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At least 307 records · Page 17

Non-gassing nickel-cadmium battery electrodes and cells

The concept of a negative limited nongassing nickel-cadmium battery was demonstrated by constructing and testing practical size experimental cells of approximately 25 Ah capacity. These batteries operated in a gas-free manner and had measured energy densities of 10-11 Wh/lb. Thirty cells were constructed for extensive testing. Some small cells were tested for over 200 cycles at 100% depth. For example, a small cell with an electrodeposited cadmium active mass on a silver screen still had 55% of its theoretical capacity (initial efficiency was 85%). There was no evidence of deterioration of gassing properties with cycling of the nickel electrodes. The charge temperature was observed to be the most critical variable governing nickel electrode gassing. This variable was shown to be age dependent. Four types of cadmium electrodes were tested: an electrodeposited cadmium active mass on a cadmium or silver substrate, a porous sintered silver substrate based electrode, and a Teflon bonded pressed cadmium electrode. The electrodeposited cadmium mass on a silver screen was found to be the best all-around electrode from a performance point of view and from the point of view of manufacturing them in a size required for a 25 Ah size battery.

Luksha, E.↗

Cell degradation quantification—a performance metric-based approach

A safe and reliable battery operation needs effective diagnostic tools. A quantitative failure analysis (FA) to enable cell qualification and quantify its effectiveness for reliable and safe operation of rechargeable Li batteries (RLB) is shown here. The method can identify and quantify potential failure based on the state of charge (SOC) under any operating conditions. A precise and accurate electrochemical analytic diagnosis (eCAD) of 14 rechargeable Li || NMC622 cells of the same build are used as an example. The FA by eCAD can quantitatively decipher good, bad and ugly cells in cycle aging. The cell qualification is based on thermodynamic SOC, not experimental conditions. The method provides a quantitative failure mode and effect analysis (FMEA) to reveal diverse “dead Li” formation that affects the reversibility of the Li anode and charge retention in the cell. This cell qualification method highlights the potential to improve cell quality for safe operation, with strong implications for early fault detection, FA, risk mitigation, state estimation and life prediction for reliable and safe RLB operations

25 ENERGY STORAGE↗

Shallow Water Optical Water Quality Buoy

This NASA grant was funded as a result of an unsolicited proposal submission to Kennedy Space Center. The proposal proposed the development and testing of a shallow water optical water quality buoy. The buoy is meant to work in shallow aquatic systems (ponds, rivers, lagoons, and semi-enclosed water areas where strong wind wave action is not a major environmental During the project period of three years, a demonstration of the buoy was conducted. The last demonstration during the project period was held in November, 1996 when the buoy was demonstrated as being totally operational with no tethered communications line. During the last year of the project the buoy was made to be solar operated by large gel cell batteries. Fund limitations did not permit the batteries in metal enclosures as hoped for higher wind conditions, however the system used to date has worked continuously for in- situ operation of over 18 months continuous deployment. The system needs to have maintenance and somewhat continuous operational attention since various components have limited lifetime ages. For example, within the last six months the onboard computer has had to be repaired as it did approximately 6 months after deployment. The spectrograph had to be repaired and costs for repairs was covered by KB Science since no ftmds were available for this purpose after the grant expired. Most recently the computer web page server failed and it is currently being repaired by KB Science. In addition, the cell phone operation is currently being ftmded by Dr. Bostater in order to maintain the system's operation. The above points need to be made to allow NASA to understand that like any sophisticated measuring system in a lab or in the field, necessary funding and maintenance is needed to insure the system's operational state and to obtain quality factor. The proposal stated that the project was based upon the integration of a proprietary and confidential sensor and probe design that was developed by KB Science and Engineering and is currently patented by KB Science. The buoy's purpose was to collected hyperspectral optical signatures for analysis and resulting estimation of water quality parameters such as chlorophyll-a, seston and dissolved organic matter (DOC). The ultimate goal of the project was to develop a buoy that would integrate a probe to measure upwelling light from a source and thus relate this backscattered light to water quality parameters.

