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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 847 records · Page 47

3D-Printed Graded Electrode with Ultrahigh MnO 2 Loading for Non-Aqueous Electrochemical Energy Storage

Electrolytic manganese dioxide is one of the promising cathode candidates for electrochemical energy storage devices due to its high redox capacity and ease of synthesis. Yet, high-loading MnO 2 often suffers from sluggish reaction kinetics, especially in non-aqueous electrolytes. The non-uniform deposition of MnO 2 on a porous current collectors also makes it difficult to fully utilize the active materials at high mass loading. Here, a 3D printed graded graphene aerogel (3D GA) that contains sparsely separated exterior ligaments is developed to create large open channels for mass transport as well as densely arranged interior ligaments providing large ion-accessible active surface. The unique structural design homogenizes the thickness of electro deposited MnO 2 even at an ultrahigh mass loading of ≈70 mg cm -2 . The electrode achieves a remarkable volumetric capacity of 29.1 mA h cm -3 in the non-aqueous electrolyte. A Li-ion hybrid capacitor device assembled with a graded 3D GA/MnO2 cathode and graded 3D GA/VO x anode exhibits a wide voltage window of 0–4 V and a superior volumetric energy density of 20.2 W h L -1 . The findings offer guidance on 3D printed electrode design for supporting ultrahigh loading of active materials and developments of high energy density energy storage devices.

electrochemical energy storage↗

Materials science applications of Neutron Depth Profiling at the PGAA facility of Heinz Maier-Leibnitz Zentrum

Highlights: • Exploiting the range of NDP from thin films to electrodes for Li-ion batteries • Adopting an analytical method to probe undisturbed depth profiles from thick films • Revealing depth-dependent lithium immobilization in Li-ion battery electrodes Neutron depth profiling (NDP) is a non-destructive, isotope-sensitive profiling technique to monitor concentration profiles in almost any material matrix. Since NDP is sensitive to {sup 6}Li and lithium is widely used for different material science applications such as ceramics, optical waveguides or energy-storage systems, NDP offers answers to a broad spectrum of research questions. In the present work, the recently developed instrument N4DP at MLZ is used to address two research questions which are hardly accessible by conventional analytical techniques. First, the homogeneity of lithium formations within lithium niobate thin films for optical waveguide applications is investigated. Afterwards, the accumulation of inactive lithium in the solid-electrolyte-interphase (SEI) of silicon-graphite electrodes for lithium-ion batteries is studied ex situ. Since the material mass loading differs considerably between the two applications, a new analytical technique is introduced which mathematically separates the different particle signals and thus allows to investigate samples with high mass loadings.

36 MATERIALS SCIENCE↗

Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells

One promising approach to reduce the cost of fuel cell systems is to develop hydroxide exchange membrane fuel cells (HEMFCs), which open up the possibility of platinum-group-metal-free catalysts and low-cost bipolar plates. However, scalable alkaline polyelectrolytes (hydroxide exchange membranes and hydroxide exchange ionomers), a key component of HEMFCs, with desired properties are currently unavailable, which presents a major barrier to the development of HEMFCs. Here we show hydroxide exchange membranes and hydroxide exchange ionomers based on poly(aryl piperidinium) (PAP) that simultaneously possess adequate ionic conductivity, chemical stability, mechanical robustness, gas separation and selective solubility. Here, these properties originate from the combination of the piperidinium cation and the rigid ether-bond-free aryl backbone. A low-Pt membrane electrode assembly with a Ag-based cathode using PAP materials showed an excellent peak power density of 920 mW cm -2 and operated stably at a constant current density of 500 mA cm -2 for 300 h with H 2 /CO 2 -free air at 95 °C.

25 ENERGY STORAGE↗

Hydration Mechanisms in Nanoparticle Interaction and Surface Energetics

Work on the project advanced molecular level understanding, prediction and control of nanoscale hydration in salt solutions under electric stimuli or ionic patterning. Permeation of nanoporous electrodes at preset voltage underlies the function of ultracapacitors. Transitory regulation of wetting in nanoporous media by electric field spans an array of applications in materials, energy storage, and separation sciences. The physically related modulation of nanoparticle solubility by surface charges can significantly extend the range of the nanomaterial applications, improve processing techniques, and potentially alleviate environmental concerns. Pore/solution equilibria, and activated kinetics of liquid gating by nanoconfined electrolytes are challenging problems at the forefront of experimental and theoretical research. Addressing these problems from a molecular perspective required the development of state-of-the-art simulation algorithms in statistical mechanics to capture complex processes in open systems under electric control. Parallel studies of wetting and dispersibility of polar and ionizing particles aim to uncover predictive relations between electrowetting, chemical functionalization, and geometry of nanomaterial particles. By nonequilibrium dynamic modeling, we elucidated electrolyte flow in nanochanels and associated electrokinetic energy conversion. Research on the program provided training opportunities for the next generation of scientists in computational chemistry. Insights, and methods from the project implicate broad segment of researchers in energy and nanosciences, materials and surface chemistry.

