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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Controlling swelling in mixed transport polymers through alkyl side-chain physical cross-linking

Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

In-situ visualization of the transition metal dissolution in layered cathodes

Transition metal dissolution in layered cathodes is one of the most intractable issues that deteriorates the battery performance and lifetime. It not only aggravates the structure degradation in cathode, but also damages the solid electrolyte interphase in anode and even induce the formation of lithium dendrites. In this work, we investigate the dissolution behaviors of polycrystalline and single-crystalline layered cathode via operando X-ray imaging techniques. The described cathode particle morphology appears to have a significant impact on the evolution of the dissolution dynamics. As a mitigation strategy, we reveal that doping with trace amount of Zr in the layered cathode could improve its robustness against the transition metal dissolution. Our finding provides valuable insights for designing the next-generation highly-stable layered battery cathodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Carbon Utilization: Electrochemical Approach Using Novel Catalyst and System Integration

The environmental footprint from power generation can be mitigated by capturing emitted carbon dioxide (CO2) and converting it to value-added fuel sources. A multitude of different fuels can be produced from CO2 depending on the chemical reaction catalysts. Typically, these pathways can be developed electrochemically, or through hydrogenation. In recent years the electrochemical reduction of CO2 has grown exponentially, as it has shown potential to decrease atmospheric pollution and provide an additional means of on-demand electricity storage. Formic acid (FA) in particular has industrial applications such as in fuel cells or as a hydrogen storage medium, and requires a lower thermodynamic energy input than any other fuel produced for electrochemical CO2 reduction. However, product selectivity remains a challenge for conventional electrocatalysts, making FA production efficiencies above 50% difficult. To address the challenge of catalytic selectivity, UK CAER employs enzymatic catalysts to facilitate the FA production and minimize unwanted byproducts. Our process couples the catalyst with a charge mediator which is necessary to shuttle electrons, and an electrolyte pH buffer to prevent the catalyst from degrading. Presently, production efficiencies have approached 60% at a rate of over 10 mM FA/hour. System design considerations (flow rate, bulk volume) will also be discussed.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2012

Prognostics of Power Electronics, Methods and Validation Experiments

Abstract Failure of electronic devices is a concern for future electric aircrafts that will see an increase of electronics to drive and control safety-critical equipment throughout the aircraft. As a result, investigation of precursors to failure in electronics and prediction of remaining life of electronic components is of key importance. DC-DC power converters are power electronics systems employed typically as sourcing elements for avionics equipment. Current research efforts in prognostics for these power systems focuses on the identification of failure mechanisms and the development of accelerated aging methodologies and systems to accelerate the aging process of test devices, while continuously measuring key electrical and thermal parameters. Preliminary model-based prognostics algorithms have been developed making use of empirical degradation models and physics-inspired degradation model with focus on key components like electrolytic capacitors and power MOSFETs (metal-oxide-semiconductor-field-effect-transistor). This paper presents current results on the development of validation methods for prognostics algorithms of power electrolytic capacitors. Particularly, in the use of accelerated aging systems for algorithm validation. Validation of prognostics algorithms present difficulties in practice due to the lack of run-to-failure experiments in deployed systems. By using accelerated experiments, we circumvent this problem in order to define initial validation activities.

Kulkarni, Chetan S.↗
DOE OSTI2022

Differences in the Interfacial Mechanical Properties of Thiophosphate and Argyrodite Solid Electrolytes and Their Composites

Interfacial mechanics are a significant contributor to the performance and degradation of solid-state batteries. Spatially resolved measurements of interfacial properties are extremely important to effectively model and understand the electrochemical behavior. Herein, we report the interfacial properties of thiophosphate (Li 3 PS 4 )- and argyrodite (Li 6 PS 5 Cl)-type solid electrolytes. Using atomic force microscopy, we showcase the differences in the surface morphology as well as adhesion of these materials. Additionally we investigate solvent-less processing of hybrid electrolytes using UV-assisted curing. Physical, chemical, and structural characterizations of the materials highlight the differences in the surface morphology, chemical makeup, and distribution of the inorganic phases between the argyrodite and thiophosphate solid electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Stabilizing and understanding the interface between nickel-rich cathode and PEO-based electrolyte by lithium niobium oxide coating for high-performance all-solid-state batteries

