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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Nanoscale Measurements of Charge Transfer at Cocatalyst/Semiconductor Interfaces in BiVO 4 Particle Photocatalysts

Semiconductor photocatalyst particles convert solar energy to fuels like H 2 . The particles are often assumed to provide crystalline-facet-dependent electron-hole separation. A common strategy is to deposit HER electrocatalyst on electron-selective facets and OER electrocatalyst on hole-selective facets. A precise understanding of how charge-carrier-selective contacts emerges and how they rationally designed, however, is missing. Using a combination of ex-situ and in-situ conducting-AFM experiments and new ionomer/catalyst-semiconductor test structures, we show how heterogeneity in charge-carrier selectivity can be measured at the nanoscale. We discover that the presence of interface water/electrolyte is critical to induce hole selectivity between the CoO x water-oxidation catalyst and the BiVO 4 light absorber. pH-dependent measurements suggest that negative surface charge on the semiconductor is central to inducing hole selectivity. Furthermore, the work also demonstrates a new approach to control local pH and introduce water using thin-film ionomers compatible with conductive-AFM measurements.

14 SOLAR ENERGY↗

DOE OSTI2025

High Throughput Solvent-free Manufacturing of Battery Electrodes

The project goal is to develop and demonstrate an advanced solvent-free lithium-ion battery electrode process through proposed Advanced Dry Electrode Process (ADEP) equipment, which is expected to exhibit a better binder fibrillization and high throughput and suitable for high performance electrode manufacturing, and commonize the anode and cathode dry processing equipment, supply chain and operation for lithium-ion battery OEMs for replacing the solvent-based slurry casting. Our proposed approach will facilitate low-cost battery production by addressing the following gaps in present dry electrode processing: • Extend the dry electrode fabrication process to lithium-ion battery anode manufacturing • Increase the active material content for anodes and cathodes • Intensify the process through improved mixing, powder rheology and surface modifications • Enable processing of next-generation electrode materials that are not stable to solvent or ambient air exposure. The project objectives include the development of anode-compatible binder and binder fibrillization promoter for low irreversible capacity loss, low electrode binder content yet higher film mechanical strength, and the optimization of solvent-free anode and cathode process for low cost (>60% electrode cost reduction), high performance (10% increase in energy density without sacrificing cycle life) and high throughput to enable next generation lithium-ion battery electrode production. Solvent-free electrode manufacturing will also enable next-generation cell designs based on prelithiated anodes or solid-state electrolytes.

25 ENERGY STORAGE↗

DOE OSTI2024

Ameliorating the sodium storage performance of hard carbon anode through rational modulation of binder

Hard carbon anodes have emerged as promising candidates for sodium-ion batteries due to their inherent advantages. Nevertheless, the surface imperfections in these materials often culminate in irreversible electrolyte consumption, fostering the development of a heterogeneous and fragile solid electrolyte interface (SEI), thereby compromising the initial Coulombic efficiency (ICE). Here, drawing inspiration from the catalytic potential of C=O (carbonyl) bonds in directing preferential salt reduction, we introduce a novel strategy that leverages the modulation of the binder, a long-term overlooked pivotal components in the electrode process. Specifically, Polymethyl methacrylate (PMMA), abundant in C=O groups, is partially substituted for PVDF, ensuring robust adhesion of the electrode material to the current collector while preserving superior mechanical properties. The accurate combination of two binders with delightful compatibility in the state-of-art electrode process, can promote a uniform formation of the SEI on the hard carbon surface enriched in inorganic components, which can ensure long-term interfacial stability and suppresses excessive solvent decomposition and facilitates Na + transfer at the interface. Consequently, the initial Coulombic efficiency of the hard carbon anode with 70 %PMMA binder achieves 86 %, with prominent cycling stability (88 % capacity retention over 500 cycles) at a high current density of 1.2 A g −1 . When paired with high loading cathodes to assemble the pouch cell, it also demonstrates stable operational scenarios.

