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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 163 records · Page 9

Synergy of carbonyl and azo chemistries for wide-temperature-range rechargeable aluminum organic batteries

Rechargeable aluminum organic batteries (RAOBs) are promising for developing cost-effective and sustainable energy storage devices due to the low cost, abundance, and high sustainability of aluminum and organic resources. In this study, we designed and synthesized a redox-active polymer bearing carbonyl and azo groups as a cathode material for RAOBs. The polymeric cathode exhibits a high reversible specific capacity, superior cyclic stability, fast charging capability, and a wide operation temperature range (₋40°C to 100°C). X-ray photoelectron spectroscopy (XPS), pair distribution function (PDF) analysis, and soft X-ray absorption near edge structure (XANES) were employed to gain fundamental insight into the carbonyl and azo chemistries in RAOBs, as well as the cathode electrolyte interphase (CEI) structure. We demonstrated a step-by-step alumination/de-alumination reaction for carbonyl and azo groups in the polymer cathode and unraveled a Al 2 O 3⁻ and AlN-rich CEI, which is critical for the impressive performance of RAOBs.

25 ENERGY STORAGE↗

Multilayer screen gives cathode ray tube high contrast

Fabrication method for cathode ray tubes uses low-cost siloxane resin formulations. The resins contain sufficient methyl or phenyl groups for solubility in organic solvents. After vaporization and baking, the polymerized material is stable under vacuum and under temperatures required for tube fabrication.

Bullinger, H.↗

Sustainable Electric Vehicle Batteries for a Sustainable World: Perspectives on Battery Cathodes, Environment, Supply Chain, Manufacturing, Life Cycle, and Policy

Abstract Li‐ion batteries (LIBs) can reduce carbon emissions by powering electric vehicles (EVs) and promoting renewable energy development with grid‐scale energy storage. However, LIB production and electricity generation still heavily rely on fossil fuels at present, resulting in major environmental concerns. Are LIBs as environmentally friendly and sustainable as expected at the current stage? In the past 5 years, a skyrocketing growth of the EV market has been witnessed. LIBs have garnered huge attention from academia, industry, government, non‐governmental organizations, investors, and the general public. Tremendous volumes of LIBs are already implemented in EVs today, with a continuing, exponential growth expected for the years to come. When LIBs reach their end‐of‐life in the next decades, what technologies can be in place to enable second‐life or recycling of batteries? Herein, life cycle assessment studies are examined to evaluate the environmental impact of LIBs, and EVs are compared with internal combustion engine vehicles regarding environmental sustainability. To provide a holistic view of the LIB development, this Perspective provides insights into materials development, manufacturing, recycling, legislation and policy, and beyond. Last but not least, the future development of LIBs and charging infrastructures in light of emerging technologies are envisioned.

36 MATERIALS SCIENCE↗

On Proton Defects and the Phase Transformation of NiO 2

One approach to high-capacity Li-ion battery cathodes is to increase the Ni content. Unfortunately, Ni-rich materials undergo a phase transition and volume collapse at a high state of charge (SOC), which degrades battery performance. At a high SOC, NiO 2 undergoes a phase transition from the O 3 to the O 1 phase. The O 1 phase appears to be more thermodynamically stable than the O 3 phase. However, density functional theory (DFT) often predicts higher stability for O 3 , depending on the DFT approximation. The energy difference between the O 1 and O 3 phases is on the order of 10 meV/atom. Furthermore, we find that proton defects are more stable in the O 1 phase than in the O 3 phase by about 90 meV per proton. Defects in NiO 2 energetically favor the O 3 -O 1 phase transition observed in a high SOC in Li $x$ NiO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Garnet solid electrolyte blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 as high-voltage stable cathodes for advanced lithium-ion batteries

