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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 181 records · Page 10

A failure model for sealed nickel-cadmium batteries

A model has been developed to describe failure in electrochemical batteries. The model is based on the concept of the existence and subsequent growth of flaws which ultimately lead to battery failure. This model provides, in a natural way, for the statistical variability of lifetime data. The model as applied to the Crane data indicates that when the effects of temperature and depth of discharge are taken into account, the observed variability in lifetime data is due almost entirely to statistical variability inherent in the battery itself.

Fedors, R. F.↗

Ionic conductive polymers as artificial solid electrolyte interphase films in Li metal batteries – A review

Lithium (Li) metal has been considered as the ultimate anode material for next-generation rechargeable batteries due to its ultra-high theoretical specific capacity (3860 mAh g -1 ) and the lowest reduction voltage (-3.04 V vs the standard hydrogen electrode). However, the dendritic Li formation, uncontrolled interfacial reactions, and huge volume variations lead to unstable solid electrolyte interphase (SEI) layer, low Coulombic efficiency and hence short cycling lifetime. Designing artificial solid electrolyte interphase (artificial SEI) films on the Li metal electrode exhibits great potential to solve the aforementioned problems and enable Li–metal batteries with prolonged lifetime. Polymer materials with good ionic conductivity, superior processability and high flexibility are considered as ideal artificial SEI film materials. In this review, according to the ionic conductive groups, recent advances in polymeric artificial SEI films are summarized to afford a deep understanding of Li ion plating/stripping behavior and present design principles of high-performance artificial SEI films in achieving stable Li metal electrodes. Perspectives regarding to the future research directions of polymeric artificial SEI films for Li–metal electrode are also discussed. The insights and design principles of polymeric artificial SEI films gained in the current review will be definitely useful in achieving the Li–metal batteries with improved energy density, high safety and long cycling lifetime toward next-generation energy storage devices.

25 ENERGY STORAGE↗

Maximising the investment returns of a grid‐connected battery considering degradation cost

Energy storage systems (ESSs) are being deployed widely due to numerous benefits including operational flexibility, high ramping capability, and decreasing costs. This study investigates the economic benefits provided by battery ESSs when they are deployed for market‐related applications, considering the battery degradation cost. A comprehensive investment planning framework is presented, which estimates the maximum revenue that the ESS can generate over its lifetime and provides the necessary tools to investors for aiding the decision making process regarding an ESS project. The applications chosen for this study are energy arbitrage and frequency regulation. Lithium‐ion batteries are considered due to their wide popularity arising from high efficiency, high energy density, and declining costs. A new degradation cost model based on energy throughput and cycle count is developed for Lithium‐ion batteries participating in electricity markets. The lifetime revenue of ESS is calculated considering battery degradation and a cost–benefit analysis is performed to provide investors with an estimate of the net present value, return on investment and payback period. The effect of considering the degradation cost on the estimated revenue is also studied. The proposed approach is demonstrated on the IEEE Reliability Test System and historical data from PJM Interconnection.

25 ENERGY STORAGE↗

Final Technical Report

This research project aims to understand the structure and properties of hidden intermediates in amorphous oxides grown by atomic layer deposition (ALD), and apply what is learned to achieve predictive phase and property control in the ALD synthesis of amorphous oxide thin films. The one-year renewal is to further this understanding to understand how amorphous TiO2 thin films by ALD turn into crystalline phase in correlation to the presence of medium range ordering (MRO) and other impurities. This fundamental study is expected to produce a predictive synthesis science for amorphous thin films with substantially improved uniformity and thereby achieve higher stability as a new surface coating strategy used for electrochemical catalysis. In this final technical report, we summarize the key achievements in this project to meet the research goals. This includes (1) a new approach to achieve homogeneous nanometer-scale amorphous coating leading to a new record of lifetime for photoelectrochemical hydrogen fuel generation; (2) A advancement in scanning transmission electron microcopy (STEM) that led to new understanding of intermediate phase in amorphous films; and (3) a computational model for understanding the local structure ordering in amorphous TiO2 films. In addition, this project also yielded relevant technical innovations including a development of bioresorbable zinc primary batteries that can self-degrade after depletion; and a ferroelectric membrane that provides active dendrites suppression to substantially improve the lifetime of rechargeable batteries. Collaboration with Lam Research also yield a new understanding of how built-in strain influences the amorphous films’ quality, bringing direct impacts to semiconductor manufacturing industry.