25 ENERGY STORAGE↗

NASA NTRS2010

NASA Tech Briefs, January 2010

Topics covered include: Cryogenic Flow Sensor; Multi-Sensor Mud Detection; Gas Flow Detection System; Mapping Capacitive Coupling Among Pixels in a Sensor Array; Fiber-Based Laser Transmitter for Oxygen A-Band Spectroscopy and Remote Sensing; Low-Profile, Dual-Wavelength, Dual-Polarized Antenna; Time-Separating Heating and Sensor Functions of Thermistors in Precision Thermal Control Applications; Cellular Reflectarray Antenna; A One-Dimensional Synthetic-Aperture Microwave Radiometer; Electrical Switching of Perovskite Thin-Film Resistors; Two-Dimensional Synthetic-Aperture Radiometer; Ethernet-Enabled Power and Communication Module for Embedded Processors; Electrically Variable Resistive Memory Devices; Improved Attachment in a Hybrid Inflatable Pressure Vessel; Electrostatic Separator for Beneficiation of Lunar Soil; Amorphous Rover; Space-Frame Antenna; Gear-Driven Turnbuckle Actuator; In-Situ Focusing Inside a Thermal Vacuum Chamber; Space-Frame Lunar Lander; Wider-Opening Dewar Flasks for Cryogenic Storage; Silicon Oxycarbide Aerogels for High-Temperature Thermal Insulation; Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C; Designs and Materials for Better Coronagraph Occulting Masks; Fuel-Cell-Powered Vehicle with Hybrid Power Management; Fine-Water-Mist Multiple-Orientation-Discharge Fire Extinguisher; Fuel-Cell Water Separator; Turbulence and the Stabilization Principle; Improved Cloud Condensation Nucleus Spectrometer; Better Modeling of Electrostatic Discharge in an Insulator; Sub-Aperture Interferometers; Terahertz Mapping of Microstructure and Thickness Variations; Multiparallel Three-Dimensional Optical Microscopy; Stabilization of Phase of a Sinusoidal Signal Transmitted Over Optical Fiber; Vacuum-Compatible Wideband White Light and Laser Combiner Source System; Optical Tapers as White-Light WGM Resonators; EPR Imaging at a Few Megahertz Using SQUID Detectors; Reducing Field Distortion in Magnetic Resonance Imaging; Fluorogenic Cell-Based Biosensors for Monitoring Microbes; A Constant-Force Resistive Exercise Unit; GUI to Facilitate Research on Biological Damage from Radiation; On-Demand Urine Analyzer; More-Realistic Digital Modeling of a Human Body; and Advanced Liquid-Cooling Garment Using Highly Thermally Conductive Sheets.

Source record↗

DOE OSTI2023

Conjugated Imine Polymer Synthesized via Step‐Growth Metathesis for Highly Stable Silicon Nanoparticle Anodes in Lithium‐Ion Batteries

Abstract This work reports a new method to synthesize polyphenylmethanimine (polyPMI) as a linear or a hyperbranched, conjugated polymer using an aldehyde‐imine metathesis reaction. This work details the reaction mechanisms of this polymerization by characterizing a red‐shift in its absorption spectrum as polymer conjugation length increases and verifies that this optical shift results from extended π‐condensation using density functional theory. This new synthetic approach provides a polymer that can potentially be depolymerized for facile recyclability and is compatible with air‐ and water‐sensitive chemistries. As an example of the utility of this new approach, this work demonstrates that this polymer can be directly grown on silicon nanoparticles to create silicon anodes for lithium‐ion batteries with a high degree of electrochemical interfacial passivation. These silicon anodes exhibit Coulombic efficiencies above 99.9% and can accommodate silicon nanoparticle expansion and contraction during lithiation and delithiation as demonstrated by stable reversible capacities for 500 cycles. Finally, this work demonstrates that polyPMI facilitates the formation of a lithium fluoride rich solid electrolyte interphase that remains chemically and mechanically stable after long term cycling.