Bostater, Charles↗

Revealing causes of macroscale heterogeneity in lithium ion pouch cells via synchrotron X-ray diffraction

Heterogeneous battery performance is a critical issue for maximization of cell lifetime capacity and safety. Using high energy synchrotron X-ray diffraction, the influence of charge rate, voltage limit, uneven stack pressure, and gas generation on the lithium transport properties was quantified in single-layer graphite/LiNi 0.5 Mn 0.3 Co 0.2 O 2 pouch cells. A freshly formatted cell tracked in operando during initial fast charge cycles indicated variable position-dependent performances, while lateral mapping showed a significant fast charge (6C) heterogeneity compared to slow charge (C/2). Pressure effects were non-dominant compared to charge rate. Maps of previously aged and rested cells indicate that lateral heterogeneity slowly equilibrates at rest, but regenerates upon further cycling at fast charge rate. Furthermore, an unformatted cell was mapped at charge and discharge during its first formation cycle to analyze the effect of byproduct gases on the heterogeneous lithium transport. Gas was observed as randomly interspersed “bubbles” which locally hindered lithium intercalation and caused significant heterogeneity. Electrode architectures and charging protocols that promote homogeneous intercalation are critical for predictable high-performance and long-life batteries.

25 ENERGY STORAGE↗

Nanoporous Carbon Coatings Direct Li Electrodeposition Morphology and Performance in Li Metal Anode Batteries

Li metal anodes could significantly improve battery energy density. However, Li generally electrodeposits in poorly controlled morphology, leading to safety and performance problems. One factor that controls Li anode performance and electrodeposition morphology is the nature of the electrolyte–current collector interface. Herein, we modify the Cu current collector interface by depositing precisely controlled nanoporous carbon (NPC) coatings using pulsed laser deposition to develop an understanding of how NPC coating density and thickness impact Li electrodeposition. We find that NPC density and thickness guide Li morphological evolution differently and dictate whether Li deposits at the NPC-Cu or NPC-electrolyte interface. NPC coatings generally lower overpotential for Li electrodeposition, though thicker NPC coatings limit kinetics when cycling at a high rate. Lower-density NPC enables the highest Coulombic efficiency (CE) during calendar aging tests, and higher-density NPC enables the highest CE during cycling tests.

25 ENERGY STORAGE↗

High accuracy in-situ direct gas analysis of Li-ion batteries

Cycling of lithium-ion batteries containing Ni-rich NMC cathodes at high voltage involves intense gas generation. From the safety standpoint, it is critical to understand how different gas species respond to changes of upper cut-off voltages. In this manuscript, we introduce a novel experimental set up for real-time analysis of gas generation in prismatic pouch cells. In a typical experiment, a lithium-ion pouch cell is directly connected to a quadruple mass spectrometer by glass capillary. Pressure difference helps move the generated gases to the mass spectrometer column for full analysis. The gaseous species are probed during both formation cycle and aging cycles in Li-ion pouch cells comprising NMC811 cathode and graphite anode. The gases are generated upon the creation of the solid electrolyte interphase on graphite during the first formation charge. Besides ethylene gas, C 2 H 4 , whose occurrence is related to the decomposition of ethylene carbonate, a minor solvent decomposition happened at a lower voltage is demonstrated to be associated with residue water on the electrode. For aging cycles, three upper cut-off voltages have been selected to investigate the gas evolution behavior upon charging to 4.2, 4.4 and 4.6 V. Higher upper cut-off voltages do not affect the amount of O 2 measured as a part of the generated oxygen could have reacted with electrolytes. Quite similar and low amounts of O 2 remain in the cells upon charging to the selected cut-off voltages. On the other hand, the generation of CO 2 has been found to be very sensitive to upper cut-off voltage. During similar aging cycles, 6167 nmol $g_{NMC}^{-1}$ of CO 2 is generated at 4.6 V, versus 1650 nmol $g_{NMC}^{-1}$ of CO 2 at 4.4 V, versus 91 nmol $g_{NMC}^{-1}$ of CO 2 at 4.2 V.