36 MATERIALS SCIENCE↗

Sustainable bioleaching of lithium-ion batteries for critical materials recovery

The demand for lithium-ion batteries (LIBs) has increased substantially over the last few decades due to their longer lifetime, greater resistance to self-discharge, and higher output voltage compared to other battery types. With the global trend of electrifying vehicle fleets, the number of LIBs reaching their end-of-life (EOL) is expected to grow substantially in the next decade. These EOL LIBs represent a significant secondary source of materials (e.g., Li, Co, Ni, Mn) that can be recovered and reused in LIBs or other products. In this study, we developed a bioleaching process that could recover critical materials from EOL LIBs in an economical and environmentally sustainable manner under industrially relevant conditions. Black mass, i.e., cathode-containing powder, prepared from EOL LIBs was leached using a biolixiviant produced from corn stover by Gluconobacter oxydans bacteria. Iron(II) was used as a reducing agent to promote metal dissolution. Techno-economic analysis (TEA) estimated a potential average profit margin of 21% for processing 10,000 t of black mass per year, which represents approximately 30% of the available black mass in the US in 2020. Life cycle assessment (LCA) demonstrated that bioleaching of spent LIBs could be more environmentally sustainable than alternative hydrometallurgical recovery methods such as hydrochloric acid leaching (16-19 kg vs. 43-91 kg CO 2 equivalent global warming potential per kg of recovered cobalt). The TEA results are highly dependent on the cost of black mass production, which varies by EOL LIB collection and transportation costs. Finally, emerging technologies for deactivating used LIBs for fire safety at collection centers will allow the transport of EOL LIBs as non-hazardous materials, lower the cost of preparing black mass and thereby increase economic prospects for EOL LIBs recycling using this approach.

25 ENERGY STORAGE↗

Engineering block co-polymer anion exchange membrane domains for highly efficient electrode-decoupled redox flow batteries

We report, anion exchange membranes (AEMs) with high permselectivity, chemical stability and mechanical robustness are a key enabling technology for a variety of electrochemical energy conversion and storage systems such as fuel cells, redox flow batteries and water electrolyzers. Herein we examine well understood chemically stable triblock co-polymer AEMs derived by the chloromethylation (CM-) and subsequent trimethylamine (TMA) functionalization of polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) block co-polymers. We show using small angle X-ray scattering (SAXS) that the introduction of a hydrophobic reinforcement matrix disrupts phase segregation and decreases ionic domain sizes in these AEM separators. The reinforcement matrix simultaneously causes the ultimate tensile strength (UTS) of the reinforced separator to increase by almost 600% compared to the unreinforced form, while maintaining comparable elasticity (ca. 500% elongation at break). Such reinforced r-SEBS30-TMA separators enable electrode-decoupled redox flow batteries (ED-RFBs) with significantly improved lifetimes by decreasing per cycle capacity fade from 0.5% to <0.05%. This 10× improvement in operando permselectivity opens the door to ED-RFBs employing inexpensive elemental actives achieving decades-long usable lifespans.

25 ENERGY STORAGE↗

Wireless Data-Acquisition System for Testing Rocket Engines

A prototype wireless data-acquisition system has been developed as a potential replacement for a wired data-acquisition system heretofore used in testing rocket engines. The traditional use of wires to connect sensors, signal-conditioning circuits, and data acquisition circuitry is time-consuming and prone to error, especially when, as is often the case, many sensors are used in a test. The system includes one master and multiple slave nodes. The master node communicates with a computer via an Ethernet connection. The slave nodes are powered by rechargeable batteries and are packaged in weatherproof enclosures. The master unit and each of the slave units are equipped with a time-modulated ultra-wide-band (TMUWB) radio transceiver, which spreads its RF energy over several gigahertz by transmitting extremely low-power and super-narrow pulses. In this prototype system, each slave node can be connected to as many as six sensors: two sensors can be connected directly to analog-to-digital converters (ADCs) in the slave node and four sensors can be connected indirectly to the ADCs via signal conditioners. The maximum sampling rate for streaming data from any given sensor is about 5 kHz. The bandwidth of one channel of the TM-UWB radio communication system is sufficient to accommodate streaming of data from five slave nodes when they are fully loaded with data collected through all possible sensor connections. TM-UWB radios have a much higher spatial capacity than traditional sinusoidal wave-based radios. Hence, this TM-UWB wireless data-acquisition can be scaled to cover denser sensor setups for rocket engine test stands. Another advantage of TM-UWB radios is that it will not interfere with existing wireless transmission. The maximum radio-communication range between the master node and a slave node for this prototype system is about 50 ft (15 m) when the master and slave transceivers are equipped with small dipole antennas. The range can be increased by changing to larger antennas and/or greater transmission power. The battery life of a slave node ranges from about six hours during operation at full capacity to as long as three days when the system is in a "sleep" mode used to conserve battery charge during times between setup and rocket-engine testing. Batteries can be added to prolong operational lifetimes. The radio transceiver dominates the power consumption.