25 ENERGY STORAGE↗

NASA NTRS2008

Progress in Development of Improved Ion-Channel Biosensors

Further improvements have recently been made in the development of the devices described in Improved Ion-Channel Biosensors (NPO-30710), NASA Tech Briefs, Vol. 28, No. 10 (October 2004), page 30. As discussed in more detail in that article, these sensors offer advantages of greater stability, greater lifetime, and individual electrical addressability, relative to prior ion-channel biosensors. In order to give meaning to a brief description of the recent improvements, it is necessary to recapitulate a substantial portion of the text of the cited previous article. The figure depicts one sensor that incorporates the recent improvements, and can be helpful in understanding the recapitulated text, which follows: These sensors are microfabricated from silicon and other materials compatible with silicon. Typically, the sensors are fabricated in arrays in silicon wafers on glass plates. Each sensor in the array can be individually electrically addressed, without interference with its neighbors. Each sensor includes a well covered by a thin layer of silicon nitride, in which is made a pinhole for the formation of a lipid bilayer membrane. In one stage of fabrication, the lower half of the well is filled with agarose, which is allowed to harden. Then the upper half of the well is filled with a liquid electrolyte (which thereafter remains liquid) and a lipid bilayer is painted over the pinhole. The liquid contains a protein that forms an ion channel on top of the hardened agarose. The combination of enclosure in the well and support by the hardened agarose provides the stability needed to keep the membrane functional for times as long as days or even weeks. An electrode above the well, another electrode below the well, and all the materials between the electrodes together constitute a capacitor. What is measured is the capacitive transient current in response to an applied voltage pulse. One notable feature of this sensor, in comparison with prior such sensors, is a relatively thick dielectric layer between the top of the well and the top electrode. This layer greatly reduces the capacitance of an aperture across which the ion channels are formed, thereby increasing the signal-to-noise ratio. The use of a relatively large aperture with agarose support makes it possible to form many ion channels instead of only one, thereby further increasing the signal-to-noise ratio and effectively increasing the size of the available ionic reservoir. The relatively large reservoir makes it possible to measure AC rather than DC. This concludes the recapitulation from the cited previous article.

Nadeau, Jay L.↗

DOE OSTI2021

Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

The drive to reduce consumption of fossil resources, coupled with expanding capacity for renewable electricity, invites the exploration of new routes to utilize this energy for the sustainable production of fuels, chemicals, and materials. Biomass represents a possible source of platform precursors for such commodities due to its inherent ability to fix CO2 in the form of multi-carbon organic molecules. Electrochemical methods for the valorization of biomass are thus intriguing, but there is a need to objectively evaluate this field and define the opportunity space by identifying pathways suited to electrochemistry. In this contribution we offer a comprehensive, critical review of recent advances in low-temperature (liquid phase), electrochemical reduction and oxidation of biomass-derived intermediates (polyols, furans, carboxylic acids, amino acids, and lignin), with emphasis on identifying the state-of-the-art for each documented reaction. Progress in computational modeling is also reviewed. We further suggest a number of possible reactions that have not yet been explored but which are expected to proceed based on established routes to transform specific functional groups. We conclude with a critical discussion of technological challenges for scale-up, fundamental research needs, process intensification opportunities (e.g., by pairing compatible oxidations and reductions), and new benchmarking standards that will be necessary to accelerate progress toward application in this still-nascent field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Anion sublattice design enables superionic conductivity in crystalline oxyhalides

Solid-state batteries are attractive energy storage systems as a result of their inherent safety, but their development hinges on advanced solid-state electrolytes (SSEs). Most SSEs remain largely confined to single-anion systems (e.g., sulfides, oxides, halides, and polymers). Through mixed-anion design strategy, we develop crystalline Li 3 Ta 3 O 4 Cl 10 (LTOC) and its derivatives with excellent ionic conductivities (up to 13.7 millisiemens per centimeter at 25°C) and electrochemical stability. The LTOC structure features mixed-anion spiral chains, consisting of corner-shared oxygen and terminal chlorine atoms, which induces continuous “tetrahedron-tetrahedron” Li-ion migration pathways with low energy barriers. Additionally, LTOC demonstrates holistic cathode compatibility, enabling solid-state batteries operation at 4.9 volts versus Li/Li + and low temperature, down to −50°C. In conclusion, these findings describe a promising class of superionic conductors for high-performance solid-state batteries.

