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At least 19 records

Potential-Dependent Adhesion Forces between dsDNA and Electroactive Surfaces

A promising approach to regulating the interactions between polyelectrolytes and materials is the use of electroactive surfaces that can change their charge state. However, common electroactive groups are too unstable to be practical for this purpose. Here we have performed a single molecule force spectroscopy study of the interactions between dsDNA and an 1,1'-biferrocenylene (BFD = bis(fulvalene)diiron)-terminated self-assembled monolayer surface that allows us to reversibly change the charge state. We found that the interaction force between DNA and the surface is correlated to the oxidation state of the BFD groups, which is conveniently controlled by the electrochemical potentials. We discovered that the electroactive SAM produces much stronger interaction forces than its nonelectroactive counterpart. A model based on the Grahame equation was able to quantitatively reproduce the experimentally observed relation between the applied potentials and adhesion forces. Our electroactive surface provides a model system for quantitative studies of the interactions between polyelectrolyte and charged surfaces in liquid. Furthermore, these insights may enable new opportunities for actively manipulating the binding, orientations, and conformations of polyelectrolytes for biosensing, nanomotors, and other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Functionalized Metal–Organic Framework Thin Films for Stable and Efficient Electrochemical Water Oxidation under Near-Neutral Conditions

The development of molecularly modified metal− organic frameworks (MOFs) for electrochemical water oxidation has emerged as a promising strategy for efficient artificial photosynthesis. In this study, a ruthenium-based water oxidation catalyst (WOC) was incorporated into the UiO-67 framework, forming RuM−UiO-67 films grown directly on conductive FTO substrates. These modified films demonstrate efficient water oxidation activity at near-neutral pH (pH 6), operating at a low overpotential of ∼600 mV. The catalyst exhibits a turnover frequency (TOF) of (0.32 ± 0.02) s −1 at 1.5 V versus the normal hydrogen electrode (NHE) in buffered solution (pH 6) for the oxygen evolution reaction. Notably, incorporation into the MOF results in a 12-fold increase in electroactive surface coverage compared to a monolayer of the same catalyst on bare FTO. Faradaic efficiency analysis revealed incomplete conversion to O 2 , and follow-up iodometric analysis confirmed the formation of H 2 O 2 as a competing two-electron oxidation product during electrocatalysis. These results highlight the utility of MOF-based architectures for maximizing the catalyst accessibility and stability under electrochemical water oxidation conditions.

catalysts↗

Protective coatings for lithium metal electrodes

Double-layered protective coatings for lithium metal electrodes, as well as methods of formation relating thereto, are provided. The negative electrode assembly includes an electroactive material layer including lithium metal and a protective dual-layered coating. The protective dual-layered coating includes a polymeric layer disposed on a surface of the electroactive material layer and an inorganic layer disposed on an exposed surface of the polymeric layer. The polymeric layer has an elastic modulus of greater than or equal to about 0.01 GPa to less than or equal to about 410 GPa. The inorganic layer has an elastic modulus of greater than or equal to about 10 GPa to less than or equal to about 1000 GPa.

Xiao, Xingcheng↗

Backed Bending Actuator

Bending actuators of a proposed type would partly resemble ordinary bending actuators, but would include simple additional components that would render them capable of exerting large forces at small displacements. Like an ordinary bending actuator, an actuator according to the proposal would include a thin rectangular strip that would comprise two bonded layers (possibly made of electroactive polymers with surface electrodes) and would be clamped at one end in the manner of a cantilever beam. Unlike an ordinary bending actuator, the proposed device would include a rigid flat backplate that would support part of the bending strip against backward displacement; because of this feature, the proposed device is called a backed bending actuator. When an ordinary bending actuator is inactive, the strip typically lies flat, the tip displacement is zero, and the force exerted by the tip is zero. During activation, the tip exerts a transverse force and undergoes a bending displacement that results from the expansion or contraction of one or more of the bonded layers. The tip force of an ordinary bending actuator is inversely proportional to its length; hence, a long actuator tends to be weak. The figure depicts an ordinary bending actuator and the corresponding backed bending actuator. The bending, the tip displacement (d(sub t)), and the tip force (F) exerted by the ordinary bending actuator are well approximated by the conventional equations for the loading and deflection of a cantilever beam subject to a bending moment which, in this case, is applied by the differential expansion or contraction of the bonded layers. The bending, displacement, and tip force of the backed bending actuator are calculated similarly, except that it is necessary to account for the fact that the force F(sub b) that resists the displacement of the tip could be sufficient to push part of the strip against the backplate; in such a condition, the cantilever beam would be effectively shortened (length L*) and thereby stiffened and, hence, made capable of exerting a greater tip force for a given degree of differential expansion or contraction of the bonded layers. Taking all of these effects into account, the cantilever-beam equations show that F(sub b) would be approximately inversely proportional to d(sup 1/2) for d less than a calculable amount, denoted the transition displacement (dt). For d less than d(sub t), part of the strip would be pressed against the backplate. Therefore, the force F(sub b) would be very large for d at or near zero and would decrease as d increases toward d(sub t). At d greater than d(sub t), none of the strip would be pressed against the backplate and F(sub b) would equal the tip force F of the corresponding ordinary bending actuator. The advantage of the proposal is that a backed bending actuator could be made long to obtain large displacement when it encountered little resistance but it could also exert a large zero-displacement force, so that it could more easily start the movement of a large mass, throw a mechanical switch, or release a stuck mechanism.

