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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 433 records · Page 24

A reversible perovskite air electrode for active and durable oxygen reduction and evolution reactions via the A-site entropy engineering

The performance of reversible solid oxide electrochemical cells (R-SOECs) is largely hindered by the insufficient electroactivity and poor durability of the bifunctional air electrodes, where the oxygen reduction and evolution reactions (ORR and OER) occur. Here, we report our findings in boosting the electrochemical activity and durability of an air electrode with Pr 0.2 Ba 0.2 Sr 0.2 La 0.2 Ca 0.2 CoO 3-δ (PBSLCC) via an A-site entropy engineering. The PBSLCC electrode shows enhanced oxygen reaction activity and excellent durability compared to binary and ternary double perovskites (PrBaCo 2 O 5+δ and Pr 0.8 Ba 0.8 Ca 0.4 Co 2 O 5+δ , respectively). A low and nearly unchanged area-specific resistance of 0.042Ωcm 2 is achieved at 750 °C during the 225-h stability test. La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ electrolyte-supported cells with the PBSLCC air electrode show remarkable performance at 800 °C, demonstrating a peak power density of 1.2Wcm -2 in the fuel cell mode, and a current density of -1.1 Acm -2 at 1.3 V in the electrolysis mode while maintaining the excellent cycling durability of 228 h at ±0.5 Acm -2 under humidified H 2 (10% H 2 O). A bulk oxygen p-band center model is applied to verify that tailoring of the A-site entropy strongly influences the surface exchange coefficients (k* chem ), leading to higher oxygen reaction activity of PBSLCC than the binary and ternary perovskites. Finally, this study opens a new class of high-entropy perovskites for the rational design of air electrodes for R-SOECs with high activity and durability.

30 DIRECT ENERGY CONVERSION↗

High-throughput Li plating quantification for fast-charging battery design

Fast charging of most commercial lithium-ion batteries is limited due to fear of lithium plating on the graphite anode, which is difficult to detect and poses considerable safety risk. In this report we demonstrate the power of simple, accessible and high-throughput cycling techniques to quantify irreversible Li plating spanning data from over 200 cells. We first observe the effects of energy density, charge rate, temperature and state of charge on lithium plating, use the results to refine a mature physics-based electrochemical model and provide an interpretable empirical equation for predicting the plating onset state of charge. We then explore the reversibility of lithium plating and its connection to electrolyte design for preventing irreversible Li accumulation. Finally, we design a method to quantify in situ Li plating for commercially relevant graphite|LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC) cells and compare with results from the experimentally convenient Li|graphite configuration. The hypotheses and abundant data herein were generated primarily with equipment universal to the battery researcher, encouraging further development of innovative testing methods and data processing that enable rapid battery engineering.

25 ENERGY STORAGE↗

Director's Discretionary Fund Report for Fiscal Year 1996

Topics covered include: Waterproofing the Space Shuttle tiles, thermal protection system for Reusable Launch Vehicles, computer modeling of the thermal conductivity of cometary ice, effects of ozone depletion and ultraviolet radiation on plants, a novel telemetric biosensor to monitor blood pH on-line, ion mobility in polymer electrolytes for lithium-polymer batteries, a microwave-pumped far infrared photoconductor, and a new method for measuring cloud liquid vapor using near infrared remote sensing. Also included: laser-spectroscopic instrument for turbulence measurement, remote sensing of aircraft contrails using a field portable imaging interferometer, development of a silicon-micromachined gas chromatography system for determination of planetary surface composition, planar Doppler velocimetry, chaos in interstellar chemistry, and a limited pressure cycle engine for high-speed output.