Zhao, Feipeng [Western University, London, ON (Can↗

DOE OSTI2021

Multimodal imaging of oil-in-water bilgewater emulsion and biofilms

Bilgewater emulsions, consisting of oil and surfactant mixtures in water, affect many aquatic species. Thus development of methods and techniques to treat or mitigate the formation and undesired consequences of shipboard emulsions are urgently needed. This work presents new results of the evolution of the bilgewaer chemical and physical properties using in situ imaging. A Navy O/W emulsion consisting of three oils and a detergent mixture was used as the synthetic bilgewater model [1, 2]. Synthetic oil-in-water (O/W) emulsion droplets were seled in a vacuum compatible microfluidic sample holder and imaged using a suite of tools including scanning electron microscopy (SEM), time-of-flight secondary ion mass spectrometry (ToF-SIMS), confocal laser scanning microscopy, and optical microscopy, highlighting the advantage of multiscale analysis and its applications in waste reduction and treatment in the environment. The transferrable and vacuum compatible microfluidic interface, System for Analysis at the Liquid Vacuum Interface (SALVI), was used in this study. SALVI enabled surface analysis of liquids and liquid-solid interactions using ToF-SIMS and SEM [3, 4]. Its detection window is an aperture of 2 ?m in diameter open to vacuum, permitting direct detection of the liquid surface. Liquid is withheld by surface tension within the aperture. The interface is composed of a silicon nitride membrane and polydimethylsiloxane microchannel [3, 4]. A variety of samples including complex liquid mixtures, ionic liquids, single mammalian cells, live biofilms, and solid-electrolyte interface have been analyzed using in situ imaging [5, 6]. The feasibility of using SALVI for in situ SEM imaging of nanoparticles and colloids in liquid was recently demonstrated [7]. This paper shows new findings of multimodal imaging and analysis of synthesized emulsion particles in water. Figure 1 depicts a schematic of multimodal in situ imaging of bilgewater emulsion using SEM and ToF-SIMS. Furthermore, we study the interactions of microbes and bilgewater emulsion. Microbes play an important role in the ocean. We hypothesize that microbes release organics that can act as surfactants that affect bilgewater formation or weakening. We present the first systematic study of emulsions and biofilms and investigate the effects of biofilms on bilgewater emulsions. Pseudomonas was selected as a model strain. Biofilms were cultured in a microchannel to allow culture [8]. Once a thick layer of biofilms was formed, the medium solution was changed to a mixture consisting of 50 % bilgewater emulsion. Dispersed biofilms were collected at 24 hrs. and 48 hrs. after emulsions were introduced into the channel. Bilgewater emulsions, biofilms, and mixtures of bilgewater emulsions and biofilms were analyzed using multiple in situ and ex situ techniques as described earlier. Our findings indicate that biofilms change the chemical makeup of the emulsion surface compositions and emulsion droplet size distribution, confirming the hypothesis that extracellular polymeric substance (EPS) related components released from biofilms can function as surfactants and change the oil-in-water interfaces.

bilgewater, multimodal imaging, biofilms↗

NASA NTRS1984

NASA's plans for life sciences research facilities on a Space Station

A Life Sciences Research Facility on a Space Station will contribute to the health and well-being of humans in space, as well as address many fundamental questions in gravitational and developmental biology. Scientific interests include bone and muscle attrition, fluid and electrolyte shifts, cardiovascular deconditioning, metabolism, neurophysiology, reproduction, behavior, drugs and immunology, radiation biology, and closed life-support system development. The life sciences module will include a laboratory and a vivarium. Trade-offs currently being evaluated include (1) the need for and size of a 1-g control centrifuge; (2) specimen quantities and species for research; (3) degree of on-board analysis versus sample return and ground analysis; (4) type and extent of equipment automation; (5) facility return versus on-orbit refurbishment; (6) facility modularity, isolation, and system independence; and (7) selection of experiments, design, autonomy, sharing, compatibility, and integration.

Arno, R.↗

DOE OSTI2020

Developing the Next Generation of High-Performance Solid-State Batteries

The project team conducted cutting-edge battery research on electrode materials, electrolyte formulations, and cell designs for next-generation rechargeable lithium metal batteries designed for high energy density and safety. The research has focused on two separate but related technologies: 1) a high-temperature lithium metal battery designed for extreme environments, and 2) a high-energy lithium metal battery designed for more general applications (including aerospace, defense, transportation, electronics, etc.). We took these projects from the conceptual stage (an idea on paper) all the way to high performing lab prototypes and early commercial-format pouch and cylindrical cell prototypes. Both chemistries were improved substantially in terms of materials compatibility, lithium metal cyclability, high-voltage stability, high-temperature stability, and scalability.