Lin, Chujen↗

Ion-Depleted Microenvironments During Lithium Deposition Revealed by Operando Freezing Cryogenic Electron Microscopy

Local structures and chemistry at active electrochemical interfaces are critical to determining safety, lifetime, and energy density in lithium metal batteries and other devices, but they are challenging to characterize at the nanoscale. We address this issue by developing operando freezing cryogenic electron microscopy (cryo-EM) to preserve battery interfaces in an active state for subsequent high-resolution characterization. We find that ion-depleted microenvironments form locally in the electrolyte adjacent to the lithium deposition interface in lithium metal batteries and are linked to heterogenous growth morphologies. These depleted environments arise locally even under conditions for which ion depletion is not predicted at steady state; this provides a mechanistic explanation for why dangerous lithium morphologies can still propagate in such systems and lead to thermal runaway. Operando freezing cryo-EM thus provides a method to directly visualize nanoscale heterogeneities that arise locally at electrochemical interfaces and play key roles in device failure.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,E↗

Storing Electricity with Salt and Iron (CRADA Final Report)

As part of the Cyclotron Road program, Inlyte Energy, Inc. investigated low-cost energy storage for the electricity grid via batteries manufactured from abundant materials. Low-cost energy storage can solve the problem of the intermittency of wind and solar power, thereby allowing these sources of energy to scale more rapidly. The project team explored development of a Na-FeCl 2 battery—which had as its starting redox-active materials the abundant materials table salt (NaCl) and iron—that can operate safely and efficiently over a long lifetime, and be produced at very low-cost. The Na-FeCl 2 battery is architecturally similar to the commercialized Zebra (Na-NiCl 2 ) batteries, which have demonstrated safety, efficiency, and long lifetime. This project explored and assessed key design changes, including the use of planar Na-β’’-alumina solid electrolyte and lower temperatures (~200 °C) with polymer seals aimed at decreasing costs.

25 ENERGY STORAGE↗

High-Throughput Electrochemical Characterization of Aqueous Organic Redox Flow Battery Active Material

The development of redox-active organics for flow batteries providing long discharge duration energy storage requires an accurate understanding of molecular lifetimes. Herein we report the development of a high-throughput setup for the cycling of redox flow batteries. Using common negolyte redox-active aqueous organics, we benchmark capacity fade rates and compare variations in measured cycling behavior of nominally identical volumetrically unbalanced compositionally symmetric cells. We propose figures of merit for consideration when cycling sets of identical cells, and compare three common electrochemical cycling protocols typically used in battery cycling: constant current, constant current followed by constant voltage, and constant voltage. Redox-active organics exhibiting either high or low capacity fade rates are employed in the cell cycling protocol comparison, with results analyzed from over 50 flow cells.

Electrochemistry↗

Diagnostics, Prognostics, and Optimization for Lithium-Ion Battery Systems

Health management of lithium-ion battery systems presents a host of challenges due to their complex physics, large numbers of components, and a wide variety of degradation behaviors across different battery types. Dr. Paul Gasper will present on research from the Electrochemical Energy Storage Group on Lithium-ion battery diagnostics, prognostics, and optimization. Diagnostics research, including state-estimation via machine-learning from electrochemical impedance spectroscopy and DC pulses as well as continuous state-estimation via Kalman filters, will highlight the ongoing challenges for accurately measuring the state of batteries without performing time-consuming characterization tests. NLR's industry-recognized battery prognostics work, which predicts real-world battery degradation by identifying degradation rate models from accelerated aging data using statistical modeling and machine-learning, will be used to demonstrate the critical impact of battery controls, thermal management, and operating strategy on durability and lifetime. Finally, the use of prognostic models for financial or lifetime optimization will be discussed.