Source record↗

In situ anodic electrodeposition of two-dimensional conductive metal-organic framework@nickel foam for high-performance flexible supercapacitor

Owing to their large specific surface area and well-defined porosity, metal-organic frameworks (MOFs) have long been considered as promising materials for energy storage. Unfortunately, their straightforward utilization in supercapacitors was hindered for years due to poor conductivity until the emergence of 2D conductive MOF materials. To date, several 2D conductive MOF-based supercapacitors have been reported. Nevertheless, almost all these supercapacitors were fabricated from MOF powders through a slurry coating method or dense packing method, which negatively affected their capacitor performance. Herein, we have developed an anodic electrodeposition (AED) approach to fabricate a uniformly deposited 2D conducting MOF on nickel foam and use it directly as electrodes for supercapacitors without any additives. Finally, the superior performance of the 2D conducting MOF on nickel foam in both aqueous and organic electrolytes was then disclosed by a series of electrochemical measurements, demonstrating the significant advantages of the AED approach over traditional methods.

2D conductive metal-organic frameworks↗

Building High-Energy Silicon-Containing Batteries Using Off-The-Shelf Materials

The technology of silicon anodes appears to be reaching maturity, with high-energy Si cells already in pilot-scale production. However, the performance of these systems can be difficult to replicate in academic settings, making it challenging to translate research findings into solutions that can be implemented by the battery industry. Part of this difficulty arises from the lack of access to engineered Si particles and anodes, as electrode formulations and the materials themselves have become valuable intellectual property for emerging companies. Here, we summarize the efforts by Argonne’s Cell Analysis, Modeling, and Prototyping (CAMP) Facility in developing Si-based prototypes made entirely from commercially available materials. We describe the many challenges we encountered when testing high-loading electrodes (>5 mAh cm −2 ) and discuss strategies to mitigate them. With the right electrode and electrolyte design, we show that our pouch cells containing ≥ 70 wt% SiO x can achieve 600–1,000 cycles at C/3 and meet projected energy targets of 700 Wh L −1 and 350 Wh kg −1 . These results provide a practical reference for research teams seeking to advance silicon-anode development using accessible materials.

25 ENERGY STORAGE↗

Fundamental Investigations of Mechanical and Chemical Degradation Mechanisms in Lithium Ion Battery Materials (Final Technical Report)

The objective of our effort under the DOE EPSCoR Implementation grant is to establish a comprehensive and internationally recognized research program at Brown University and University of Rhode Island in understanding degradation mechanisms and to improve the cycle and calendar life of lithium ion battery (LIB) materials. A series of basic investigations are undertaken to characterize the mechanical and chemical degradation mechanisms, which can help enable new higher capacity and longer lasting electrode designs. Controlling mechanical and chemical degradation is the primary challenge in developing the next generation of higher energy density batteries. The development of failure resistant battery microstructures will require a fundamental understanding of the evolution of stress, deformation, damage, and electrochemistry in battery materials during cyclic charging and discharging. In addition, controlling the reactions at the electrode/electrolyte interface is critical for the formation of a stable SEI layer. We address these issues through a combination of controlled experiments on model battery materials and practical composite electrodes, together with multi-scale computations. Our effort is organized into three focus areas that encompass many critical challenges in Lithium Ion Battery Technologies: (i) Mechanical properties, fracture and damage in electrode materials; (ii) Chemistry and Mechanics of Solid Electrolyte Interphase (SEI); (iii) Mechanical and Chemical Integrity of Solid-Solid Interfaces in Practical Electrodes.

25 ENERGY STORAGE↗

Achieving High‐Performance and 2000 h Stability in Anion Exchange Membrane Fuel Cells by Manipulating Ionomer Properties and Electrode Optimization

The primary function of the ionomers that are incorporated into fuel cell electrode catalyst layers is to provide pathways for ion transport between the catalyst active sites and the electrolyte. This is influenced by many variables, including the ion-exchange capacity, water uptake, and molecular weight. In anion exchange membrane fuel cells (AEMFCs), controlling ionomer water uptake is particularly important and tailoring this property in each electrode is an important consideration when looking to maximize cell performance. In this study, three poly(norbornene) tetrablock copolymer ionomers with a range of physical properties are synthesized and incorporated into AEMFC anode and cathode electrodes. Systematic electrode engineering with these ionomers allows the peak power density to be increased by 100% (1.6 W cm -2 → 3.2 W cm -2 ) and the current density at 0.2 V to be increased by 59% (5.9 A cm -2 → 9.4 A cm -2 ). Moreover, the top-performing electrode configuration is tested in an operating AEMFC at the US Department of Energy defined current density of 600 mA cm -2 for 2000 h, showing a record-low voltage decay rate of 15.36 µV h -1 – only 3.65% –a over 2000 h. Here, this work sets a new bar for AEMFCs, reporting the best combination of performance and durability of any AEMFC to date.