Costen, Robert C.↗

Advanced Layered Composite Polylaminate Electroactive Actuator and Sensor

The present invention relates to the mounting of pre-stressed electroactive material in such a manner that large displacement actuators or sensors result. The invention comprises mounting the pre-stressed electroactive material to a support layer. This combination of a pre-stressed electroactive material and support layer may in turn be attached to a mounting surface. The pre-stressed electroactive material may be a ferroelectric, pyroelectric, piezoelectric, or magnetostrictive material. The size, stiffness, mass, and material of the support layer is selected to result in the electroactive device having dynamic response properties, environmental capability characteristics, and the required resilience optimized for a given application. The capacity to connect the support layer to a surface expands the arenas in which the prestressed electroactive device may be used. Application for which the invention may be used include actuators, sensors, or as a component in a pumps, switches, relays, pressure transducers and acoustic devices.

Fox, Robert L.↗

Mathematical Framework Underlying the In Situ Electrochemical Diagnosis of Adsorbed Intermediates Formed during Redox Reactions at Electrode Surfaces

Previously, we have presented an electrochemical technique wherein an electroactive tracer species is employed to probe the rate-limiting factors governing redox reactions at an electrode surface. In this technique, the electrode is first held potentiostatically to facilitate a redox process (step 1), and then the potential is released to open circuit conditions (step 2) so as to monitor the time-dependent re-equilibration of the electrode potential in the presence of the tracer. The time-dependent potential response in step 2 has been shown to contain information about diffusion—limited or desorption—limited steps, enabling in situ probing of the electrochemistry at the electrode surface during step 1. In the present contribution, a theoretical model governing the transient response in step 2 is developed for two limiting cases: diffusion—limited and desorption—limited recovery of the electrode potential. Mathematical modeling shows that, during re-equilibration, the step 2 potential transient corresponding to a case where step 1 involves surface adsorbed species which undergo desorption in step 2 exhibits a much longer time constant than that when re-equilibration occurs under diffusion limitations. The mathematical framework presented herein provides a sound fundamental basis for applying the aforementioned technique to studying adsorption-desorption processes during electrochemistry. Also, technique limitations are presented in light of the modeling findings.

25 ENERGY STORAGE↗

2D Graphene Sheets as a Sensing Material for the Electroanalysis of Zileuton

Zileuton (ZLT) is an active oral inhibitor of enzyme 5-lipoxygenase, and long-term intake and overdose of ZLT cause adverse effects, leading to critical conditions in patients. This is a well-recognized issue that necessitates a better approach for ZLT sensing. Given the increasing interest in ZLT sensing and the limitations of previous techniques, there is a need for a highly sensitive, robust, and fast operation method that is inexpensive and easy to use. Thus, for the sensitive detection and determination of ZLT, an electrochemical sensor based on graphene was fabricated. Graphene has excellent properties, such as high surface area, low toxicity, conductivity, and electroactive conjugation with biomolecules, making it suitable for sensing. The electrocatalytic property of graphene promotes the redox-coupled reaction of ZLT. Electrochemical investigation of the modifier was carried out by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). An optimization and analysis of the influence of different parameters on the electrochemical behavior of ZLT were carried out using the CV approach. The scan rate study aided in exploring the physicochemical properties of the electrode process, and two electrons with two protons were found to be involved in the electrooxidation of ZLT. The fabricated sensor showed a wide range of linearity with ZLT, from 0.3 µM to 100.0 µM, and the detection limit was evaluated as 0.03 µM under optimized conditions. The analysis of spiked urine samples, with good recovery values for percent RSD, provided support for the efficiency and applicability of the developed electrode.

2D Material↗

Composite electrodes and methods of making the same

Disclosed herein is a composite electrode comprising a charge-conducting material, a charge-providing material bound to the charge-conducting material, and a plurality of single-walled carbon nanotubes bound to a surface of the charge-providing material. High-capacity electroactive materials that assure high performance are a prerequisite for ubiquitous adoption of technologies that require high energy/power density lithium (Li)-ion batteries, such as smart Internet of Things (IoT) devices and electric vehicles (EVs). Improved electrode performance and lifetimes are desirable. The disclosed electrode can have a Coulombic efficiency of 99% or greater, and a stable capacity retention after 100 cycles or more. Also disclosed herein are methods of making a composite electrode.