Ni-rich LiNi 1-x Co x/2 Mn x/2 O 2 layered materials have been widely adopted as cathodes for current electric vehicles (EVs) due to their high gravimetric and volumetric energy densities. However, their high-voltage instability (e.g., > 4.3 V vsLi ) limited their usable capacities corresponding to about 60 – 70 % of theoretical capacities. The major problems of high-voltage operation stem from instability of Ni 3+/4+ at cathode-electrolyte interphase (CEI) in contact with electrolytes. Here we propose garnet-type Li 6.7 La 3 Zr 1.7 Ta 0.3 O 12 (LLZT) solid-electrolyte-blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC) as high-voltage stable cathodes. The LLZT not only passivates the CEI but scavenges protons and moisture in electrolytes. From well-balanced ionic and electronic transport properties, 5 wt% LLZT blended NMC cathodes delivered enhanced electrochemical performances in full-cells. Unlike other complicated coating processes, our proposed solid-electrolyte blending approach can be readily implementable in commercial Li-ion batteries due to its manufacturing friendliness, energy saving, and cost effectiveness.

33 ADVANCED PROPULSION SYSTEMS↗

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↗

Impact of Nickel Ions on the Oxygen Reduction Reaction Kinetics of Pt and on Oxygen Diffusion through Ionomer Thin Films

The effects of dissolved nickel on the oxygen reduction reaction (ORR) kinetics and oxygen transport properties of perfluorosulfonic acid (PFSA) thin films were investigated using rotating disk electrode (RDE) measurements of ORR on a PFSA-coated platinum electrode. The electrochemical characterization in 0.1 M perchloric acid (HClO 4 ) with and without added Ni 2+ quantitatively measured the impact of ionic interactions between the Ni 2+ cations and sulfonate (SO 3 - ) anions on oxygen transport through the PFSA thin film. Cyclic voltammetry (CV) curves in deaerated electrolyte showed that Ni 2+ cations diffusing through the PFSA thin film interact with the Pt surface altering the hydrogen underpotential deposition and stripping processes and decreasing ORR kinetics. The RDE limiting current results point to reduced permeability of oxygen through PFSA-Ni 2+ compared to PFSA-H + . Furthermore, the results indicate that transition metals leached from Pt alloy catalyst may be detrimental not only to the intrinsic ORR kinetics of the PEFC cathode catalyst through loss of the ORR-enhancing transition metal, but may also inhibit the diffusion of oxygen to the catalytic sites and poison the ORR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilization of a co-bound intermediate via molecular tuning promotes CO2-to-ethylene conversion

Aspects included herein include an electrolytic system for electrochemical reduction of carbon dioxide, the system comprising: a cathode comprising: a porous gas-diffusion membrane permeable to CO 2 ; an electrocatalyst layer adjacent to a second side of the gas-diffusion membrane; the electrocatalyst layer comprising: an electrically conductive catalyst; and a selectivity-determining organic material attached to at least a portion of the electrically conductive catalyst; wherein: the organic material is formed of a plurality of oligomers; each oligomer comprises a plurality of covalently bonded base units; each base unit comprises at least one heterocyclic group having at least one nitrogen in its structure; and an anion exchange membrane adjacent to the electrocatalyst layer and positioned between the anode and the cathode; wherein anion exchange membrane is characterized by anion conductivity and the cathode is in ionic communication with the anode via the anion exchange membrane.

Agapie, Theodor↗

Calorimetric Study of Mixed Phosphates Na 4 M 3 (PO 4 ) 2 P 2 O 7 (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ) to Evaluate the Electrochemical Trends

Mixed polyanionic compounds have been studied extensively as viable cathode materials for sodium-ion batteries. Mixed phosphates, Na 4 M 3 (PO 4 ) 2 P 2 O 7 (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ), provide a low barrier for Na-ion diffusion, being advantageous in comparison to phosphates and pyrophosphates. The reported order of sodium extraction is ambiguous and remains unclear. Despite being structurally similar, electrochemical performance differs for all four analogues with different degrees of (de)sodiation, according to the transition element present. High-temperature oxide melt solution calorimetry has been used to establish the relation between thermodynamic phase stability and observed capacity for this series of mixed phosphates. Thermodynamic phase stability largely depends on the kind of structure, type of bonding, and size of the cations present. So, according to our results, the thermodynamic phase stability follows the order Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 > Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 > Na 4 Co 3 (PO 4 ) 2 P 2 O 7 > Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 . The thermodynamic studies serve as guidelines for the selection of compositions with the potential for fabricating advanced cathode materials with maximum performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Thermal-Driven Structural and Chemical Degradation of Ni-Rich Layered Cathodes by Co/Mn Exchange