08 HYDROGEN↗

Atomic layer deposition of nickel sulfide thin films and their thermal and electrochemical stability

Nickel sulfides (NiS x ) show promise for a range of energy and other applications, but their (in)stability under processing and operating conditions is scarcely studied. Herein, we have developed a new NiS x atomic layer deposition process using an easily synthesized NiCl 2 (TMPDA) precursor (TMPDA = N,N,N′,N′-tetramethyl-1,3-propanediamine) with H 2 S. Thin films deposited at 165–225 °C consist mostly of the β-NiS phase and display low resistivity (∼40–120 μΩ cm), high purity (<3 at% impurities), and a rough morphology. The thermal stability of the NiS x thin films is studied using high-temperature X-ray diffraction, revealing that structural and compositional changes occur in reducing, inert, and oxidizing atmospheres at approximately 300–400 °C. Under electrochemical water splitting conditions, the films are unstable in acid due to dissolution, especially at oxidizing potentials. In an alkaline electrolyte, we do not observe Ni dissolution, but β-NiS transforms to Ni 3 S 2 under HER conditions, possibly supplemented with Ni and/or Ni(OH) 2 species. Under alkaline OER, all sulfur is lost and NiOOH is formed. In addition to offering an attractive, scalable route to the synthesis of NiS x thin films, our work highlights the importance of thermal and electrochemical (in)stability of sulfides as a crucial step for understanding and engineering materials for energy and other applications.

Mattinen, Miika [Univ. of Helsinki (Finland); Stan↗

Monofluorinated acetal electrolyte for high-performance lithium metal batteries

High degree of fluorination for ether electrolytes has resulted in improved cycling stability of lithium metal batteries due to stable solid electrolyte interphase (SEI) formation and good oxidative stability. However, the sluggish ion transport and environmental concerns of high fluorination degree drive the need to develop less fluorinated structures. Here, we depart from the traditional ether backbone and introduce bis(2-fluoroethoxy)methane (F2DEM), featuring monofluorination of the acetal backbone. High coulombic efficiency and stable long-term cycling in Li||Cu half cells can be achieved with F2DEM even under fast Li metal plating conditions. The performance of F2DEM is further compared with diethoxymethane (DEM) and 2-[2-(2,2-difluoroethoxy)ethoxy]-1,1,1-trifluoroethane (F5DEE). A significantly lower overpotential is observed with F2DEM, which improves energy efficiency and enables its application in high-rate conditions. Comparative studies of F2DEM with DEM and F5DEE in anode-free lithium iron phosphate (LiFePO4) LFP pouch cells and high-loading LFP coin cells further show improved capacity retention of F2DEM electrolyte, demonstrating its practical applicability. More importantly, we also extensively investigate the underlying mechanism for the superior performance of F2DEM through various techniques, including X-ray photoelectron spectroscopy, scanning electron microscopy, cryogenic electron microscopy, focused ion beam, electrochemical impedance spectroscopy, and titration gas chromatography. Overall, F2DEM facilitates improved Li deposition morphology with reduced amount of dead Li. This enables F2DEM to show superior performance, especially under higher charging and slower discharging rate conditions.