25 ENERGY STORAGE↗

Quantifying Graphite Solid-Electrolyte Interphase Chemistry and its Impact on Fast Charging

The solid-electrolyte interphase (SEI) enables the remarkable capacity retention of lithium-ion batteries, yet a comprehensive quantitative description of the SEI composition remains elusive. Using a combination of differential electrochemical mass spectrometry and mass spectrometry titration, we quantify graphite SEI components formed under electrolytes of varying salt concentrations. We find that, regardless of salt concentration, a conversion of initially deposited lithium ethylene dicarbonate to monocarbonates (likely lithium ethylene monocarbonate) and noncarbonate species occurs, and the extent of this conversion increases with electrolyte aging. Here, we additionally demonstrate that as the concentration increases (up to 2.0 M LiPF6), the SEI becomes progressively thinner with more LiF and less solid carbonates deposited. Finally, we reveal that less dead lithium formation and less solid carbonate deposition occur during prolonged fast charging for higher-concentration electrolytes. Because of the advantages imparted by a thinner SEI, the onset state of charge for lithium plating for the 2.0 M electrolyte is later than that predicted by a standard electrochemical model, underscoring the importance of explicit SEI effects in future electrochemical models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extended cycle life implications of fast charging for lithium-ion battery cathode

Enabling extreme fast charging (XFC, =10–15 min charging) requires a comprehensive understanding of its implications. While lithium plating is a key bottleneck for the anode, the full extent of limitations for the cathode are not well-understood, particularly in extended-cycle settings with well-defined battery designs and conditions. This article presents cycle-life implications of XFC on cathodes at multiple length scales, combining electrochemical analyses, degradation modeling, and post-test characterizations. The comprehensive test matrix includes 41 well-defined gr/NMC pouch cells under varied fast-charge rates (1–9C) and state-of-charges cycled up to 1000 times. Cathode issues remain minimal in early cycling, but begin to accelerate in later life, when distinct cracking is found and identified as a fatigue mechanism. The bulk structure of cathodes remains intact, but distinct particle surface reconstruction is observed; however, this shows less pronounced effect on cathode aging than does cracking.

25 ENERGY STORAGE↗

Can an Efficient Nuclear Energy Industry Still be Resilient? On the Nature of Efficiency and Resiliency in Complex Systems

At the time of writing, the nuclear industry is on the precipice of a long-hoped for, but as-yet-unrealized, “nuclear renaissance.” Nuclear power plants in the United States and around the globe are aging, emphasizing the criticality of this moment. The importance of carbon free power sources combined with advancements in nuclear technology and innovation have brought a new potential landscape. As existing reactors and utilities cope with increased economic pressure by seeking out efficiencies the push towards novel nuclear platforms like microreactors and fission batteries will only increase this quest for efficiency gains, potentially at the detriment of safety. This paper argues that the concepts of efficiency and resiliency are fundamentally linked and that the change in one necessarily affects the other. As nuclear power is known for being incredibly resilient, this dichotomy needs attention from the current wave of research towards nuclear power efficiencies. This paper argues for resiliency at any cost. We argue that this resilience-first approach is the right path for nuclear power to take in this net-zero future. The paper is laid out as follows. Section 1 introduces the economic context and resilient nature of nuclear power. Section 2 discusses efficiency, resiliency, and the struggle between the two in nuclear power. Section 3 exemplifies our argument through case studies in the aviation and manufacturing industries and extends the argument to the nuclear industry. Section 4 concludes with a discussion of the implications of this idea.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

Application of First Principles Model to Spacecraft Operations

Previous models use a single phase reaction; cycled cell predicts cannot be met with a single phase; interphase conversion provides means for film aging; aging cells predictions display typical behaviors: pressure changes in NiH² cells; voltage fading upon cycling; second plateau on discharge of cycled cells; negative limited behavior for Ni-Cds.

batteries electrodes First Principles Model Ni-Cd ↗

Calendar Life Aging of Two Models of 18650 Lithium Ion Cells

This study will analyze calendar life aging performance of two 18650 lithium ion cell models deployed in human space flight applications. Test conditions of voltage and temperature were selected based on product application. The cell test campaign includes storage of a cell model produced in April 2007 and initial calendar life performance for a cell produced in December 2013. Mechanistic aging models will be considered. The results of this study are applicable to applications requiring extended low state of charge storage and low cycle life.

