the polarized pure metals experienced uniform surface recession while corrosion in the alloys resulted in preferential elemental dissolution depending on the applied potential with respect to the K/K + reference reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the complex interplay between thermodynamics, kinetics, and electrochemistry in battery electrodes through phase-field modeling

Abstract This article highlights applications of phase-field modeling to electrochemical systems, with a focus on battery electrodes. We first provide an overview on the physical processes involved in electrochemical systems and applications of the phase-field approach to understand the thermodynamic and kinetic mechanisms underlying these processes. We employ two examples to highlight how realistic thermodynamics and kinetics can naturally be incorporated into phase-field modeling of electrochemical processes. One is a composite battery cathode with an intercalation compound (Li x FePO 4 ) as the electrochemically active material, and the other is a displacement reaction compound (Li–Cu–TiS 2 ). With the input parameters mostly from atomistic calculations and experimental measurements, phase-field simulations allowed us to untangle the interactions among transport, reaction, electricity, chemistry, and thermodynamics that lead to highly complex evolution of the materials within battery electrodes. The implications of these observations for battery performance and degradation are discussed. Graphical abstract

Andrews, W. Beck (ORCID:0000000287824621)↗

Gas-Phase Composition as a Predictive Metric for Calendar Life Behavior of Next-Generation Silicon Anodes

The expansion of renewable technologies and electrification of the transportation sector is driving increased demand for next-generation battery materials that provide higher power and energy density with superior cycling and calendar life stability. Silicon (Si) has a theoretical capacity nearly 10x that of graphite, and is therefore a promising anode material candidate to meet these rigorous performance demands. While leading Si anode battery demonstrations are approaching target metrics for cycle life, a series of complex and interrelated modes of reactivity lead to reduced calendar life and therefore challenge practical adoption of these materials. Deconvoluting the degradation processes that impact Si calendar life is critical to informing the rational and accelerated design of improved Si materials. In the present work, we employ novel sampling techniques and GC-MS-FID characterization to measure gas-phase composition during initial Si cycling, which we tie to selective mechanisms of Si passivation. We utilize a tiered analysis approach to identify and quantify the gas-phase reaction products associated with three advanced Si material candidates under practical operating conditions. Ex situ analysis of Si powders (pure chemical reactivity) is coupled with nondestructive in situ sampling of Si electrodes in a practical pouch-cell format (coupled chemical and electrochemical reactivity). We link the observed gas-phase species evolution to electrochemical behavior and measured calendar life of the three Si materials. Further, we evaluate the voltage-resolved evolution of gas-phase species for one such Si nanomaterial, where nonmonotonic gas generation implies competition between passivating reaction pathways. The measured gas-phase compositional data serves as a critical input for our advanced electrochemical SEI models to identify favorable vs unfavorable reaction pathways to stabilize Si. In addition to bolstering a fundamental understanding of Si reactivity, the present approach informs specific and quantifiable gas-phase metrics tied to calendar life improvements in Si, which can streamline and accelerate the process of next-generation material development.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗

Dual 3D Ceramic Textile Electrodes: Fast Kinetics for Carbon Oxidation Reaction and Oxygen Reduction Reaction in Direct Carbon Fuel Cells at Reduced Temperatures

Abstract Direct carbon fuel cells (DCFCs) are an efficient energy‐conversion technology capable of generating electricity with carbon‐dioxide‐capture chemistry with solid carbon as fuels. The efficiency and performance of DCFCs depend on the kinetics of the carbon oxidation reactions (COR) and the oxygen reduction reactions (ORR), each occurring at anode and cathode, respectively. The limited active sites paired with reduced temperatures greatly decrease the efficiency of the electrochemical reactions. Ultraporous dual‐3D ceramic textiles (dual‐3DCT) are integrated into electrolyte‐supported DCFCs to enhance charge and mass transfer at the electrodes. Improved COR at the anode is achieved by the synergy between the 3DCT NiO–Ce 0.8 Gd 0.2 O 1.95 (GDC) structure and optimal carbon fuel choice. In a comparative study, DCFCs using graphitic carbon (GC) as fuel show the best COR performance when compared to DCFCs utilizing alternative fuels such as carbon black (CB) and activated carbon (AC). The 3DCT Sm 0.5 Sr 0.5 CoO 3‐δ –GDC (SSC–GDC) composite cathode shows electrochemical performance superior to that of the conventional screen‐printed SSC–GDC. A peak power density of 392 mW cm −2 at 600 °C is obtained in a DCFC using the 3DCT‐anode/electrolyte/3DCT‐cathode configuration, an unprecedented value for any reported DCFC as of yet. This points toward promising applications of dual‐3DCT electrodes for reduced‐temperature DCFCs.