The pursuit of high energy density and safe lithium ion batteries (LIBs) is the urgent goal for the development of next-generation electric vehicles (EVs). All-solid-state batteries (ASSBs) with the combination of poly(ethylene oxide) (PEO)-based solid polymer electrolyte (SPE) and Ni-rich lithium nickel manganese cobalt oxide LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode are promising candidates for EVs due to their improved energy density and safety. However, the low electrochemical oxidation window of PEO-based SPE and the instability of NMC811 at the charge/discharge process seriously restrict the battery performance. Herein, a high voltage stable solid-state electrolyte layer lithium niobium oxide (LNO) is coated on the NMC811 electrode surface by atomic layer deposition for stabilizing NMC811-PEO solid polymer batteries. Electrochemical tests show that LNO coating can stabilize the NMC811 active materials and mitigate the decomposition of SPE upon the cycling process, rendering a good performance of NMC811-PEO solid polymer battery. Mechanism studies by SEM, STEM, XAS, and XPS disclose that the uncoated NMC811 suffers from chemomechanical degradations along with oxygen release triggering the decomposition of SPE, which results in unstable cathodic electrolyte interphase. With LNO coating, chemomechanical degradations and oxygen release are inhibited and the decomposition of SPE is mitigated. This paper renders a stable and high-performance high-energy-density SSB for high voltage application, which paves the way toward next-generation solid-state LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.

25 ENERGY STORAGE↗
DOE OSTI2024

Capacity Fade of Graphite/NMC811: Influence of Particle Morphology, Electrolyte, and Charge Voltage

LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is an important Li-ion battery cathode material; however, there is a tradeoff between delivered capacity and capacity retention. As the charge potential increases the capacity rises but at the expense of capacity retention. The decrease in capacity retention has been ascribed to several factors including particle cracking, surface reconstruction, transition metal dissolution, and electrolyte reactivity. The present study compares 4.1 and 4.3 V charging limits in commercially relevant graphite/NMC811 pouch cells for single crystal (SC) and polycrystalline (PC) NMC811 with ethylene carbonate (EC)-containing or EC-free electrolytes. The electrochemistry is rationalized through analysis of electrochemical impedance spectroscopy, positive electrode X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, X-ray diffraction, and negative electrode mapping by X-ray fluorescence. Graphite/SC-NMC811 cells show high-capacity retention at 4.1 V but exhibit degradation at 4.3 V charging potentials. The EC-free electrolyte cells led to higher capacity fade, especially when charged to 4.3 V. Cathode dissolution and deposition on the negative electrode from PC-NMC811 cells was higher than for samples from SC-NMC811 cells. This study reveals the impact of material type, charge voltage, and electrolyte composition on the reactions at the positive electrode, their influence on the negative electrode, and evolution with cycle number.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries

Solid-state batteries with desirable advantages, including high-energy density, wide temperature tolerance, and fewer safety-concerns, have been considered as a promising energy storage technology to replace organic liquid electrolyte-dominated Li-ion batteries. Solid-state electrolytes (SSEs) as the most vital component in solid-state batteries largely lead the future battery development. Among different types of solid-state electrolytes, garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) solid-state electrolytes have particularly high ionic conductivity (10 –3 to 10 –4 S/cm) and good chemical stability against Li metal, offering a great opportunity for solid-state Li-metal batteries. Since the discovery of garnet-type LLZO in 2007, there has been an increasing interest in the development of garnet-type solid-state electrolytes and all solid-state batteries. Garnet-type electrolyte has been considered one of the most promising and important solid-state electrolytes for batteries with potential benefits in energy density, electrochemical stability, high temperature stability, and safety. In this Review, we will survey recent development of garnet-type LLZO electrolytes with discussions of experimental studies and theoretical results in parallel, LLZO electrolyte synthesis strategies and modifications, stability of garnet solid electrolytes/electrodes, emerging nanostructure designs, degradation mechanisms and mitigations, and battery architectures and integrations. We will also provide a target-oriented research overview of garnet-type LLZO electrolyte and its application in various types of solid-state battery concepts (e.g., Li-ion, Li–S, and Li–air), and we will demonstrate opportunities and perspectives as guides for future development of solid electrolytes and solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Multiple Functional Bonds Integrated Interphases for Long Cycle Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have garnered significant interest as one of the most promising energy suppliers for power grid energy storage. However, the poor electrode/electrolyte interfacial stability leads to continual electrolyte decomposition and transition metal dissolution, resulting in rapid performance degradation of SIBs. In this work, we propose a strategy integrating multiple functional bonds to regulate electrode/electrolyte interphase by triple-coupling of succinonitrile (SN), sodium hexafluorophosphate (NaPF 6 ) and fluorinated ethylene carbonate (FEC). Theoretical calculation and experiment results show that the solvation structure of Na + and ClO 4 – is effectively reconfigured by the solvated FEC, SN and PF 6 – in PC-based carbonate electrolyte. The newly developed electrolyte demonstrates increased Na + -FEC coordination, weakened interaction of Na + -PC and participation of SN and PF 6 – anions in solvation, resulting in the formation of a conformal interfacial layer comprising of sodium oxynitrides (NaN x O y ), sodium fluoride (NaF) and phosphorus oxide compounds (NaP x O y ). Consequently, a 3 Ah pouch full cell of hard carbon//NaNi 1/3 Fe 1/3 Mn 1/3 O 2 exhibits an excellent capacity retention of 90.4 % after 1000 cycles. Detailed postmortem analysis of interface chemistry is further illustrated by multiple characterization methods. Finally, this study provides a new avenue for developing electrolyte formulations with multiple functional bonds integrated interphases to significantly improve the long-term cycling stability of SIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Nonintrusive thermal-wave sensor for operando quantification of degradation in commercial batteries