18650↗

Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

Affordable, long-lasting energy storage has become critical to support increased electricity demand in recent years. Cobalt-free, lithium- and manganese-rich lithium nickel manganese oxide (LMR-NM) cathodes stand to reduce cost and supply-chain concerns associated with traditional cobalt-containing cathodes for lithium-ion batteries by leveraging more earth-abundant materials; however, they have shown issues with long-term cycling stability. Here, we investigate lithium difluoro(oxalate)borate (LiDFOB), tris(trimethylsilyl) phosphite (TMSPi), and vinylene carbonate (VC) electrolyte additives for their ability to improve cycling performance of LMR-NM (0.3 Li 2 MnO 3 + 0.7 LiMn 0.5 Ni 0.5 0 2 ) cells. Cryogenic scanning transmission electron microscopy (cryo-STEM) with electron energy loss spectroscopy enables the construction of a structure–function relationship between cathode electrolyte interphase (CEI) characteristics and the electrochemical performance of cells aged with these additives. We find the combination of 2 wt % TMSPi + 1 wt % LiDFOB performs better than any single additive, achieving a 28% improvement in specific capacity over the baseline electrolyte after long-term cycling. We attribute this to LiDFOB mitigating Mn ion dissolution, with cryo-STEM showing Mn stabilized up to the CEI surface, coupled with improved CEI structure and chemistry enabled by TMSPi, evidenced by a moderately thick (∼7–15 nm) CEI that appears to protect against further electrolyte reactions with the particle. These results, achieved through site-specific nanoscale characterization, directly reveal mechanisms through which electrolyte engineering can improve the performance of earth-abundant cathodes, enabling informed development of more affordable and reliable batteries to meet future energy storage needs.

25 ENERGY STORAGE↗

The influence of electrochemical cycling protocols on capacity loss in nickel-rich lithium-ion batteries

The transition towards electric vehicles and more sustainable transportation is dependent on lithium-ion battery (LIB) performance. Ni-rich layered transition metal oxides, such as NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ), are promising cathode candidates for LIBs due to their higher specific capacity and lower cost compared with lower Ni content materials. However, complex degradation mechanisms inhibit their use. In this work, tailored aging protocols are employed to decouple the effect of electrochemical stimuli on the degradation mechanisms in graphite/NMC811 full cells. Using these protocols, impedance measurements, and differential voltage analysis, the primary drivers for capacity fade and impedance rise are shown to be large state of charge changes combined with high upper cut-off voltage. Focused ion beam-scanning electron microscopy highlights that extensive microscale NMC particle cracking, caused by electrode manufacturing and calendering, is present prior to aging and not immediately detrimental to the gravimetric capacity and impedance. Scanning transmission electron microscopy electron energy loss spectroscopy reveals a correlation between impedance rise and the level of transition metal reduction at the surfaces of aged NMC811. The present study provides insight into the leading causes for LIB performance fading, and highlights the defining role played by the evolving properties of the cathode particle surface layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Developing rapid electrochemical relithiation protocols for scalable relithiation of lithium-ion battery cathode materials

The recent and ongoing boom in electric vehicle sales has caused the circularity of the supply chain for electric vehicle battery materials to come under a great deal of scrutiny. Innovative recycling processes, or direct recycling, that offer the possibility of reducing the cost of recycling are one possible solution to regaining resources from end-of-life (EoL) electric vehicle batteries. Electrochemically shuttling lithium back into the cathode, or electrochemical relithiation, is a possible technique for restoring lithium content to NMC materials (EoL) in a direct recycling process. This study provides essential understanding towards developing an electrochemical relithiation protocol that will restore lithium loss in intercalation cathode materials that reach EoL by loss of lithium inventory (LLI) as opposed to other degradation mechanisms like loss of active material (LAM), cation mixing or phase transition. Electrochemically aged NMC cathode materials have been prepared and characterized to establish the extent of EoL material structural degradation and lithium loss. A model-informed experimental process is used to identify the optimal electrochemical relithiation protocol to minimize the time taken to relithiate EoL materials and maximize the amount of lithium restored. Protocols were evaluated based on their ability to enable rapid lithium intercalation, maintain structural uniformity in the EoL material and fully restore lithium content. An optimal protocol was identified at elevated temperatures utilizing a novel scanning voltage step.