Bian, Wenjuan↗

Elucidating the Synergic Effect in Nanoscale MoS 2 /TiO 2 Heterointerface for Na‐Ion Storage

Abstract Interface engineering in electrode materials is an attractive strategy for enhancing charge storage, enabling fast kinetics, and improving cycling stability for energy storage systems. Nevertheless, the performance improvement is usually ambiguously ascribed to the “synergetic effect”, the fundamental understanding toward the effect of the interface at molecular level in composite materials remains elusive. In this work, a well‐defined nanoscale MoS 2 /TiO 2 interface is rationally designed by immobilizing TiO 2 nanocrystals on MoS 2 nanosheets. The role of heterostructure interface between TiO 2 and MoS 2 by operando synchrotron X‐ray diffraction (sXRD), solid‐state nuclear magnetic resonance, and density functional theory calculations is investigated. It is found that the existence of a hetero‐interfacial electric field can promote charge transfer kinetics. Based on operando sXRD, it is revealed that the heterostructure follows a solid‐solution reaction mechanism with small volume changes during cycling. As such, the electrode demonstrates ultrafast Na + ions storage of 300 mAh g −1 at 10 A g −1 and excellent reversible capacity of 540 mAh g −1 at 0.2 A g −1 . This work provides significant insights into understanding of heterostructure interface at molecular level, which suggests new strategies for creating unconventional nanocomposite electrode materials for energy storage systems.

25 ENERGY STORAGE↗

Direct writing of PVBVA/Ti 3 C 2 T x (MXene) triboelectric nanogenerators for energy harvesting and sensing applications

Triboelectric nanogenerators (TENGs) have gained recognition for their potential to convert mechanical energy into electrical energy, making them attractive for applications in healthcare, robotics, and human-device interfaces. However, many TENG devices rely on fluorinated polymers for high charge generation and involve complex fabrication processes, which limit their practicality and environmental sustainability. Here, we developed an eco-friendly composite of poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (PVBVA) and Ti 3 C 2 T x MXene for extrusion printing onto aluminum foil substrates, enabling the additive manufacturing of TENGs. Experimental results indicate that integrating 5.5 mg mL -1 of MXene (P-MX 5.5) into PVBVA resulted in a power density of 760 mW·m -2 , with simultaneous improvements in open-circuit voltage (129 %) and short-circuit current (250 %), demonstrating enhanced charge transfer efficiency. Beyond aluminum foil-based devices, we further explored the fully printed P-MX 5.5 TENG by utilizing silver ink electrodes, eliminating the need for aluminum foil. This fully printed, flexible TENG was successfully used for real-time human motion sensing, demonstrating its ability to detect activities such as walking, running, knee bending, and jumping. Collectively, our additively manufactured and sustainable PVBVA-MXene TENG composites, including both aluminum-based and fully printed versions, show promise for future energy harvesters, sensors, wearable electronics, healthcare, and robotic applications.

Additive manufacturing↗

Scalable and Highly-Efficient Microbial Electrochemical Reactor for Hydrogen Generation from Wastes

The overall goal of this project was to develop a scalable and highly efficient hybrid microbial electrochemical reactor for hydrogen recovery from waste streams at a cost of less than $\$$2/kg H₂. The specific objectives were: (1) to design and fabricate a scalable and highly efficient microbial electrochemical cell (MEC) reactor, and (2) to determine the techno-economic feasibility of the system for H₂ generation from organic-rich waste streams. We achieved the first objective by (a) developing low-cost electrode materials, (b) synthesizing a highly efficient cathode catalyst in a scalable manner, (c) evaluating and validating the developed electrode material and catalyst in MEC reactors, and (d) designing and fabricating a larger reactor that incorporates (a) to (c). We met the second objective by (a) identifying the impacts of wastewater composition and operational conditions on H₂ production, and (b) developing a cost-performance model that identified critical parameters affecting the system's performance and cost, providing a pathway for further improvement.

08 HYDROGEN↗

Study of the capacitance technique for measuring high-temperature blade tip clearance on ceramic rotors

Higher operating temperatures required for increased engine efficiency can be achieved by using ceramic materials for engine components. Ceramic turbine rotors are subject to the same limitations with regard to gas path efficiency as their superalloy predecessors. In this study, a modified frequency-modulation system is proposed for the measurement of blade tip clearance on ceramic rotors. It is expected to operate up to 1370 C (2500 F), the working temperature of present engines with ceramic turbine rotors. The design of the system addresses two special problems associated with nonmetallic blades: the capacitance is less than that of a metal blade and the effects of temperature may introduce uncertainty with regard to the blade tip material composition. To increase capacitance and stabilize the measurement, a small portion of the rotor is modified by the application of 5-micron-thick platinum films. The platinum surfaces on the probe electrodes and rotor that are exposed to the high-velocity gas stream are coated with an additional 10-micron-thick protective ceramic topcoat. A finite-element method is applied to calculate the capacitance as a function of clearance.

