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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Zinc-iodine secondary energy storage methods, devices, and electrolytes

Disclosed are cathodes having electron-conductive high-surface-area materials, aqueous non-halide-containing electrolytes, secondary zinc-iodine energy storage devices using the same, and methods for assembling the same. The disclosed high-surface-area materials and the aqueous non-halide-containing electrolyte solutions can contribute together to the confinement of the active iodine species in the cathode and to the minimization of shuttle effects and self-discharging. The non-halide-containing electrolyte salts can facilitate preferential adsorption of the iodine species to the cathode material rather than dissolution in the aqueous electrolyte solution, thereby contributing to the confinement of the active iodine species.

25 ENERGY STORAGE↗
NASA NTRS1972

A study of gas solubilities and transport properties in fuel cell electrolytes

An analysis of the rate of heat generation on the dissolution of sparingly soluble gas in electrolytes was made, and it leads to the conclusion that the temperature changes to be expected are much too small to be measured with precision owing to the slowness of the gas dissolution. It appears that more accurate gas solubility measurements are the only real hope of improved precision in heats of solution and other thermodynamic properties.

Walker, R. D. J.↗
DOE OSTI2022

Hydroxyl Conducting Hydrogels Enable Low-Maintenance Commercially Sized Rechargeable Zn–MnO2 Batteries for Use in Solar Microgrids

Zinc (Zn)–manganese dioxide (MnO2) rechargeable batteries have attracted research interest because of high specific theoretical capacity as well as being environmentally friendly, intrinsically safe and low-cost. Liquid electrolytes, such as potassium hydroxide, are historically used in these batteries; however, many failure mechanisms of the Zn–MnO2 battery chemistry result from the use of liquid electrolytes, including the formation of electrochemically inert phases such as hetaerolite (ZnMn2O4) and the promotion of shape change of the Zn electrode. This manuscript reports on the fundamental and commercial results of gel electrolytes for use in rechargeable Zn–MnO2 batteries as an alternative to liquid electrolytes. The manuscript also reports on novel properties of the gelled electrolyte such as limiting the overdischarge of Zn anodes, which is a problem in liquid electrolyte, and finally its use in solar microgrid applications, which is a first in academic literature. Potentiostatic and galvanostatic tests with the optimized gel electrolyte showed higher capacity retention compared to the tests with the liquid electrolyte, suggesting that gel electrolyte helps reduce Mn3+ dissolution and zincate ion migration from the Zn anode, improving reversibility. Cycling tests for commercially sized prismatic cells showed the gel electrolyte had exceptional cycle life, showing 100% capacity retention for >700 cycles at 9.5 Ah and for >300 cycles at 19 Ah, while the 19 Ah prismatic cell with a liquid electrolyte showed discharge capacity degradation at 100th cycle. We also performed overdischarge protection tests, in which a commercialized prismatic cell with the gel electrolyte was discharged to 0 V and achieved stable discharge capacities, while the liquid electrolyte cell showed discharge capacity fade in the first few cycles. Finally, the gel electrolyte batteries were tested under IEC solar off-grid protocol. It was noted that the gelled Zn–MnO2 batteries outperformed the Pb–acid batteries. Additionally, a designed system nameplated at 2 kWh with a 12 V system with 72 prismatic cells was tested with the same protocol, and it has entered its third year of cycling. This suggests that Zn–MnO2 rechargeable batteries with the gel electrolyte will be an ideal candidate for solar microgrid systems and grid storage in general.

25 ENERGY STORAGE↗
DOE OSTI2025

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↗
DOE OSTI2025

In-Situ FTIR Detection of Transition Metal (TM)-Ion Dissolution From Cathodes in Li-Ion Batteries