The intrinsic poor thermal stability of layered LiNi x Co y Mn 1-x-y O 2 (NCM) cathodes and the exothermic side reactions triggered by the associated oxygen release are the main safety threats for their large-scale implantation. In NCM family, it is widely accepted that Ni is the stability troublemaker, while Mn has long been considered as a structure stabilizer, whereas the role of Co remains elusive. Here, via Co/Mn exchange in Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 cathode, we demonstrate that, the chemical and structural stability of the deep delithiated NCM cathodes are significantly affected by Co, rather than the widely reported Mn. Operando synchrotron X-ray characterization coupling with in situ mass spectrometry reveal that the Co 4+ reduces prior to the reduction of Ni 4+ , and could thus prolong the Ni migration by occupying the tetrahedra sites, and hence postpone the oxygen release and thermal failure. In contrast, the Mn itself is stable, but barely stabilizes the Ni 4+ . Our results highlight the importance of evaluating the intrinsic role of compositional tuning on Ni-rich/Co-free layered oxide cathode materials to guarantee the safe operation of high-energy Li-ion batteries.

25 ENERGY STORAGE↗

Layered oxide cathode-inspired secondary hard carbon microsphere anode material for high-power and long-life rechargeable batteries

A new anode material that will provide lithium ion (Li-ion) batteries with high energy and power density is urgently needed. In this work, a layered oxide cathode-inspired secondary hard carbon microsphere (CMS) anode material was designed, and exhibited excellent rate performance and long cyclability. Polyacrylonitrile/poly(styrene-co-acrylonitrile) (PAN/SAN) compositions displaying the meatball-like shape of the PAN precursor were carbonized into CMSs having turbostratic microstructures. The CMS carbonized at 1,000°C (CMS1000) displayed high specific capacity at the highest current density of 1,000mAg -1 , i.e., 77.6 % of its average charge capacity at 100 mA g -1 , and considerable cycling retention after 500 cycles, i.e., 83.8 % of the specific capacity at cycle 25. In conclusion, our work demonstrates that the design of new anode materials is a fruitful route to improve commercial Li-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance

Abstract Metal oxides are an important class of functional materials, and for many applications, ranging from solid oxide fuel/electrolysis cells, oxygen permeation membranes, and oxygen storage materials to gas sensors (semiconducting and electrolytic) and catalysts, the interaction between the surface and oxygen in the gas phase is central. Ubiquitous Si‐impurities are known to impede this interaction, commonly attributed to the formation of glassy blocking layers on the surface. Here, the surface oxygen exchange coefficient ( k chem ) is examined for Pr 0.1 Ce 0.9 O 2‐δ (PCO), a model mixed ionic electronic conductor, via electrical conductivity relaxation measurements, and the area‐specific resistance (ASR) by electrochemical impedance spectroscopy. It is demonstrated that even low silica levels, introduced by infiltration, depress k chem by a factor 4000, while the ASR increases 40‐fold and we attribute this to its acidity relative to that of PCO. The ability to fully regenerate the poisoned surface by the subsequent addition of basic Ca‐ or Li‐species is further shown. This ability to not only recover Si‐poisoned surfaces by tuning the relative surface acidity of an oxide surface, but subsequently outperform the pre‐poisoned response, promises to extend the operating life of materials and devices for which the catalytic oxygen/solid interface reaction is central.