Barranger, John P.↗

Electrochemical polymer pen lithography

Disclosed herein is a massively parallel patterning tool for the deposition of single metals or metal alloys with size and composition control. Methods of the disclosure use a hydrogel array of pyramidal pen tips as a medium for localized electrodeposition, in conjunction with a scanning probe lithography platform and a three-electrode cell. This versatile technique can be used for high-throughput 3D printing, biomolecule patterning, or screening of catalyst nanoparticles or thin films.

Mirkin, Chad A.↗

Highly Ordered Carbon Coating Prepared with Polyvinylidene Chloride Precursor for High‐Performance Silicon Anodes in Lithium‐Ion Batteries

Abstract A highly ordered carbon structure based on polyvinylidene chloride precursor has been developed to host silicon nanoparticles. The stoichiometric ratio of sacrificial H and Cl elements facilitated full utilization of the carbon content of the precursor that produced robust carbon coatings on silicon nanoparticles with excellent mechanic properties and electrochemical stabilities. The optimal sintering temperature and carbon content have been investigated. When evaluated as the anode of a lithium‐ion battery (LIB), the Si : C 1 : 2 composite sintered at 800 °C (SiC12‐800) provided excellent capacity retention of 85 % at 0.1 C after 50 cycles with an enhanced CE, which reached 99 % only after 10 cycles. The SiC12‐800 electrode maintained a specific capacity of 709.2 mAh/g after 300 cycles at 0.3 C, and delivered a high rate performance of 737.9 mAh/g and 485.6 mAh/g at 5 C and 10 C, respectively. The results indicate that polymer precursors with stoichiometric ratio of sacrificial elements have high potential for generating highly robust carbon coatings for silicon anodes in high energy density LIBs.

Zhou, Shuo↗

Revealing Coexisting Cu0–Cu+ Sites in Cu3N Nanoensembles for Selective CC Coupling of CO2 Under Low Overpotential

To address a long-existing debate on what copper species are responsible for efficient CC coupling, especially ethanol formation, in electrochemical CO2 reduction reaction, herein, a comprehensive study using Cu3N nanocubes with a uniform size and shape, alongside a single crystalline phase is reported. The Cu3N nanoensemble electrode has a remarkable Faradaic efficiency (FE) of 64% for ethanol production at a relatively low potential of -0.6 V versus reversible hydrogen electrode. Through in-operando X-ray absorption spectroscopy study, a dynamic phase evolution that directly correlates with changes in FE across varying applied potentials is observed. Notably, the nanoensemble with a composition of ≈71% Cu+ and 29% Cu0 is identified as being selective for ethanol formation at the low overpotential. Conversely, a predominantly metallic Cu phase formed at potentials more negative than -0.6 V favors the hydrogen evolution reaction. Density functional theory calculations at the Cu3N-Cu interface substantiate that the coexistence of Cu0-Cu+ not only energetically favors the ethanol reaction pathway but also destabilizes the intermediates for ethylene pathway.

*CH-CHO as an intermediate for ethanol production↗

Multifunctional approaches for safe structural batteries

Recent advancements in Li and Li-ion based energy storage resulted in development of novel electrode materials for higher energy density which are finding their applications in transportation. There appears to be a limitation in improvement of specific energy of the system based solely on design of material compositions for multivalent intercalation compounds. In addition, higher energy stored by the system implies need for addressing safety concerns especially when it comes to large automotive battery packs. New approaches for improvement of both energy density and safety of batteries are emerging, where multifunctionality of the materials and/or architectures is utilized. Here, we present a review for such approaches from multifunctional current collectors to design of batteries capable of supporting mechanical loads and thus possessing ability to be used as a structural component.