25 ENERGY STORAGE↗

Techno-Economic Analysis of Recuperated Joule-Brayton Pumped Thermal Energy Storage

This article describes a techno-economic model for pumped thermal energy storage systems based on recuperated Joule-Brayton cycles and two-tank liquid storage. Models have been developed for each component, with particular emphasis on the heat exchangers. Economic metrics such as the power and energy capital costs (i.e., per-kW and per-kWh capacity) and levelized cost of storage are evaluated by gathering numerous cost correlations from the literature, thereby enabling estimates of uncertainty. It is found that the use of heat exchangers with effectivenesses up to 0.95 is economically worthwhile, but higher values lead to rapidly escalating component size and system cost. Several hot storage fluids are considered; those operating at the highest temperatures (chloride salts) improve the round-trip efficiency but the benefit is marginal and may not warrant the additional material costs and risk when compared to lower-temperature nitrate salts. Cost-efficiency trade-offs are explored using a multi-objective optimization algorithm, yielding optimal designs with round-trip efficiencies in the range 59-72% and corresponding levelized storage costs of 0.12 0.03 and 0.38 0.10 $/kWhe. Lifetime costs are competitive with lithium-ion batteries for discharging durations greater than 6 h under current scenarios.

Carnot battery↗

A Cation-Tethered Flowable Polymeric Interface for Enabling Stable Deposition of Metallic Lithium

A fundamental challenge, shared across many energy storage devices, is the complexity of electrochemistry at the electrode–electrolyte interfaces that impacts the Coulombic efficiency, operational rate capability, and lifetime. Specifically, in energy-dense lithium metal batteries, the charging/discharging process results in structural heterogeneities of the metal anode, leading to battery failure by short-circuit and capacity fade. In this work, we take advantage of organic cations with lower reduction potential than lithium to build an electrically responsive polymer interface that not only adapts to morphological perturbations during electrodeposition and stripping but also modulates the lithium ion migration pathways to eliminate surface roughening. As a result, we find that this concept can enable prolonging the long-term cycling of a high-voltage lithium metal battery by at least twofold compared to bare lithium metal.

25 ENERGY STORAGE↗

Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers

Irreparable chemical damage to redox-active monomers, oligomers, and polymers (i.e. redoxmers) limits the lifetime of energy storage devices (e.g. redox flow batteries) by causing electrode and membrane fouling, as well as irreversible capacity loss. To predictably restore device and materials performance, it is desirable to add programmed destruction capabilities into these damage-prone materials. Here, we report the use of triggerable retrograde reactions to achieve programmable end-of-life function in redoxmers. Retrograde reactions are intended to break up damaged redoxmer materials into more soluble small-molecule constituents to prevent irreparably fouling battery interfaces. We investigated the redox-triggered mesolytic cleavage of homobenzylic ethers (HBEs) for this purpose. Combining experimental methods with simulations, we probed the influence of ring substituents on the programmable bond-scission behavior of HBEs. Variation of para-substituents on the HBEs allowed us to modify the oxidation potential, degradation pathway, and electrochemical mechanisms of the generated products. Given its ideal oxidation potential, we selected the para-methoxy-based HBE as the cleavage scaffold and integrated it with dialkoxybenzene, TEMPO, viologen, and para-nitrobenzene redox centers for compatibility, bulk deconstruction, and electrode defouling tests. Upon applying a high oxidation potential, the redox-active pendant is cleaved from the backbone via HBE bonds; of the four redox centers tested, three of them remained fully redox active. Viologen-appended redox active polymers with HBE linkers were cleaved to fully separate the redox centers from the backbone. Polymer-filmed electrodes were partially restored following HBE oxidation defouling. Here these studies highlight the co-design of new materials functions for developing sustainable energy storage materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling interphase-driven failure pathways in LiMn0.6Fe0.4PO4/graphite pouch cells

LiMnxFe1−xPO4 (LMFP) is a promising high-voltage, thermally stable, and earth-abundant cathode material, yet its practical application is limited by interphase instability and Mn dissolution. In this work, we systematically evaluate LiMn0.6Fe0.4PO4/graphite pouch cells using three electrolyte formulations including control carbonate electrolyte, control + 2 wt% vinylene carbonate (VC), and control + 2 wt% VC + 1 wt% 1,3,2-dioxathiolane 2,2-dioxide (DTD), to establish how electrolyte composition governs interphase chemistry and long-term degradation. Electrochemical testing shows that both additives are preferentially reduced prior to ethylene carbonate (EC) during cell formation, generating robust cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) layers that suppress gas evolution and raise the first-cycle coulombic efficiency to 89.3%. Additionally, the dual-additive electrolyte delivers the most stable performance, retaining over 85% capacity after 600 cycles while minimizing impedance growth under long-term cycling at C/3 and 40 °C. Soft X-ray absorption spectroscopy confirms that VC + DTD effectively suppresses electrolyte oxidation at the cathode surface, and micro-X-ray fluorescence shows substantially reduced Mn dissolution and deposition on the graphite anode. Density functional theory simulations further provided insights into the structural and energetic influences of alkoxide species on the cathode surface, proposing a Mn2+ extraction mechanism. The combined experimental and computational findings establish a mechanistic link between electrolyte composition and interphase evolution, highlighting the effectiveness of electrolyte engineering for extending the operational lifetime of LMFP-based lithium-ion batteries.