74 ATOMIC AND MOLECULAR PHYSICS↗

Method of manufacturing a shapeable short-resistant capacitor

A method that employs a novel combination of conventional fabrication techniques provides a ceramic short-resistant capacitor that is bendable and/or shapeable to provide a multiple layer capacitor that is extremely compact and amenable to desirable geometries. The method allows thinner and more flexible ceramic capacitors to be made. The method includes forming a first thin metal layer on a substrate; depositing a thin, ceramic dielectric layer over the metal layer; depositing a second thin metal layer over the dielectric layer to form a capacitor exhibiting a benign failure mode; and separating the capacitor from the substrate. The method may also include bending the resulting capacitor into a serpentine arrangement with gaps between the layers that allow venting of evaporated electrode material in the event of a benign failure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Metal-air flow batteries using oxygen enriched electrolyte

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

25 ENERGY STORAGE↗

Metal-air flow batteries using oxygen enriched electrolyte

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

25 ENERGY STORAGE↗

Benzothiophene-based redox molecules for flow battery

The present invention provides a redox flow battery comprising a negative electrode (also referred to herein as an “anode”) immersed in a first liquid electrolyte (also referred to herein as a “negative electrolyte” or “anolyte”), a positive electrode (also referred to herein as a “cathode”) immersed in a second liquid electrolyte (also referred to herein as a “positive electrolyte” or “catholyte”), and a cation-permeable separator (e.g., a membrane or other cation-permeable material) partitioning the negative electrode/anolyte from the positive electrode/catholyte. The redox reactant of the catholyte comprises a compound of Formula (I) as described herein.

25 ENERGY STORAGE↗

Systems and methods of long-duration energy storage and regeneration of energy-bearing redox pairs

Described herein are systems and methods of storing and delivering electrical using hydrogen at low-cost and for long-durations. The systems and methods use energy-bearing redox pairs that electrochemically bear energy through decoupled hydrogen and oxygen consumption and/or evolution reactions, which are typically associated with fuel cells. Each species of the energy-bearing redox pair is associated with a standard electrode potential within a water electrolysis voltage window for the electrolyte solution. Electrical energy delivery, hydrogen generation, electrolyte regeneration, or combinations thereof can be performed by logically or physically separated unit operations in a continuous manner, batch manner, or semi-batch manner facilitated by the energy-bearing redox pair.

08 HYDROGEN↗

Organic redox molecules for flow batteries

The present invention provides a redox flow battery comprising a negative electrode (also referred to herein as an “anode”) immersed in a first liquid electrolyte (also referred to herein as a “negative electrolyte” or “anolyte”), a positive electrode (also referred to herein as a “cathode”) immersed in a second liquid electrolyte (also referred to herein as a “positive electrolyte” or “catholyte”), and a cation-permeable separator (e.g., a membrane or other cation-permeable material) partitioning the negative electrode/anolyte from the positive electrode/catholyte. The redox reactant of the catholyte comprises a compound of Formula (I) as described herein.

25 ENERGY STORAGE↗

Electrochemical Energy Storage with an Aqueous Quinone–Air Chemistry

We present that organic electrode materials such as quinones are drawing rising attention as promising redox-active materials for the development of rechargeable batteries. In aqueous solutions, the redox potential of quinones is dependent on the alkalinity and acidity of the medium. Under an alkaline condition, the oxidation potential of hydroquinone (existing as diphenolate) is ca. 0.8 V lower than that under an acidic condition. On the other hand, under an acidic condition, the reduction potential of oxygen is ca. 0.8 V higher than that under an alkaline condition. By taking these advantages, a Quinone-air cell with a rational voltage is strategically demonstrated with an alkaline anode electrolyte and an acidic cathode electrolyte, which are physically separated by a Na + -ion conductive solid-state electrolyte membrane. Finally, the Na + -ions shuttling through the solid-state membrane act as ionic media-tors/messengers to sustain and link the redox reactions at the two electrodes.

25 ENERGY STORAGE↗

Additive manufacturing of LiCoO 2 electrodes via vat photopolymerization for lithium ion batteries

Additive manufacturing has the potential to revolutionize the fabrication of lithium-ion batteries for a diversity of applications including in portable, biomedical, aerospace, and the transportation fields. Standard commercial batteries consist of stacked layers of various components (current collectors, cathode, anode, separator and electrolyte) in a two-dimensional manner. By leveraging the latest advances in additive manufacturing and computer-aided design, an improved geometric and electrochemical configuration of these batteries can maximize energy efficiency while allowing design optimization to reduce dead space for a given application. In this work, a composite UV photosensitive resin was prepared and used as feedstock in a vat photopolymerization system. The resin was loaded with LiCoO 2 acting as electrochemically active material for the cathode of a lithium-ion battery, and was further improved with the addition of conductivity-enhancing carbonaceous additives. Challenges to additive manufacturing arise from the opacity and high viscosity of the composite nature of these electrochemically-active resins, which cause light refraction during selective UV curing. Subsequently, items were printed and subjected to a thermal post-processing step to obtain an adequate compromise between electrochemical performance and mechanical integrity. Both sintered and green state 3D printed cathodes were assembled into half-cell lithium-ion batteries using lithium metal as a reference and counter electrode. Electrochemical cycling of these batteries yielded satisfactory results approaching commercial LiCoO 2 cathodes’ performance, with the potential advantages of additive manufacturing – high surface area anode–cathode configurations for power performance as well as shape conformability.