25 ENERGY STORAGE↗

Impacts of Solvent Washing on the Electrochemical Remediation of Commercial End-of-Life Cathodes

Changes to surface structure and chemistry occurring throughout the functional lifetime of lithium-ion batteries (LIBs) may impact the effectiveness of end-of-life rejuvenation methods. Solvent washing prior to electrochemical relithiation is shown to both increase relithiation efficacy and beneficially alter the interfacial chemistry of heavily degraded industrial cathode material. Four common solvents (acetone, diethyl carbonate, isopropyl alcohol, propylene carbonate) are employed to investigate the role of varying physicochemical solvent properties on the mechanism of capacity recovery. Electrochemical (dQ/dV, EIS), structural (XRD), and chemical (SPME-GC-MS) analysis techniques are employed to comprehensively analyze solvent-cathode interactions. Highly nucleophilic solvents (acetone, DEC) are found to reduce cathode charge-transfer impedance and enable stable impedance growth throughout subsequent cycling. The use of nucleophilic solvents under mechanically aggressive washing conditions may also enable the reintroduction of bulk lattice oxygen, thereby restoring anionic redox capacity. Further, the four solvents are found to selectively remove a subset of surface species from the aged cathode material, including residual electrolyte, additives, and electrolyte-additive reaction products, which are qualitatively analyzed. Surface species removal by each solvent is correlated with the electrochemical performance of the correspondingly washed cathode, highlighting the importance of an optimized washing protocol to effective remediation in the context of direct LIB recycling. For the material under study, the use of a simple acetone washing protocol prior to electrochemical relithiation enables up to 174% capacity recovery relative to unwashed/relithiated black mass.

ADVANCED PROPULSION SYSTEMS↗

Impacts of Dissolved Ni 2+ on the Solid Electrolyte Interphase on a Graphite Anode

Transition metal (e.g. Ni) ions dissolved from layered-structured Ni-rich cathodes can migrate to the anode side and accelerate the failure of lithium-ion batteries. The investigations of the impact and distribution of Ni species on the solid electrolyte interphase (SEI) on the anode are crucial to understand the failure mechanism. Herein, we used time-of-flight secondary ion mass spectroscopy (TOF-SIMS) coupled with multivariate curve resolution (MCR) analysis to intuitively characterize the distribution of Ni species in the SEI. We find that the SEI on the graphite electrode using an EC-based electrolyte exhibits a multi-stratum structure. During accelerated aging of the LiNi 0.88 Co 0.08 Mn 0.04 O 2 /graphite full cell, the dissolution of Ni aggravates significantly upon cycling. A strong correlation between the dissolved-Ni and organic species in the SEI on graphite is illustrated. Here, the ion-exchange reaction between Ni 2+ and Li + ions in the SEI is demonstrated to be the main reason for the increase of SEI resistivity.