Abstract Monitoring real-world battery degradation is crucial for the widespread application of batteries in different scenarios. However, acquiring quantitative degradation information in operating commercial cells is challenging due to the complex, embedded, and/or qualitative nature of most existing sensing techniques. This process is essentially limited by the type of signals used for detection. Here, we report the use of effective battery thermal conductivity ( k eff ) as a quantitative indicator of battery degradation by leveraging the strong dependence of k eff on battery-structure changes. A measurement scheme based on attachable thermal-wave sensors is developed for non-embedded detection and quantitative assessment. A proof-of-concept study of battery degradation during fast charging demonstrates that the amount of lithium plating and electrolyte consumption associated with the side reactions on the graphite anode and deposited lithium can be quantitatively distinguished using our method. Therefore, this work opens the door to the quantitative evaluation of battery degradation using simple non-embedded thermal-wave sensors.

25 ENERGY STORAGE↗
DOE OSTI2025

Effect of high scandium doping in barium zirconate on nickel diffusion and performance of proton-conducting solid oxide electrolyzer cells

Proton-conducting solid oxide electrolyzer cells (p-SOECs) are emerging but promising technologies for hydrogen production. However, due to the lack of a robust electrolyte, p-SOECs struggle simultaneously to display high performance, Faradaic efficiency, and durability. Motivated by its high proton concentrations and stability as a barium zirconate, we have investigated BaZr 0.6 Sc 0.4 O 3-δ (BZSc40) as a potential next-generation p-SOEC electrolyte. Here, we found elevated levels of NiO diffusion through BZSc40 electrolytes during high-temperature sintering, attributed to the large oxygen vacancy concentrations present in BZSc40, as revealed by first-principle computational results. Controlling NiO diffusion is critical, as it can facilitate densification and grain size growth, but it may also detrimentally impact performance by causing electronic leakage. By optimizing sintering temperature when fabricating BZSc40 cells, we successfully controlled NiO diffusion, achieving sufficient electrolyte densification along with high performance and Faradaic efficiency. BZSc40 cells reached −0.99 A/cm 2 at 1.3 V and 600 °C and exhibited enhanced durability with a 3.37 mV/kh degradation rate at −0.8 A/cm 2 over a 200-h testing period. BZSc40 electrolytes demonstrated superior performance over BaZr 0.8 Y 0.2 O 3-δ (BZY20). In addition to elevated current densities and grain sizes, BZSc40 cells achieved Faradaic efficiencies of 76 % compared to 54 % for BZY20 at −0.2 A/cm 2 and 600 °C. This work lays the foundation for BZSc40 as a potential electrolyte due to its advantages over BZY20 while demonstrating the significance of controlling NiO diffusion when fabricating p-SOECs.

Electrolyzer↗
DOE OSTI2026

Passivation‐Induced Species Dynamics and Microstructural Evolution in Solid‐State Lithium–Sulfur Cathodes

Solid-state lithium–sulfur (SSLS) batteries offer high theoretical energy density, yet their practical viability is hindered by poor sulfur utilization and limited rechargeability. At the core of this challenge lies the passivating nature of Li 2 S, which restricts ionic and electronic transport, suppresses interfacial activity, and severely impedes the reversibility of electrochemical reactions. In this study, we elucidate the mechanistic origins of these limitations by resolving how charge and discharge species form, grow, and spatially evolve within the cathode microstructure under varied current densities and electrode compositions. By resolving the species distribution at the particle scale and coupling it with Raman spectroscopy and X-ray diffraction, we demonstrate how Li 2 S formation induces localized surface passivation that progressively limits electrochemical accessibility within the cathode microstructure. Sulfur utilization is found to be strongly governed by the interplay between sulfur loading, residual porosity, and interfacial architecture. High sulfur contents result in buried, electrochemically isolated domains due to poor solid electrolyte (SE) percolation, while low sulfur contents trigger SE degradation via parasitic reactions. The resulting sulfur-porosity maps delineate the mechanistic boundaries between reversible and transport-limited regimes, offering actionable design guidance for SSLS cathodes with enhanced sulfur utilization.

electrode microstructure↗
DOE OSTI2020

Locally developed electronic conduction in a yttria stabilized zirconia (YSZ) electrolyte for durable solid oxide fuel cells