30 DIRECT ENERGY CONVERSION↗

Electrochemical-driven green recovery of lithium, graphite and cathode from lithium-ion batteries using water

The expected exponential increase in consumption of lithium-ion batteries (LIBs) would pose a unique challenge to the availability of near-critical resources like lithium and graphite in the upcoming decade. In this work, we present a lithium recovery process that utilizes a degradation mechanism, i.e., lithium plating, as a tool to concentrate metallic lithium at the anode/separator interface for convenient extraction at room temperature – using only water. Electrochemical characterization of fast charged (1–6 C) LIBs yielded a maximum capacity fade of 50% over ten cycles. The lithium plating was confirmed via voltage plateau analysis, coulombic efficiency, and DC resistance measurements. A maximum lithium plating condition was observed to exist between 4C and 5C, thereby limiting the energy consumption in the extraction process. Post-mortem film thickness measurement showed an incrementing film deposition with a maximum of 35 µm thickness. SEM and XPS analysis confirmed increasing concentration of a dense dendritic metallic lithium deposition on the anode/separator interface with C-rate. A green recovery process was adopted to extract the concentrated metallic lithium using distilled water. The lithium from the plated film, solid/electrolyte interface (SEI), electrolyte, anode, and cathode, was extracted as salts. A 37% improvement in lithium recoverability was achieved with fast charging under ambient conditions. XPS analysis showed ~92% of lithium yield with no residual lithium in the graphite. In addition, the battery-grade graphite was recovered with 97% purity after heat treatment of the washed anode film, and concentrated transition metals oxides in the cathode to 93% purity for convenient extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Lithium Local Environments in LiMn 0.5 Ni 0.5 O 2 Cathodes: A DFT-Supported 6 Li Solid-State NMR Study

LiMn 0.5 Ni 0.5 O 2 has been plagued by the structural failure driven by the irreversible phase change upon subsequent cycling and the structural degradation caused by the seemingly unavoidable Li/Ni exchange. This begs for a better understanding of the correlation between lithium local structures, synthesis conditions, and overall electrochemical properties of materials. In this study, we use density functional theory (DFT) to assist experimental 6 Li solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy to understand the nature and change in lithium local structures with extended annealing times (168 vs 15 h) synthesized at 900 °C. To correlate the NMR peak changes after different synthesis conditions, we calculated the NMR spectra of representative low-energy model configurations of LiMn 0.5 Ni 0.5 O 2 composition–zigzag, row, and flower structures–as well as the influence of Ni/Mn ordering and Li/Ni exchange on each spectrum using a supercell that is large enough to allow us to consider the effect of different relative configurations of adjacent transition metal (TM) layers. The analysis based on a combination of the calculated NMR and the experimental spectra suggests that most configurations contributing to the experimental spectra are in fact composed of a blend of configurations higher in energy than the classical well-ordered ground-state structures. Further, the extended annealing of LiMn 0.5 Ni 0.5 O 2 slightly enhances Ni/Mn and Li/Mn orderings while reducing the Li/Ni mixing ratio. This study shows how DFT calculations are crucial in providing a better understanding of the experimental characterization data and therefore local environments and domain structures in oxide materials, such as Li-ion battery cathodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chasing protons in lithium-ion batteries

Parasitic reactions between delithiated cathode materials and non-aqueous electrolytes have been a major barrier that limits the upper cutoff potential of cathode materials. It is of great importance to suppress such parasitic reactions to unleash the high-energy-density potential of high voltage cathode materials. Although major effort has been made to identify the chemical composition of the cathode electrolyte interface using various cutting edge characterization tools, the chemical nature of parasitic reactions remains a puzzle. This severely hinders the rational development of stable high voltage cathode/electrolyte pairs for high-energy density lithium-ion batteries. This report highlights our latest effort in understanding the chemical/electrochemical role of the cathode electrolyte interface using protons as a chemical tracer for parasitic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water production for coffee brewing by electrodeionization