Chak, Chanmonirath Michael↗

Laser Calibration Experiment for Small Objects in Space

The Air Force Research Laboratory/Directed Energy Directorate (AFRL/DE) and NASA/Marshall Space Flight Center (MSFC) are looking at a series of joint laser space calibration experiments using the 12J 15Hz CO2 High Performance CO2 Ladar Surveillance Sensor (FU-CLASS) system on the 3.67 meter aperture Advanced Electro-Optics System (AEOS). The objectives of these experiments are to provide accurate range and signature measurements of calibration spheres, demonstrate high resolution tracking capability of small objects, and support NASA in technology development and tracking projects. Ancillary benefits include calibrating radar and optical sites, completing satellite conjunction analyses, supporting orbital perturbations analyses, and comparing radar and optical signatures. In the first experiment, a Global Positioning System (GPS)/laser beacon instrumented microsatellite about 25 cm in diameter will be deployed from a Space Shuttle Hitchhiker canister or other suitable launch means. Orbiting in low earth orbit, the microsatellite will pass over AEOS on the average of two times per 24-hour period. An onboard orbit propagator will activate the GPS unit and a visible laser beacon at the appropriate times. The HI-CLASS/AEOS system will detect the microsatellite as it rises above the horizon, using GPS-generated acquisition vectors. The visible laser beacon will be used to fine-tune the tracking parameters for continuous ladar data measurements throughout the pass. This operational approach should maximize visibility to the ground-based laser while allowing battery life to be conserved, thus extending the lifetime of the satellite. GPS data will be transmitted to the ground providing independent location information for the microsatellite down to sub-meter accuracies.

Campbell, Jonathan↗

STARSAT: A Joint NASA/AF Project for Laser Calibration of Small Objects in Space

The Air Force Research Laboratory/Directed Energy Directorate (AFRL/DE) and the NASA/Marshall Space Flight Center are planning a joint laser space calibration experiments using the HI-CLASS ladar system and the Advanced Electro-Optical System (AEOS) located at Maui Space Surveillance System (MSSS). These experiments will use ladar data to provide accurate range and signature measurements of calibration spheres with known sizes. Ancillary experiment benefits could include calibrating operational sensors, analyzing effects of orbital perturbations on micro-satellites, and correlating radar and optical signatures. In the first experiment, a GPS/laser beacon instrumented micro-satellite about 20 cm in diameter would be deployed from a Space Shuttle Hitchhiker canister. Orbiting in LEO, the micro-satellite would pass over MSSS on the average of two times per 24 hour period. A timing circuit would activate the GPS unit that would in turn activate the laser beacon at the appropriate time. The HI-CLASS/AEOS system will detect and acquire the micro-sat as it rises above the horizon and demonstrate that continuous track can be maintained throughout the pass. Orbital parameters will be obtained. This operational approach should maximize visibility to the ground-based laser while allowing battery life to be conserved thus extending the lifetime of the satellite. GPS data will be transmitted to the ground, providing independent location information down to cm accuracies for comparison and evaluation purposes.

Campbell, Jonathan W.↗

Localized Hydrophobicity in Aqueous Zinc Electrolytes Improves Zinc Metal Reversibility

The rechargeability of aqueous zinc metal batteries is plagued by parasitic reactions of the zinc metal anode and detrimental morphologies such as dendritic or dead zinc. To improve the zinc metal reversibility, hereby we report a new solution structure of aqueous electrolyte with hydroxyl-ions scavengers and hydrophobicity localized in solvent clusters. In this work we show that although hydrophobicity sounds counterintuitive for an aqueous system, hydrophilic pockets may be encapsulated inside a hydrophobic outer layer and a hydrophobic anode-electrolyte interface can be generated through the addition of a cation-philic, strongly anion-phobic, and OH - -reactive diluent. The localized hydrophobicity enables less active water and less absorbed water on the Zn anode surface, which suppresses the parasitic water reductions; while the hydroxyl-ion-scavenging functionality further minimizes undesired passivation layer formation, thus leading to superior reversibility (an average Zn plating/stripping efficiency of 99.72% for 1000 cycles) and lifetime (80.6% capacity retention after 5000 cycles) of zinc batteries.

25 ENERGY STORAGE↗