Transition metal (TM) ions, commonly Ni and Mn, play a crucial role in Li-ion battery cathodes as the reaction centers for rapid redox reactions. A major challenge with TM-based cathodes is capacity degradation, particularly at higher operating voltages. This degradation is closely linked to the dissolution of TMs from the cathode materials and their subsequent deposition on the anode. This process not only modifies the surface structure of the cathode but, more significantly, alters the SEI composition on the anode [1-2]. The dissolution of TMs cations into a liquid electrolyte from cathode materials, such as Mn-ion dissolution from Mn-rich cathode (LMR), is detrimental to the cycling performance of Li-ion batteries [3-4]. Much attention has been paid to this issue but there remains a lack of characterization techniques which can detect the TM-ion dissolution from the cathode during electrochemical measurements. In our study, we use in-situ ATR-FTIR as an effective technique to probe the TM-ion dissolution from the cathode. We have first demonstrated the detrimental effects of TM ions on the electrochemical performance of Li-ion batteries by adding a small amount of TM salt (50 mM Mn(PF6)) to the electrolyte of a Li-ion coin cell with LFP and graphite electrode. We observed a rapid capacity fade after the first delithiation cycle. To investigate TM ion dissolution, we established a baseline IR spectrum for various TM solvation states (such as Mn and Ni) by measuring concentration-dependent IR spectra. This baseline spectrum helps us detect TM ion dissolution during battery cycling. In this work, we discuss in detail the effect of TM ions on the electrochemical performance of Li-ion batteries and the detection of TM ions during battery cycling using in-situ FTIR spectroscopy. We will compare TM dissolution between coated and uncoated cathodes to examine the effect of cathode coatings to mitigate degradation due to TM dissolution and cross-over from cathode to anode. References: (1) Zhan, C.; Wu, T.; Lu, J.; Amine, K. Dissolution, migration, anddeposition of transition metal ions in Li-ion batteries exemplified byMn-based cathodes - a critical review. Energy Environ. Sci. 2018, 11,243-257. (2) Jung, R.; Linsenmann, F.; Thomas, R.; Wandt, J.; Solchenbach,S.; Maglia, F.; Stinner, C.; Tromp, M.; Gasteiger, H. A. Nickel,Manganese, and Cobalt Dissolution from Ni-Rich NMC and TheirEffects on NMC622-Graphite Cells. J. Electrochem. Soc. 2019, 166,A378-A389. (3) Zhao, L.; Chenard, E.; Capraz, O. O.; Sottos, N. R.; White, S.R. Direct Detection of Manganese Ions in Organic Electrolyte by UV-Vis Spectroscopy. J. Electrochem. Soc. 2018, 165, A345-A348 (4) Zhang, Y.; Hu, A.; Xia, D.; Hwang, S.; Sainio, S.; Nordlund, D.;Michel, F. M.; Moore, R. B.; Li, L.; Lin, F. Operando characterization and regulation of metal dissolution and redeposition dynamics nearbattery electrode surface. Nat. Nanotechnol. 2023, 18, 790.

25 ENERGY STORAGE↗
NASA NTRS1993

Electrochemical characterization of p(+)n and n(+)p diffused InP structures

The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.

Wilt, David M.↗
NASA NTRS2005

Moisture-Induced Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

Thermal expansion mismatch stresses and interfacial sulfur activity are the major factors producing primary Al2O3 scale spallation on high temperature alloys. However, moisture-induced delayed spallation appears as a secondary, but often dramatic, illustration of an additional mechanistic detail. A historical review of delayed failure of alumina scales and TBC s on superalloys is presented herein. Similarities with metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al+3H2O=Al(OH)3+3H(+)+3e(-), is the operative mechanism. This proposal was tested by standard cathodic hydrogen charging in 1N H2SO4, applied to Rene N5 pre-oxidized at 1150 C for 1000 1-hr cycles, and monitored by weight change, induced current, and microstructure. Here cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the electrolyte alone produced neither scale spallation nor alloy dissolution. These experiments thus highlight the detrimental effects of hydrogen charging on alumina scale adhesion. It is proposed that interfacial hydrogen embrittlement is produced by moist air and is the root cause of both moisture-induced, delayed scale spallation and desktop TBC failures.

Smialek, James L.↗
NASA NTRS2008

Moisture-Induced Delayed Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

While interfacial sulfur is the primary chemical factor affecting Al2O3 scale adhesion, moisture-induced delayed spallation appears as a secondary, but impressive, mechanistic detail. Similarities with bulk metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al(sub alloy)+3(H2O)(sub air) = Al(OH)(-) (sub 3) +3H(+) may be the operative mechanism. This proposal was tested on pre-oxidized Rene N5 by standard cathodic hydrogen charging in 1N H2SO4, as monitored by weight change, induced current, and microstructure. Cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the acid electrolyte produced neither scale spallation nor alloy dissolution. Thus, hydrogen charging was detrimental to alumina scale adhesion. Moisture-induced interfacial hydrogen embrittlement is concluded to be the cause of delayed scale spallation and desktop thermal barrier coating failures.