25 ENERGY STORAGE↗

Techno-economic analysis of non-aqueous hybrid redox flow batteries

Renewable energy has become indispensable to improving human life, but its growth is hampered by a lack of cost-effective energy storage systems to solve the intermittency problem. Non-aqueous hybrid redox flow batteries (NAqHRFBs), based on lithium metal anode and organic redox molecules (redoxmers), have been investigated as an attractive energy storage option because of their high cell voltages and energy densities compared to other redox flow battery candidates. However, little is known about the economic potential of NAqHRFBs, as well as the operational and materials impacts. This research establishes a techno-economic model to analyze the capital costs of NAqHRFBs with selected organic redoxmers, including 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). Sensitivity analyses for current density, area-specific resistance, cell voltage, electrolyte composition, redoxmer price, and equivalent molecular weight indicate the key factors in controlling NAqHRFB capital cost. To make the current NAqHRFB cost-effective, the first priority is to increase the operation current density over 10 times of those used in lab-scale tests, followed by adjusting redoxmer-related characteristics to afford more cost reduction space such as decreasing the unit price by ~20 fold. The results have shed light on potential material development and system engineering directions to make NAqHRFBs viable for renewable energy storage.

25 ENERGY STORAGE↗

Revitalizing interface in protonic ceramic cells by acid etch

Protonic ceramic electrochemical cells hold the promise to be operated at intermediate temperatures below 600 °C. Although the high proton conductivity of the bulk electrolyte has been demonstrated, it cannot be fully utilized in electrochemical full cells due to unknown causes. A practical solution is thus urgently needed. Here we showed that it comes from poor contacts between the low-temperature processed oxygen electrode-electrolyte interface. We demonstrated that a simple acid treatment can effectively rejuvenate the high-temperature annealed electrolyte surface, resulting in reactive bonding between the oxygen electrode and the electrolyte and improved electrochemical performance and stability. This enables exceptional protonic ceramic fuel-cell performance down to 350 °C, with peak power densities of 1.6 W cm -2 at 600 °C, 650 mW cm -2 at 450 °C, and 300 mW cm -2 at 350 °C, as well as stable electrolysis operations at large current densities above 3.9 A cm -2 under 1.4 V applied voltage at 600 °C. Furthermore, our work highlights the critical role of interfacial engineering in ceramic electrochemical devices and offers new understanding and practices towards sustainable energy infrastructure.

08 HYDROGEN↗

Development of Aluminum/Air Battery as High-Capacity Primary Battery Energy Source for SUSAN Electrofan Project

High-capacity, high-performance, and safe battery technologies are demanded by the Subsonic Single Aft eNgine (SUSAN) Electrofan concept design project under National Aeronautics and Space Administration (NASA) electrified aircraft development program. These battery technologies, including both secondary (i.e., rechargeable) batteries for hybrid/electric propulsion and primary batteries (i.e. non-rechargeable or single-use) for backup/emergency use in case of turbine engine failure, are important and vital components in SUSAN concept design. This paper is focused on aluminum (Al)-air battery, which is considered to be the most promising candidate to meet the energy goal of primary batteries for SUSAN project. However, there are challenges for Al-air batteries, including aluminum self-corrosion with hydrogen (H2) gassing and sluggish kinetics of oxygen reduction reaction (ORR) in air-cathode. In this paper, the preliminary results on investigation of electrolytes and additives on controlling aluminum self-corrosion/H2 gassing suppression and the study of air-cathode design for ORR improvement are presented and discussed.

James Wu↗

ElectroCat: Platinum-Group-Metal-Free Engineered Framework Nano-Structure Catalyst (Final Technical Report)

Traditional synthesis methodologies that produce durable, highly active PGM-free electrocatalysts typically consist of a top-down approach utilizing a nitrogen-coordinating precursor, a metal precursor, and a support material. Nitrogen-coordinated transition metal complexes typically are absorbed onto a support material, which is then activated via high-temperature pyrolysis. Selection of the support and the nitrogen coordinating precursor has long been the focal point of efforts to maximize the number of accessible, catalytically active sites. In this project, GWE in collaboration with SRNL and NU will develop durable, highly active, low-cost, PGM-free electrocatalysts for polymer electrolyte membrane fuel cells designed and synthesized using a unique, bottom-up, rationally designed approach. Electrocatalysts are produced via polymerization reaction followed by a high-temperature pyrolysis step. Additionally, this project focuses on catalyst site and ORR mechanistic modeling to better understand the structure-property relationship.