25 ENERGY STORAGE↗

Microscale Electrochemical Corrosion of Uranium Oxide Particles

Understanding the corrosion of spent nuclear fuel is important for the development of long-term storage solutions. However, the risk of radiation contamination presents challenges for experimental analysis. Adapted from the system for analysis at the liquid–vacuum interface (SALVI), we developed a miniaturized uranium oxide (UO 2 )-attached working electrode (WE) to reduce contamination risk. To protect UO 2 particles in a miniatured electrochemical cell, a thin layer of Nafion was formed on the surface. Atomic force microscopy (AFM) shows a dense layer of UO 2 particles and indicates their participation in electrochemical reactions. Particles remain intact on the electrode surface with slight redistribution. X-ray photoelectron spectroscopy (XPS) reveals a difference in the distribution of U(IV), U(V), and U(VI) between pristine and corroded UO 2 electrodes. The presence of U(V)/U(VI) on the corroded electrode surface demonstrates that electrochemically driven UO 2 oxidation can be studied using these cells. Our observations of U(V) in the micro-electrode due to the selective semi-permeability of Nafion suggest that interfacial water plays a key role, potentially simulating a water-lean scenario in fuel storage conditions. This novel approach offers analytical reproducibility, design flexibility, a small footprint, and a low irradiation dose, while separating the α-effect. This approach provides a valuable microscale electrochemical platform for spent fuel corrosion studies with minimal radiological materials and the potential for diverse configurations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

History-dependent ion transport through conical nanopipettes and the implications in energy conversion dynamics at nanoscale interfaces

The dynamics of ion transport at nanostructured substrate–solution interfaces play vital roles in high-density energy conversion, stochastic chemical sensing and biosensing, membrane separation, nanofluidics and fundamental nanoelectrochemistry. Advancements in these applications require a fundamental understanding of ion transport at nanoscale interfaces. The understanding of the dynamic or transient transport, and the key physical process involved, is limited, which contrasts sharply with widely studied steady-state ion transport features at atomic and nanometer scale interfaces. Here we report striking time-dependent ion transport characteristics at nanoscale interfaces in current–potential (I–V) measurements and theoretical analyses. First, a unique non-zero I–V cross-point and pinched I–V curves are established as signatures to characterize the dynamics of ion transport through individual conical nanopipettes. Moreoever, ion transport against a concentration gradient is regulated by applied and surface electrical fields. The concept of ion pumping or separation is demonstrated via the selective ion transport against concentration gradients through individual nanopipettes. Third, this dynamic ion transport process under a predefined salinity gradient is discussed in the context of nanoscale energy conversion in supercapacitor type charging–discharging, as well as chemical and electrical energy conversion. Our analysis of the emerging current–potential features establishes the urgently needed physical foundation for energy conversion employing ordered nanostructures. The elucidated mechanism and established methodology can be generalized into broadly-defined nanoporous materials and devices for improved energy, separation and sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

08 HYDROGEN↗

Reports From The Frontier: Overcoming Limitations for Pure-water Anion-exchange-membrane Electrolysis

Anion-exchange-membrane electrolysis is positioned to play a key role in the predicted exponential growth of green hydrogen technology with essential R&D advances. We reveal key design parameters essential to commercialization. First, stable alkaline oxygen-evolution reaction catalysts with high electronic conductivity and minimal surface reconstruction during operation must be designed. Alkaline catalyst layers must also be applied to the membrane electrode assembly with scalable, industrially relevant techniques. Second, ionomer oxidation mitigation strategies must be developed. Furthermore, this approach could also target other creative catalyst layer design, such as phase-separation control to protect oxidation-prone organic components or catalyst engineering to direct selectivity for hydroxide over polymer oxidation. If competitive efficiency and durability can be achieved in pure water, AEM electrolysis has the potential to become a dominant electrolyzer technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrasonic transducer with a two-dimensional Gaussian field profile

A transducer is described which generates a two-dimensional Gaussian field by controlling both the position of multiple circular electrodes and the voltage applied to each electrode. The transducer is constructed by depositing concentric rings electrodes onto one flat surface of a circular piezoelectric crystal disk and attaching the rings to an impedance matching network which acts as a voltage divider. Geometrical inter-ring separations and electrical inter-ring impedances are designed to minimize the error between the generated acoustic field, modeled as a piecewise linear function, and the desired Gaussian distribution. Total mean squared error between the averaged far-field data and a Gaussian shape is less than two percent.

Claus, R. O.↗