In the present work, anode supported solid oxide fuel cells (SOFCs) based on a YSZ single layer electrolyte with locally developed electronic conduction near the anode side is fabricated to improve the cell durability under negative voltage conditions. A ceria added Ni/YSZ anode functional layer is utilized and co-sintered with the YSZ electrolyte at 1460 °C. Cerium ions are diffused into a limited region of the YSZ layer (~6 μm), establishing a ceria doped YSZ region. We successfully demonstrate that this YSZ single layer cell can operate stably for ~100 h without anode/electrolyte interface delamination, even under a negative voltage. The embedded probe technique and theoretical calculation reveal that the internal oxygen partial pressure (near the anode) is substantially reduced (stabilized) by means of local electronic conduction of ceria doped YSZ. Thus, we propose an SOFC electrolyte design comprising a YSZ single layer with a ceria added anode functional layer (locally formed ceria doped YSZ in the electrolyte) as a protection method against fuel cell stack degradation caused by negative voltage operation.

25 ENERGY STORAGE↗
DOE OSTI2022

Diffusional lithium trapping as a failure mechanism of aluminum foil anodes in lithium-ion batteries

Aluminum foils are an appealing anode for lithium-ion batteries due to high capacity and low-cost, but their viability has been limited due to poor cyclability arising from pulverization and solid-electrolyte interphase growth. Here, we show that significant capacity degradation of aluminum foil anodes during electrochemical cycling also occurs due to diffusional lithium trapping. Scanning electron microscopy of cross-sectioned, cycled foils in the delithiated state reveals large regions of β-LiAl that are passivated by a surface layer of α-Al, which has poor Li + diffusivity. It is found that lithium diffusion occurs preferentially along the β-LiAl grain boundaries, so the grain structure after initial lithiation significantly affects the trapping behavior. Diffusional lithium trapping is exacerbated by both higher delithiation rates and higher areal capacity, presenting a challenge towards commercialization of aluminum foil anodes. We further demonstrate that diffusional trapping in aluminum foil anodes can be mitigated through alloy design, with the addition of 2–3 wt% Li yielding improved first cycle efficiency, and the addition of 1 wt% Si yielding improved cycle life. These results provide a mechanistic understanding of diffusional lithium trapping in aluminum foil anodes and highlight compositional design of alloys as a promising strategy to overcome it.

25 ENERGY STORAGE↗
DOE OSTI2024

Pure-Water-Fed Forward-Bias Bipolar Membrane CO 2 Electrolyzer

Coupling renewable electricity to reduce carbon dioxide (CO 2 ) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO 2 reduction, the widespread deployment of CO 2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO 2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO 2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchangelayer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO 2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm –2 at less than 3.0 V with negligible CO 2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h –1 decay rates at 150 and 300 mA cm –2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer– electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. Furthermore, all these results point to the future research direction and show a promising pathway to deploy CO 2 electrolyzers at scale for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Effect of Si Content on Extreme Fast Charging Behavior in Silicon–Graphite Composite Anodes

Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon (Si)-based materials in the composite graphite-based anode to increase the energy density of the battery. However, very little is known about the effects of Si on the fast-charging behavior of composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from 1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in constant current charging cycles. The impacts of Si content on fast-charging aging were identified by Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are used in fast-charging applications and guides further research in the area by designing an optimized composition of Si incorporated in a mature graphite matrix.

25 ENERGY STORAGE↗
DOE OSTI2023

Characterization of Cycle-Aged Commercial NMC and NCA Lithium-ion Cells: I. Temperature-Dependent Degradation

Lithium-ion batteries are widely used in applications from consumer electronic devices to stationary energy storage. Appropriate management of batteries is challenging due to limited data on their performance and materials degradation. Previous studies have focused on characterization of single cells under specific operating conditions. In the present work, commercial 18650 lithium-ion cells with LiNi x Mn y Co 1-x-y O 2 (NMC) and LiNi x Co y Al 1-x-y O 2 (NCA) positive electrodes were characterized by a wide range of electrochemical and materials techniques after cycling at 15, 25, or 35 °C to ∼80% capacity. The NCA cells exhibit weak temperature dependence in their cycle aging and materials degradation. The NMC cells exhibited increased capacity fade and materials degradation as ambient temperature decreased. All cells exhibited loss of lithium inventory as their primary degradation mode. However, the NCA cells only showed evidence of solid electrolyte interphase (SEI) growth whereas the NMC cells showed signs of Li plating at 15 °C, transitioning to SEI growth at 35 °C. The NMC cells displayed signs of loss of active material at the positive electrode at lower temperatures, suggesting that Li plating is correlated to additional processes that increase the rate of degradation. These results highlight the importance of avoiding broad generalizations about Li-ion battery temperature dependence.

25 ENERGY STORAGE↗