08 HYDROGEN↗

Engineering Development Program of a Closed Aluminum-Oxygen Semi-cell System for an Unmanned Underwater Vehicle: An Update

Most emerging unmanned undersea vehicle (UUV) missions require significantly longer range and endurance than is achievable with existing battery technology. The Aluminum-Oxygen (Al-O2) semi-cell is a candidate technology capable of providing a significant improvement in endurance compared to the silver-zinc battery technology currently in use in UUVs and compares favorably to other proposed UUV power systems not only in performance, but also in safety and logistics. An Al-O2 semi-cell system is under development, consisting of a cell stack, gas management, oxygen storage, electrolyte management coolant and controller subsystems. It is designed to replace the existing silver-zinc battery and meet existing weight, volume, electrical and thermal requirements, therefore minimizing modification to the UUV. A detailed system design is complete. A component and material endurance test to evaluate compatibility and reliability of various materials and components is complete. Sub=scale (short stack) system testing is complete. A full-scale demonstration unit is now under construction for testing in the second half of 1995. The full scale demonstration test will simulate environmental conditions of the operational system. This paper summarizes the results of the extensive short stack and endurance test programs, describes the plan for full-scale testing, and concludes with a brief discussion of future directions for this technology.

Gregg, Dane W.↗

Measurement of the Natural Convection Heat Transfer in a Magnesium Oxide Electrolytic Cell Concept

The rate of heat transfer by natural convection between the wall and electrolyte of an electrolytic cell that produces magnesium (Mg) from magnesium oxide (MgO) at temperatures near 1000 °C in a molten fluoride salt electrolyte is presented. An experimental model of the cell was developed that enabled measurements of the heat transfer in the absence of electrolysis and at temperatures less than 100 °C over ranges of Rayleigh numbers from 1 × 10 -7 to 7 × 10 -8 and Prandtl numbers from 2 to 6200, ranges that include those anticipated in the operation of the MgO electrolytic cell. The model avoids the substantial experimental challenges associated with the high-temperature, corrosive molten salt to enable a conservative estimate of the heat transfer at a lower cost and greater accuracy than would otherwise be possible. The results are correlated by the expression Nu = 0.412Ra 0.23 Pr 0.15 with Nusselt numbers spanning 30–80. The application of the correlation shows that the heat transfer between the cell wall and the molten fluoride electrolyte at ≈1000 °C is characterized by convection coefficients between 100 and 600 W/m 2 -K and is fast enough to enable heat fluxes up to 10 W/cm 2 without compromising the structural integrity of the steel cell wall.

Engineering↗

Predictive Engineering of Interfaces and Cathodes for High-Performance All Solid-State Lithium-Sulfur Batteries

The primary goal of this project is to leverage data-driven methods and machine learning strategies to develop accurate multi-physics models for all-solid-state Li-S battery (ASLSB) materials that can capture electrochemical and transport phenomena over atomic to mesoscopic length/timescales. These models will be rigorously validated by synthesis and advanced characterization experiments. The team will leverage the predictive power of these models, alongside synthesis/characterization experiments and battery fabrication to address longstanding issues at the electrode/electrolyte interfaces in ASLSBs. The project’s proposed technology involves the following: (1) halide-doped solid sulfide electrolytes that can concurrently provide high Li + ion conductivity and suppress dendrite growth; (2) novel mesoporous cathode composed of super-P and carbon nanotubes co-infiltrated with sulfur and sulfide electrolyte, which hold potential to allow high sulfur loading and optimal ion/electron pathways; and (3) functionalization of sulfide electrolyte with ionic liquids to improve physical contact and minimize impedance at the cathode/electrolyte interface. Successful development of proposed predictive models (at multiple scales) will bridge this knowledge gap and will advance fundamental understanding of reaction chemistry, kinetics, charge transfer, and dendrite growth at electrified SSIs. This will enable predictive design of effective strategies to mitigate interfacial problems in ASSLSBs, including poor interfacial contact, interfacial impedance to Li + ion transport, and poor electron/ion conduction within cathodes. Ultimately, the fundamental knowledge gained will lead to development of high-performance ASSLSBs.