25 ENERGY STORAGE↗

Manual Crew Override of Vehicle Landings Following G-Transitions

BACKGROUND Manual control during exploration spaceflight consists of both planned automated supervisory control and unplanned crew override. This crew override capability is critical to enable overall mission success during landing contingencies. However, the introduction of manual override capabilities must be implemented to enable crews to mitigate risks introduced by human error. Adaptive changes in the sensorimotor system can manifest during g-transitions as spatial disorientation. While training and landing aids enable successful landing through disorientation, these adaptive changes may increase cognitive demand that needs to be accounted for in the manual control strategy. It is important to characterize these effects as soon as possible following the G-transition to develop appropriate countermeasures. METHODS The following study seeks to inform the risk associated with altered sensorimotor and vestibular function impacting critical mission tasks. We aim to characterize the effects of short and long-duration weightlessness on manual control following G-transitions using simulated lunar landing on a six-degree-of-freedom (6DOF) motion base, a fixed base simulation, and a supervisory control tablet task. The primary goal is to understand the impact of spaceflight on crew ability to perform manual crew override and supervisory control. This aim will be assessed by comparing pre- versus postflight simulation performance in crewmembers assigned to either short duration (< 30 day) or long duration (~6- month) missions to the International Space Station (ISS). We hypothesize there will be postflight increases in the percent time that pilots are outside of the acceptable range for recommended vehicle state parameters and the reaction time for secondary cognitive tasks. Ground-based control subjects, who are demographically matched to the crew considering age (± 5 years) and gender, will undergo the same testing schedule as the crew to examine the effects of flight phase independent of microgravity exposure. The second aim is to examine how adaptive changes in vestibular and cognitive function relate to changes in manual crew override proficiency. Crew performance for a sensorimotor perceptual test battery will evaluate motion perception tracking, roll nulling, and/or vection sensitivity using the 6DOF motion base. We hypothesize that a higher severity of vestibular alterations will be associated with increased percent time outside of guidance limits. Motion sickness severity and sleepiness will also be evaluated. To determine the impact of “just-in-time” training, the third aim seeks to compare performance during on-board lunar landing tasks conducted late in-flight to early postflight. We hypothesize that proficiency on the “just-in-time” laptop trainer late in mission will be positively correlated with early postflight proficiency on the same task. The final aim will establish assessments of performance, training protocols, and the learning progression in a ground-control cohort of first-time users. RESULTS The assessment of the learning progression associated with the piloting task on the motion base system with thirty ground subjects will be reported. Learning curves will be established across four distinct sessions and within session considering trial difficulty. The difficulty of the landing task can be modulated with the landing divert distance and cross or downrange difficulty. Results may include changes in performance across multiple trials of a multi-attribute lunar tablet supervisory control task. Preliminary investigations of eighteen subjects who completed vestibular threshold and motion perception tasks offer expected performance ranges for upcoming preflight crew evaluations. The results yielded an average roll threshold of 0.46 ± 0.30 deg/s and an average roll nulling root mean square error performance of 2.52 ± 0.52 deg/s. RELEVANCE This project will deliver an operational demonstration of crew monitoring capability following spaceflight and identify potential deficits that may require remediation. Comparison of individual vestibular and cognitive changes with crew performance will help better characterize the manual control risks associated with sensorimotor alterations. Ground testing will evaluate learning progression, refine training protocols, and serve as a control cohort for comparisons to crew performance. ACKNOWLEDGEMENTS: The authors acknowledge contributions from Draper, the Dynamic Skills Trainer (DST) Lab, and the Software, Robotics, and Simulation Division toward the development of the lunar landing simulation platforms. This project is funded by the Human Health Countermeasures Element.

Hannah M. Weiss↗

Increasing Cognitive Reserve with Software - Pilot (ICARUS-Pilot)

The ICARUS-Pilot study sought to quantify and assess the potential benefit of using commercial-off-the-shelf (COTS) cognitive training software to improve cognitive performance in an astronaut-like terrestrial population. Five volunteer research subjects were recruited from the JSC employee population to mimic characteristics of the NASA astronaut population (age, education/discipline). Subject cognitive performance was assessed before and after executing eighteen sessions of remote cognitive training using six exercises within an adaptive app-based COTS software package (BrainHQ, Posit Science) on study-provided tablets. Pre- and post-training cognitive performance was measured using internal BrainHQ assessments as well as Cognition Test Battery (CTB), an independent software test developed specifically for NASA and used currently in research studies on astronauts. BrainHQ exercises were posited to map well or partially to several CTB sub-tests. Subjects provided feedback on their study experience formally via survey at the conclusion of testing and informally throughout the study if they encountered issues.

cognitive training↗