A resin-wafer electrodeionization (RW-EDI) apparatus for purifying water for coffee brewing comprises a cathode; an anode; and multiple porous solid resin wafer exchange units arranged in a stack between the cathode and the anode, and an air distributor adapted and arranged to aerate the water to be purified. Each unit comprises a monovalent cation exchange membrane (CEM), an anion exchange membrane (AEM), and an ion exchange resin wafer between the CEM and the AEM, which is in contact with, and in fluid flow connection with the CEM and AEM. Each resin wafer comprises a cation exchange resin and an anion exchange resin. The units are oriented with the CEM facing the cathode and the AEM facing the anode, with space between the units defining ion concentrate chambers. Bipolar ion exchange membranes separate the anode and cathode from their nearest resin wafer exchange units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

VTO_2021_APR_LLNL_Ye

Traditional batteries are composed of two-dimensional films that are stacked and/or rolled. Thin film batteries display high power density while their thick film counterparts show good energy density, but it has proven difficult to concurrently achieve both within these planar form factors. In addition, conventional Li-ion batteries based on liquid organic electrolytes or gel polymer electrolytes have raised severe safety concerns due to the intrinsic flammable properties of the organic electrolytes. They are also not ideal for the use of high energy density metallic lithium (Li) anodes due to Li dendrite growth, or sulfur cathodes due to shuttling effects that result in fast capacity fade. There is an urgent need to develop safe, high-performance solid-state batteries (SSBs) with advanced electrolyte and separator technologies. Although in recent years a series of superionic conductors have been developed for electrolytes and separators, their performance does not satisfy demanding criteria due to large impedance from poor solid electrolyte-electrode contact and questionable electrochemical and mechanical stability. Unlike the well-established roll-to-roll fabrication of conventional Li-ion batteries, the processing of SSBs is unique due to the brittleness of solid-state electrolytes (SSEs). The commercially available or lab-developed SSE discs are usually very thick (hundreds of micrometers to millimeters) to overcome their brittle nature, which unfortunately increases the cell impedance and accounts for the majority of the overall cell weight and volume, leading to dramatically decreased power and energy densities. In this project, we will investigate 3D printing techniques to overcome safety, fabrication, mechanical, and electrochemical issues in SSBs. 3D printing builds complex structures in a layer-by-layer fashion, which allows rapid production of hierarchical architectures, gradient and multi-material structures, and multi-component assemblies. 3D printing is an emerging area that could fundamentally transform energy storage devices. For example, 3D printing can produce batteries with arbitrary form factors to fit a product’s specific volume requirements and can create interwoven electrode arrangements over a wide range of length scales to improve transport and increase power density for a given energy density. For SSBs, 3D printing may dramatically reduce the separator thickness from ~1 mm (by hydraulic pressing) to tens of micrometers or less. In addition, the interfacial contact area between the electrolyte and the electrode may be increased via 3D interdigitated designs. Hence, we expect a significant reduction of the overall cell impedance and enhancement of both energy and power densities of SSBs by harnessing an array of 3D printing technologies being developed at Lawrence Livermore National Laboratory (LLNL).

25 ENERGY STORAGE↗

Electrolytic pretreatment of urine

Electrolysis has been under evaluation for several years as a process to pretreat urine for ultimate recovery of potable water in manned spacecraft applications. The conclusions that were drawn from this investigation are the following: (1) A platinum alloy containing 10 percent rhodium has been shown to be an effective, corrosion-resistant anode material for the electrolytic pretreatment of urine. Black platinum has been found to be suitable as a cathode material. (2) The mechanism of the reactions occurring during the electrolysis of urine is two-stage: (a) a total Kjeldahl nitrogen and total organic carbon (TOC) removal in the first stage is the result of electrochemical oxidation of urea to CO2, H2O, and ammonia followed by chloride interaction to produce N2 from ammonia, (b) after the urea has been essentially removed and the chloride ions have no more ammonia to interact with, the chloride ions start to oxidize to higher valence states, thus producing perchlorates. (3) Formation of perchlorates can be suppressed by high/low current operation, elevated temperature, and pH adjustment. (4) UV-radiation showed promise in assisting electrolytic TOC removal in beaker tests, but was not substantiated in limited single cell testing. This may have been due to non-optimum configurations of the single cell test rig and the light source.

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