25 ENERGY STORAGE↗

NASA NTRS2009

Evaluation of Carbon Dioxide Sensors for the Constellation Space Suit Life Support System for Surface Exploration

This paper presents the findings of the trade study to evaluate carbon dioxide (CO2) sensing technologies for the Constellation (Cx) space suit life support system for surface exploration. The trade study found that nondispersive infrared absorption (NDIR) is the most appropriate high Technology Readiness Level (TRL) technology for the CO2 sensor for the Cx space suit. The maturity of the technology is high, as it is the basis for the CO2 sensor in the Extravehicular Mobility Unit (EMU). The study further determined that while there is a range of commercial sensors available, the Cx CO2 sensor should be a new design. Specifically, there are light sources (e.g., infrared light emitting diodes) and detectors (e.g., cooled detectors) that are not in typical commercial sensors due to cost. These advanced technology components offer significant advantages in performance (weight, volume, power, accuracy) to be implemented in the new sensor. The exact sensor design (light source, transmitting optics, path length, receiving optics and detector) will be specific for the Cx space suit and will be determined by the performance requirements of the Cx space suit. The paper further identifies specifications for some of the critical performance parameters as well as discussing the engineering aspects of implementing the sensor into the Portable Life Support System (PLSS). The paper then presents testing results from three CO2 sensors with respect to issues important to Extravehicular Activity (EVA) applications; stability, humidity dependence and low pressure compatibility. The three sensors include two NDIR sensors, one commercial and one custom-developed by NASA (for a different purpose), and one commercial electrochemical sensor. The results show that both NDIR sensors have excellent stability, no dependence on ambient humidity (when the ambient temperature is above the dew point) and operate in low pressure conditions and after being exposed to a full vacuum. The commercial electrochemical sensor was not suitable for the Cx space suit for surface exploration. Finally, the paper identifies a number of techniques currently under development that offer significant advantages for EVA applications. These include miniaturized, room temperature, solid electrolyte systems and advanced optical detectors.

Dietrich, Daniel L.↗

DOE OSTI2023

Electrochemical Reduction of Flue Gas Carbon Dioxide to Commercially Viable C2-C4 Products (Final Report)

This is the final scientific/technical report for a DOE project focused on the electrochemical conversion of CO 2 in non-aqueous solvents to novel products. Electrochemical reduction of CO 2 provides an attractive route to produce valuable fuels and chemicals that can simultaneously lower greenhouse gas emissions when powered by renewable electricity. While recent technological advances have shown the feasibility of industrial CO 2 electroreduction, many challenges remain to improve this technology and expand the list of economically viable products. The vast majority of electrochemical CO 2 reduction research has been conducted in aqueous media under neutral to alkaline conditions, leading to commonly reported products including carbon monoxide, formic acid, methane, methanol, ethylene, acetic acid, and ethanol. In comparison, non-aqueous media for CO 2 reduction has been underexplored but represents a possible avenue to yield new products and improved operating conditions. The aim of the project was to convert waste CO 2 in the form of flue gas to a multicarbon C2 - C4 chemical product in a reactor designed to achieve economically competitive values of current density and selectivity. The project strived to advance the technology readiness of an electrochemical CO 2 reduction process in alcohol solvents from the proof-of-concept stage to a device capable of meeting performance metrics for commercial viability. In the initial plan, the University of Louisville researchers were to focus on investigating the electrochemical process and improving the faradaic efficiency for novel C2 – C4 species, while also working on a parallel effort to build a practical electrolysis reactor to markedly increase the CO 2 reduction current density. The reactor development effort also aimed to engineer a dual-electrolyte feed strategy with non-aqueous catholyte and aqueous anolyte to promote water oxidation as the coupling anodic half-reaction to enable a sustainable and economical overall process. At the outset, the University of North Dakota was to investigate the feasibility of operating directly from coal-derived flue gas without separate capture and purification. The research team sought to determine impurity effects and test mitigation strategies, as well as engineer the gaseous feed system for high reactor tolerance to lower CO 2 concentration. In the last half year of the project, the focus was planned to shift to integrating the advances in the catalysis, electrochemical conditions, reactor design, and flue gas compatibility into a fully functional device and improve it for maximum current density and faradaic efficiency for C2 – C4 species. Knowledge of the full system components, constraints, and maximum performance was then to be used as the basis for a thorough technoeconomic analysis (TEA) and life cycle analysis (LCA) at the end of the project.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2022