Smialek, James L.↗
NASA NTRSDate not supplied

Computationally Guided Development of Components for High Energy Density Solid-State Lithium-Sulfur Batteries

All electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The most challenging of these technical barriers to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria1. The performance metrics for eVTOL craft, such as specific energy, specific power, and safety, exceed those of electric automobiles by a factor of two to four. Current state-of-the-art (SOA) lithium-ion batteries are incapable of meeting the key performance criteria of energy and safety for eVTOL. Therefore, next generation advanced chemistries and designs must be developed to meet required performance metrics for electric aviation2. Beyond lithium-ion chemistries, such as lithium-sulfur, show promise in their high energy, while limitations exist in their power and cyclability due to low electrical conductivity and high intermediate solubility in organic liquid electrolytes. Several strategies to overcome the low electrical conductivity involve the use of selenium as a dopant in the active sulfur material, along with the incorporation of 2-dimensional electron-conducting holey-graphene to improve the composite cathodes electronic conductivity. Furthermore, combining this chemistry with a solid-electrolyte avoids the components’ dissolution issues3. However, the development of composite solid-state cathodes is non-trivial as several components must be intimately mixed so that the active component has sufficient access to both electrons and lithium ions to undergo full electrochemical conversion. Mathematical modeling of battery components can assist experimental design through a robust and rigorous combination of computational modeling techniques covering multiple length scales. The objective is to leverage modern computational materials methods combined with battery multiphysics tools to develop radically advanced compatible cathode and electrolyte materials, build and test solid state lithium-sulfur cells and packs. A NASA-based cross-organizational team of high-powered experts combined integrated computational predictive modeling, fundamental chemistry analysis, advanced material science, and battery cell development to tackle this very challenging, multidisciplinary problem. This presentation will show a multiscale computational modeling approach that has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM modeling targets the 1-10 µm scale structures and provides electromechanical and grain interactions for predictive design guidelines for the manufacturing of solid-state components. Parameters such as particle size and volume fraction of the constituent materials were modeled and experimentally fabricated to optimize electrochemical performance through improved microstructure design. Experimental feedback was provided through ionic and electronic conductivity assessment and structural analysis of developed materials and cell components.

battery↗
DOE OSTI2022

A Dual–Phase Electrolyte for High–Energy Lithium–Sulfur Batteries

Dissolution of lithium polysulfides (LiPSs) is essential for fast cathode kinetics, but detrimental for anode stability, especially under lean electrolyte conditions. Here in this work, the phase separation phenomenon between solvents with different polarities (tetramethyl sulfone [TMS] and dibutyl ether [DBE]) is utilized to enable the design of a dual-phase electrolyte. High-polarity, high-density TMS–lithium bis(trifluoromethanesulfonyl)imide–ammonium trifluoroacetate as the cathode electrolyte strongly solvates LiPSs, which propel the sulfur redox reaction. Moreover, the composite of DBE and a polymeric ion conductor serves as the anode electrolyte. The addition of DBE in the anode side effectively prevents the crossover of corrosive species (LiPSs and ammonia trifluoroacetate), enabling a significant improvement in Li-metal anode stability. The electrode-specific dual-phase electrolyte design provides electrochemical performance superior to conventional electrolytes. Without additional electrode engineering, pouch cells assemble with the dual-phase electrolyte cycle under a lean electrolyte (4 µL mg –1 ) and low-Li-excess condition (N/P = 3) for 120 cycles.

25 ENERGY STORAGE↗
DOE OSTI2022

Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi 0.5 Mn 1.5 O 4 Cathode Films

The high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi x Mn y Co z O 2 (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF 6 decomposition and subsequent Mn 2+ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn 3+ sites on the LNMO particle surface that can disproportionate into Mn 2+ (dissolved) and Mn 4+ (s) . During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF 2 ) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF 2 decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Highly Reversible Sodium Ion Batteries Enabled by Stable Electrolyte-Electrode Interphases

Sodium (Na) ion battery is a very promising technology for the alternative energy storage systems because of the abundance and low cost of Na element in the Earth’s crust. However, the limited cycle life and safety concerns still hinder its large-scale applications. Here, we report a nonflammable localized high concentration electrolyte (sodium bis(fluorosulfonyl)imide - triethyl phosphate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (1:1.5:2 in molar ratio)), which enables a very high initial Coulombic efficiency (CE) of 97.8% for Na||Na-CNFM (O3-NaCu1/9Ni2/9Fe1/3Mn1/3O2) cells and stable cycling of Na||hard carbon (HC) cells with a capacity retention of 95.4% after 500 cycles. The HC||Na-CNFM full cells using this electrolyte retain 82.5% capacity after 200 cycles with a CE of ~99.9% compared to 48.4% capacity retention in the carbonate electrolyte (1 M NaPF6/EC+DMC (1:1 in weight)). The extremely high CE and stability of HC||Na-CNFM cells in this electrolyte can be attributed to the stable interphase layers formed on both HC anode and Na-CNFM cathode. These layers minimize undesirable reaction between HC and electrolyte, and block the dissolution of transition metal from cathode. The insight obtained in this work can be used to further improve cycling stability and safety of rechargeable batteries.