25 ENERGY STORAGE↗

Direct Measurement of Crossover and Interfacial Resistance of Ion-Exchange Membranes in All-Vanadium Redox Flow Batteries

Among various components commonly used in redox flow batteries (RFBs), the separator plays a significant role, influencing resistance to current as well as capacity decay via unintended crossover. It is well-established that the ohmic overpotential is dominated by the membrane and interfacial resistance in most aqueous RFBs. The ultimate goal of engineering membranes is to improve the ionic conductivity while keeping crossover at a minimum. One of the major issues yet to be addressed is the contribution of interfacial phenomena in the influence of ionic and water transport through the membrane. In this work, we have utilized a novel experimental system capable of measuring the ionic crossover in real-time to quantify the permeability of ionic species. Specifically, we have focused on quantifying the contributions from the interfacial resistance to ionic crossover. The trade-off between the mass and ionic transport impedance caused by the interface of the membranes has been addressed. The MacMullin number has been quantified for a series of electrolyte configurations and a correlation between the ionic conductivity of the contacting electrolyte and the Nafion® membrane has been established. The performance of individual ion-exchange membranes along with a stack of various separators have been explored. We have found that utilizing a stack of membranes is significantly beneficial in reducing the electroactive species crossover in redox flow batteries compared to a single membrane of the same fold thickness. For example, we have demonstrated that the utilization of five layers of Nafion ® 211 membrane reduces the crossover by 37% while only increasing the area-specific resistance (ASR) by 15% compared to a single layer Nafion ® 115 membrane. Therefore, the influence of interfacial impedance in reducing the vanadium ion crossover is substantially higher compared to a corresponding increase in ASR, indicating that mass and ohmic interfacial resistances are dissimilar. We have expanded our analysis to a combination of commercially available ion-exchange membranes and provided a design chart for membrane selection based on the application of interest (short duration/high-performance vs. long-term durability). The results of this study provide a deeper insight into the optimization of all-vanadium redox flow batteries (VRFBs).

UV/Vis spectroscopy↗

Advanced battery modeling for interfacial phenomena and optimal charging

Lithium ion batteries are one of the most promising energy storage systems for portable devices, transportation, and renewable grids. To meet the increasing requirements of these applications, higher energy density and areal capacity, long cycle life, fast charging rate and enhanced safety for lithium ion battery (LIBs) are urgently needed. To solve these challenges, the relevant physics at different length scale need to be understood. However, experimental study is time consuming and limited in small scale’s study. Modeling techniques provide us powerful tools to get a deep understanding of the relevant physics and find optimal solutions. This work focuses on studying the mechanism in advanced battery engineering techniques and developing a new charging algorithm by model-based optimization. The research topics are divided into six topics and each topic is reported as a form of journal publication. Paper Ⅰ provides a new aspect of how ALD coating improves the lithium ion diffusion at electrode particles. Paper Ⅱ explains the mechanisms by which 3D electrodes enhance battery performance and reveals guidelines for optimized 3D electrode designs by a 3D electrochemical-mechanical battery model. Paper Ⅲ investigates the electrolyte concentration impact on SEI layer growth and Li plating, especially under high charge rates. Paper Ⅳ proposes an optimized charging protocol for fast charging for reducing the charging time with minimal degradation. Paper Ⅴ reports a comprehensive degradation model for degradation estimation and life predication of energy storage system (ESS). Paper Ⅵ is a study of temperature-dependent state of charge (SOC) estimation for battery pack.

25 ENERGY STORAGE↗