Kwon, Yo-Han↗

Wirelessly Controllable Inflated Electroactive Polymer (EAP) Reflectors

Inflatable membrane reflectors are attractive for deployable, large aperture, lightweight optical and microwave systems in micro-gravity space environment. However, any fabrication flaw or temperature variation may results in significant aberration of the surface. Even for a perfectly fabricated inflatable membrane mirror with uniform thickness, theory shows it will form a Hencky curve surface but a desired parabolic or spherical surface. Precision control of the surfaceshape of extremely flexible membrane structures is a critical challenge for the success of this technology. Wirelessly controllable inflated reflectors made of electroactive polymers (EAP) are proposed in this paper. A finite element model was configured to predict the behavior of the inflatable EAP membranes under pre-strains, pressures and distributed electric charges on the surface. To explore the controllability of the inflatable EAP reflectors, an iteration algorism was developed to find the required electric actuation for correcting the aberration of the Hencky curve to the desired parabolic curve. The correction capability of the reflectors with available EAP materials was explored numerically and is presented in this paper.

Electroactive polymer (EAP)↗

Electrical resistance of the current collector controls lithium morphology

Abstract The electrodeposition of low surface area lithium is critical to successful adoption of lithium metal batteries. Here, we discover the dependence of lithium metal morphology on electrical resistance of substrates, enabling us to design an alternative strategy for controlling lithium morphology and improving electrochemical performance. By modifying the current collector with atomic layer deposited conductive (ZnO, SnO 2 ) and resistive (Al 2 O 3 ) nanofilms, we show that conductive films promote the formation of high surface area lithium deposits, whereas highly resistive films promote the formation of lithium clusters of low surface area. We reveal an electrodeposition mechanism in which radial diffusion of electroactive species is promoted on resistive substrates, resulting in lateral growth of large (150 µm in diameter) planar lithium deposits. Using resistive substrates, similar lithium morphologies are formed in three distinct classes of electrolytes, resulting in up to ten-fold improvement in battery performance. Ultimately, we report anode-free pouch cells using the Al 2 O 3 -modified copper that maintain 60 % of their initial discharge capacity after 100 cycles, displaying the benefits of resistive substrates for controlling lithium electrodeposition.

25 ENERGY STORAGE↗

Alkaline cation enrichment and water electrolysis to provide CO 2 mineralization and global-scale carbon management

Provided herein are methods of removing carbon dioxide from an aqueous stream or gaseous stream by: contacting the gaseous stream comprising carbon dioxide, when present, with an aqueous solution comprising ions capable of forming an insoluble carbonate salt; contacting the aqueous solution comprising carbon dioxide with an electroactive mesh that induces its alkalinization thereby forcing the precipitation of a carbonate solid from the solution and thereby the removal of dissolved inorganic carbon by electrolysis; and removing the precipitated carbonate solids from the solution, or the surface of the mesh where they may deposit. Also provided herein are flow-through electrolytic reactors comprising an intake device in fluid connection with a rotating cylinder comprising an electroactive mesh, and a scraping device and/or liquid-spray based device for separating a solid from the mesh surface.

Sant, Gaurav↗

Nanotube Film Electrode and an Electroactive Device Fabricated with the Nanotube Film Electrode and Methods for Making Same

Disclosed is a single wall carbon nanotube (SWCNT) film electrode (FE), all-organic electroactive device systems fabricated with the SWNT-FE, and methods for making same. The SWCNT can be replaced by other types of nanotubes. The SWCNT film can be obtained by filtering SWCNT solution onto the surface of an anodized alumina membrane. A freestanding flexible SWCNT film can be collected by breaking up this brittle membrane. The conductivity of this SWCNT film can advantageously be higher than 280 S/cm. An electroactive polymer (EAP) actuator layered with the SWNT-FE shows a higher electric field-induced strain than an EAP layered with metal electrodes because the flexible SWNT-FE relieves the restraint of the displacement of the polymeric active layer as compared to the metal electrode. In addition, if thin enough, the SWNT-FE is transparent in the visible light range, thus making it suitable for use in actuators used in optical devices.

Kang, Jin Ho↗

Methods for Making an Electroactive Device Fabricated with a Nanotube Film Electrode

Disclosed is a single wall carbon nanotube (SWCNT) film electrode (FE), all-organic electroactive device systems fabricated with the SWNT-FE, and methods for making same. The SWCNT can be replaced by other types of nanotubes. The SWCNT film can be obtained by filtering SWCNT solution onto the surface of an anodized alumina membrane. A freestanding flexible SWCNT film can be collected by breaking up this brittle membrane. The conductivity of this SWCNT film can advantageously be higher than 280 S/cm. An electroactive polymer (EAP) actuator layered with the SWNT-FE shows a higher electric field-induced strain than an EAP layered with metal electrodes because the flexible SWNT-FE relieves the restraint of the displacement of the polymeric active layer as compared to the metal electrode. In addition, if thin enough, the SWNT-FE is transparent in the visible light range, thus making it suitable for use in actuators used in optical devices.

Kang, Jin Ho↗

Photoelectrochemical electrodes

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Williams, R. M.↗