25 ENERGY STORAGE↗

Ethanol-fueled metal supported solid oxide fuel cells with a high entropy alloy internal reforming catalyst

High-performance metal supported solid oxide fuel cells (MS-SOFC) with an integrated high entropy alloy (HEA) internal reforming catalyst (IRC) are demonstrated for transportation applications using ethanol and methanol as fuels. Addition of the HEA IRC dramatically improves cell performance and stability when using ethanol/water blend fuel. Absence of carbon deposition predicted by thermodynamic calculations is confirmed by Raman spectroscopy analysis of posttest anodes. Optimal catalyst processing (deposition technique, loading, firing temperature) and cell operation conditions (flow rates, temperature, fuel compositions) are explored. Infiltrated HEA reforming catalyst provides a highly porous structure and low catalyst loading (6 mg cm –2 ). The designed structure and catalysts achieve small mass transport resistances in the fuel electrode (26.2 s m –1 ) and oxygen electrode (41.6 s m –1 ). The best ethanol concentration (60:40 v% ethanol: water) provides 0.83 W cm –1 at 700 °C, without carbon deposition. The ethanol-fueled MS-SOFC is operated for 500 h, including five thermal cycles. As a result, cell evolution is similar to that reported previously for hydrogen fuel; nickel aggregation and chromia deposition were the major observed changes, and carbon formation can be avoided even after long-term operation.

30 DIRECT ENERGY CONVERSION↗

Nanostructured Powders Made from Flame Spray Pyrolysis for Li-Ion Cathode

Flame processes are the most economic ones to produce fine powders and have been used to produce pigment titanium oxide and fused silica in large volumes. In this work a flame spray pyrolysis (FSP) process is used to make positive electrode materials for Li-ion battery, which is made of complex metal oxide powders, such as Li(Ni1/3Mn1/3Co1/3)O2. In particular, the work was focused on making the NMC materials with stoichiometric compositions and desired morphologies. During the pyrolysis process different morphologies can be formed, involving often powders with primary nanoparticles. Such nanostructures were found to have affected the battery performance. Detailed results of the synthesis, characterization, and battery testing of the NMC powder materials will be presented.

25 ENERGY STORAGE↗

NASA Tech Briefs, July 2008

Topics covered include: Torque Sensor Based on Tunnel-Diode Oscillator; Shaft-Angle Sensor Based on Tunnel-Diode Oscillator; Ground Facility for Vicarious Calibration of Skyborne Sensors; Optical Pressure-Temperature Sensor for a Combustion Chamber; Impact-Locator Sensor Panels; Low-Loss Waveguides for Terahertz Frequencies; MEMS/ECD Method for Making Bi(2-x)Sb(x)Te3 Thermoelectric Devices; Low-Temperature Supercapacitors; Making a Back-Illuminated Imager with Back-Side Contact and Alignment Markers; Compact, Single-Stage MMIC InP HEMT Amplifier; Nb(x)Ti(1-x)N Superconducting-Nanowire Single-Photon Detectors; Improved Sand-Compaction Method for Lost-Foam Metal Casting; Improved Probe for Evaluating Compaction of Mold Sand; Polymer-Based Composite Catholytes for Li Thin-Film Cells; Using ALD To Bond CNTs to Substrates and Matrices; Alternating-Composition Layered Ceramic Barrier Coatings; Variable-Structure Control of a Model Glider Airplane; Axial Halbach Magnetic Bearings; Compact, Non-Pneumatic Rock-Powder Samplers; Biochips Containing Arrays of Carbon-Nanotube Electrodes; Nb(x)Ti(1-x)N Superconducting-Nanowire Single-Photon Detectors; Neon as a Buffer Gas for a Mercury-Ion Clock; Miniature Incandescent Lamps as Fiber-Optic Light Sources; Bidirectional Pressure-Regulator System; and Prism Window for Optical Alignment. Single-Grid-Pair Fourier Telescope for Imaging in Hard-X Rays and gamma Rays Range-Gated Metrology with Compact Optical Head Lossless, Multi-Spectral Data Compressor for Improved Compression for Pushbroom-Typetruments.

Source record↗

Li-substituted layered spinel cathode materials for sodium ion batteries

Systems, methods, and compositions are disclosed for a Li-substituted layered-tunneled O3/spinel Na(NixFeyMnz)O2 cathode material, Na0.87Li0.25Ni0.4Fe0.2Mn0.4O2+∂ (LS-NFM) for enhanced sodium ion storage and cycling stability. The LS-NFM electrode is prepared by adjusting the stoichiometric ratio of the Na ion over the sum of Li and transition metal ions below 1. The Rietveld refinement of XRD data indicates that the cathode is composed of 94% layered and 6% spinel components. When cycled at a high current density of 100 mA g−1, LS-NFM cathode exhibited a first-cycle Coulombic efficiency of 88% and reversible discharge capacity of 107 mAh g−1 after 50 cycles with the capacity retention of 95%.

Xiong, Hui↗