Jin, Yan↗
DOE OSTI2021

Comprehensive Insights into Nucleation, Autocatalytic Growth, and Stripping Efficiency for Lithium Plating in Full Cells

Synchrotron high-energy X-ray diffraction is used to enable nondestructive detection and quantification of heterogeneous lithium plating in working batteries. In this study a LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite pouch cell was operated under 6C fast-charge rate for greater than 1200 cycles. The magnitude and spatial distribution of lithium plating, lithium stripping, and the effect of metallic lithium deposition on lithium intercalation into graphite were quantified. Fully intercalated graphite (LiC 6 ) was detected after discharge with a lateral distribution closely correlated with lithium plating, which can be used as a higher-sensitivity indicator for lithium plating. Over an extended cycle life, the overall metallic lithium concentration followed a sigmoidal curve indicating two-stage continuous nucleation and autocatalytic growth. The lithium stripping efficiency underwent an exponential decay as a function of cycle life as the buildup of metallic lithium hindered the efficient dissolution back into the electrolyte. The findings provide direct insights into the characteristics of lithium plating and stripping under realistic fast-charge conditions.

25 ENERGY STORAGE↗
DOE OSTI2020

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

Deployment of proton-exchange membrane fuel cells is limited by the durability of Pt-nanoscale catalysts during cathodic oxygen reduction reactions. Dissolution processes on single crystalline and thin film surfaces are now correlated leading to the design of PtAu catalysts with suppressed dissolution. A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. Finally, this mitigation strategy was applied towards 3 nm Pt 3 Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Suppressing the Shuttle Effects with FeCo/SPAN Cathodes and High-Concentration Electrolytes for High-Performance Lithium–Sulfur Batteries

The shuttle effects and the sluggish redox kinetics are two of the main challenges in lithium–sulfur (Li–S) batteries, which significantly reduce the capacity of the batteries and restrict their commercialization. Herein, FeCo/sulfurized polyacrylonitrile (SPAN) is synthesized as a cathode material via the electrospinning technique and a further heat treatment. Synchrotron X-ray absorption spectroscopy confirmed the existence of Fe–S/Fe and Co–S bonds in FeCo/SPAN, which benefit the adsorptive and catalytic activities toward lithium polysulfides (LiPSs). Here, we further investigated the effect of electrolyte concentration in inhibiting the shuttle of LiPSs in Li–S batteries. Small-angle X-ray scattering (SAXS) reveals that more contact ion pairs are formed and fewer free solvent molecules exist with the increase of the electrolyte concentration, which can inhibit the dissolution and shuttle of LiPSs. Finally, the batteries assembled with high-concentration electrolytes (3 M LiTFSI in DOL/DME) exhibit a higher specific capacity retention compared to those assembled with low-concentration electrolytes. This work enriches the route to prepare Li–S batteries with the rational design of cathode materials and electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Hydrogen-Bonding Interactions in Hybrid Aqueous/Nonaqueous Electrolytes Enable Low-Cost and Long-Lifespan Sodium-Ion Storage

Although “water-in-salt” electrolytes have opened a new pathway to expand the electrochemical stability window of aqueous electrolytes, the electrode instability and irreversible proton co-insertion caused by aqueous media still hinder the practical application, even when using exotic fluorinated salts. In this study, an accessible hybrid electrolyte class based on common sodium salts is proposed, and crucially an ethanol-rich media is introduced to achieve highly stable Na-ion electrochemistry. Here, ethanol exerts a strong hydrogen-bonding effect on water, simultaneously expanding the electrochemical stability window of the hybridized electrolyte to 2.5 V, restricting degradation activities, reducing transition metal dissolution from the cathode material, and improving electrolyte–electrode wettability. The binary ethanol–water solvent enables the impressive cycling of sodium-ion batteries based on perchlorate, chloride, and acetate electrolyte salts. Notably, a Na 0.44 MnO 2 electrode exhibits both high capacity (81 mAh g –1 ) and a remarkably long cycle life >1000 cycles at 100 mA g –1 (a capacity decay rate per cycle of 0.024%) in a 1 M sodium acetate system. The Na 0.44 MnO 2 /Zn full cells also show excellent cycling stability and rate capability in a wide temperature range. The gained understanding of the hydrogen-bonding interactions in the hybridized electrolyte can provide new battery chemistry guidelines in designing promising candidates for developing low-cost and long-lifespan batteries based on other (Li + , K + , Zn 2+ , Mg 2+ , and Al 3+ ) systems.

25 ENERGY STORAGE↗