Long–Cycling Sulfide–Based All–Solid–State Batteries Enabled by Electrochemo–Mechanically Stable Electrodes

Anode significantly determines the energy density of all-solid-state Lithium batteries (ASLBs). Silicon (Si) and Lithium (Li) metal are two of the most attractive anodes because of their ultrahigh theoretical capacities. However, most investigations focus on Li metal; the great potential of Si is underrated. This study investigates Si anode's stability, processability, and cost in ASLBs and compares them with Li metal. Moreover, the single-crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 is stabilized with a lithium silicate (Li 2 SiO x ) through a scalable sol-gel method. ASLBs with a cell-level energy density of 285 Wh kg -1 are obtained through sandwiching Si anode, thin sulfide solid-state electrolyte membrane, and interface stabilized LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The full cell delivered a high capacity of 145 mAh g -1 at C/3 and maintained stability for 1000 cycles. This work inspires commercializing the ASLBs on a large scale with exciting manufacturing lines for large-scale, safe, and economical energy storage.

25 ENERGY STORAGE↗

DOE OSTI2023

Diamonds in the Rough: Direct Surface Enhanced Infrared Spectroscopic Evidence of Nitrogen Reduction on Boron-Doped Diamond Supported Metal Catalysts

In situ investigations of electrocatalytic processes of increasing societal interest such as the nitrogen reduction reaction (NRR) re-quire aggressive experimental conditions that are not readily compatible with surface sensitive techniques such as attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). A method for performing ATR-SEIRAS studies at very negative potentials where conventional IR-active films delaminate, and fail is reported. The method relies on a thin film of very robust boron-doped diamond deposited on a micromachined Si wafer, which provides extended mid-IR transparency at long wavelengths. SEIRAS activity is achieved by electrodepositing gold nanoparticles onto the conductive BDD layer. The Au@BDD layers are shown to sustain prolonged periods of electrolysis at negative potentials with no degradation of the modifying layer. The efficacy of these substrates for electrocatalysis is demonstrated by studying the reduction of N 2 at -1.5 V vs Ag/AgCl in an aqueous-based electrolyte. So under these conditions, direct spectroscopic evidence of both NH 3 and hydrazine formed from the nitrogen reduction reaction (NRR) is provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Accurate simulation of surfaces and interfaces of ten FCC metals and steel using Lennard–Jones potentials

Abstract The earlier integration of validated Lennard–Jones (LJ) potentials for 8 fcc metals into materials and biomolecular force fields has advanced multiple research fields, for example, metal–electrolyte interfaces, recognition of biomolecules, colloidal assembly of metal nanostructures, alloys, and catalysis. Here we introduce 12-6 and 9-6 LJ parameters for classical all-atom simulations of 10 further fcc metals (Ac, Ca (α), Ce (γ), Es (β), Fe (γ), Ir, Rh, Sr (α), Th (α), Yb (β)) and stainless steel. The parameters reproduce lattice constants, surface energies, water interfacial energies, and interactions with (bio)organic molecules in 0.1 to 5% agreement with experiment, as well as qualitative mechanical properties under standard conditions. Deviations are reduced up to a factor of one hundred in comparison to earlier Lennard–Jones parameters, embedded atom models, and density functional theory. We also explain a quantitative correlation between atomization energies from experiments and surface energies that supports parameter development. The models are computationally very efficient and applicable to an exponential space of alloys. Compatibility with a wide range of force fields such as the Interface force field (IFF), AMBER, CHARMM, COMPASS, CVFF, DREIDING, OPLS-AA, and PCFF enables reliable simulations of nanostructures up to millions of atoms and microsecond time scales. User-friendly model building and input generation are available in the CHARMM-GUI Nanomaterial Modeler. As a limitation, deviations in mechanical properties vary and are comparable to DFT methods. We discuss the incorporation of reactivity and features of the electronic structure to expand the range of applications and further increase the accuracy.

Kanhaiya, Krishan (ORCID:0000000236222655)↗

NASA NTRS2024

Plasma Rapid Oxidation Technique for Extending Component Tenability (PROTECT)

Additive manufacturing (AM) is increasingly utilized in aerospace applications. However, post-processing is required for many applications, so intricate designs are limited. Plasma electrolytic oxidation (PEO) was investigated as a post-processing treatment on Ti-6-4 (or Ti-6Al-4V: Alpha-beta titanium alloy with a high specific strength and excellent corrosion resistance)additively manufactured specimens. The “Keronite Black” PEO treatment reduced the surface roughness (Ra) of test specimens by approximately 0.5 μm. This reduction in Ra compared to the as-printed sample was hypothesized to benefit corrosion and fatigue properties because increased Ra is known to negatively impact corrosion and fatigue characteristics. Up to a 101% improvement in the corrosion potential (Ɛcorr) was observed. Although fatigue characteristics varied by PEO parameters, there was no significant fatigue debit due to the PEO treatment. Additionally, no effect to adhesion characteristics was observed due to PEO treatment. It is recommended that additional studies investigate the ability of PEO treatments to improve the corrosion, fatigue, chemical compatibility, radiation hardening, particle shedding characteristics, and flammability/oxidizer compatibility of aerospace additively manufactured components.

Jennifer Williams↗

DOE OSTI2021

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Conspectus (Photo)electrochemical energy conversion is important in the development of a carbon-neutral energy economy because it can provide a pathway for mitigating the intermittency of renewable energy sources such as wind and solar. In order to operate efficiently, these technologies, which include photoelectrochemical cells, water and CO 2 electrolyzers, fuel cells, and redox flow batteries, require fast charge transfer kinetics at the electrode/electrolyte interface as well as robust ion management in the electrolyte. In conventional electrolyzers and fuel cells, the electrolyte is strongly acidic or basic and ionic current is carried by H + or OH – ions. In contrast, photoelectrodes and electrocatalysts for water splitting are often studied in buffered solutions. The question of ion balance in these systems led us to analyze the polarization losses due to ion concentration gradients in cells that employed various buffer–membrane combinations. Continuously driving the buffer ions across an ionomer membrane not only lowers the buffer capacity of an aqueous electrolyte but also introduces pH gradients that result in significant energy losses. To address the problem, we and other groups have studied the use of reverse-biased bipolar membranes (BPMs) in (photo)electrolytic cells. BPMs consist of an anion exchange layer (AEL) laminated with a cation exchange layer (CEL) and are usually equipped with a catalytic layer in between to accelerate the water dissociation reaction. At the AEL/CEL interface, water dissociates into protons and hydroxide ions, which replenish those consumed at the cathode and anode. Compared to conventional water electrolyzers with proton/anion exchange membranes (PEM/AEM), BPM electrolyzers provide the unique advantage of continuously operating the cathode and anode under different pH conditions, which is desirable when the two electrode reactions have different pH requirements. BPMs also enable the use of buffered electrolytes at pH values that are optimized for electrode stability and product selectivity in applications such as CO 2 electrolysis. Product crossover losses and CO 2 pumping can be dramatically reduced in BPM-based CO 2 electrolyzers, relative to conventional alkaline membranes, by electrostatic repulsion (of anionic products) and electroosmotic drag (for neutral products). BPM-based gas fed CO 2 electrolyzers can achieve high current density, but they suffer from low Faradaic efficiency (FE) due to the acidic local environment of the CEL. This problem can be mitigated by adding an aqueous buffering layer or by creating a weak acid cation exchange film on the CEL face of the membrane. The use of BPMs in fuel cells and redox flow batteries offers some interesting advantages. Configurations with both reverse and forward bias have been studied, but forward bias has been favored due to material compatibility, reaction kinetics, and thermodynamic considerations. The net reaction at the AEL/CEL interface is the acid–base neutralization reaction, which has a high inherent reaction rate constant, but in the BPM is limited to a nanometric space-charge layer and requires efficient catalysis to achieve high current density. Understanding the mechanism of the acid–base neutralization and the opposite process, the water dissociation reaction, will be essential for improving the performance of forward-biased BPMs. In conclusion, this Account reviews our current understanding of the working mechanisms of BPMs and discusses how we can use them to effectively manage ions for various (photo)electrochemical applications.

Yan, Zhifei↗