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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Multifunctional Utilization of Pitch-Coated Carbon Fibers in Lithium-Based Rechargeable Batteries

This work reports carbon fibers as an electrode material and current collector for dual-carbon and lithium-ion batteries. Here, fully graphitic and semigraphitic carbon fibers undergo anion intercalation beyond 4.5 V versus Li/Li + . Symmetric dual-carbon full cells using a pitch-coated fully graphitic carbon fiber mat as both cathode and anode delivers an energy-density of 276 and 322 Wh kg -1 at 342 W kg -1 power density in the voltage range of 3.0–5.0 and 3.0–5.2 V, respectively. On the other hand, nongraphitic carbon fibers do not exhibit anion intercalation up to 5.2 V and can be used as a current collector. They also possess a larger number of Li + storage sites in their randomly oriented microstructure when used as an anode. A lithium-ion full cell with double carbon-coated C-LiFePO 4 loaded on nongraphitic carbon fiber as a cathode and pitch-coated nongraphitic carbon fiber as an anode exhibits 202.6 and 75.2 Wh kg -1 energy density at power densities of 46.75 W kg -1 and 11.7 kW kg -1 , respectively in 2.0–3.5 V range. This pitch-coated carbon fiber-based battery configuration eliminates the need for metal foils and costly fluorinated binders, lowers overall weight of the cell, and is capable of sustaining mechanical stress and thermal shock.

PF6− intercalation↗
DOE OSTI2026

Effects of Concentration, Salinity and Temperature on the Conformations of Zwitterionic Poly(2-Vinylpyridine- N -Oxide) Chains in Semidilute Solutions Probed by Small-Angle X-Ray and Neutron Scattering

Polyzwitterions, composed of repeating units with equal numbers of anionic and cationic groups, have drawn considerable interest for applications ranging from antimicrobial coatings and antifouling membranes to low-friction interfaces, energy storage media, and actuators. A characteristic feature of many polyzwitterions is the anti-polyelectrolyte effect salt-induced chain expansion in aqueous solution a phenomenon often implicated in their functional behavior. In this study, we investigated the conformational behavior of poly(2-vinylpyridine-N-oxide) (P2VPNO) using smallangle X-ray and neutron scattering (SAXS and SANS). Small-angle X-ray scattering (SAXS) revealed that, in salt-free aqueous solution, P2VPNO adopts an expanded wormlike conformation stabilized by hydration. With increasing concentration, the chains contract due to screening of intrachain excluded-volume interactions, qualitatively consistent with de Gennes’ scaling predictions for neutral polymers. Small-angle neutron scattering (SANS) further demonstrated that P2VPNO exhibits the characteristic anti-polyelectrolyte response to added salt, as observed in many other polyzwitterions. At elevated temperatures, chain flexibility increases, leading to a shorter Kuhn length and reduced radius of gyration. Notably, however, salt-induced chain expansion persists, indicating that the anti-polyelectrolyte effect remains operative under elevated thermal conditions. These findings provide the first experimental evidence of scaling behavior in polyzwitterions, as well as the first observation of their altered antipolyelectrolyte response at elevated temperatures, offering new insights into the solution physics of this important class of polymers.

Conformation↗
DOE OSTI2020

Breaking Scaling Relationships in CO 2 Electroreduction with Isoelectronic Analogs [Fe 4 N(CO) 12 ] – and [Fe 3 MnO(CO) 12 ] –

[Fe 4 N(CO) 12 ] – and [Fe 3 MnO(CO) 12 ] – have the same total electron count and overall charge, as well as similar reduction potentials of –1.21 and –1.17 V vs SCE in MeCN, respectively. Both clusters form the reduced hydride upon single electron transfer (ET) and proton transfer (PT). It is known that [Fe 4 N(CO) 12 ] – is an electrocatalyst for selective CO 2 reduction to formate at –1.2 V vs SCE in either pH 7 buffered water or in MeCN/H 2 O (95:5) and an effective electrocatalyst for H + reduction to H 2 under N 2 under the same conditions. In contrast, [Fe 3 MnO(CO) 12 ] – affords no products upon electrolysis, beyond [H-Fe 3 MnO(CO) 12 ] – . Herein, we determine that [H-Fe 3 MnO(CO) 12 ] – is a weaker hydride donor than [H-Fe 4 N(CO) 12 ] – by about 4 kcal mol –1 , and this is a breaking of the hydricity versus reduction potential scaling relationship previously established for a series of metal carbonyl clusters electrocatalysts.

14 SOLAR ENERGY↗
DOE OSTI2022

Morphology and Dynamics in Hydroxide-Conducting Polysulfones

In alkaline zinc–manganese dioxide batteries, there is a need for selective polymeric separators that have good hydroxide ion conductivity but that prevent the transport of zincate (Zn(OH) 4 ) 2- . Here we investigate the nanoscale structure and hydroxide transport in two cationic polysulfones that are promising for these separators. We present the synthesis and characterization for a tetraethylammonium-functionalized polysulfone (TEA-PSU) and compare it to our previous work on an N-butylimidazolium-functionalized polysulfone (NBI-PSU). We perform atomistic molecular dynamics (MD) simulations of both polymers at experimentally relevant water contents. The MD simulations show that both polymers develop well phase separated nanoscale water domains that percolate through the polymer. Calculation of the total scattering intensity from the MD simulations reveal weak or nonexistent ionomer peaks at low wave vectors. The lack of an ionomer peak is due to a loss of contrast in the scattering. The small water domains in both polymers, with median diameters on the order of 0.5–0.7 nm, lead to hydroxide and water diffusion constants that are 1–2 orders of magnitude smaller than their values in bulk water. This confinement lowers the conductivity but also may explain the strong exclusion of zincate from the PSU membranes seen experimentally.

25 ENERGY STORAGE↗
NASA NTRS1975

Development of anion-selective membranes

Methods were studied of preparing anion-exchange membranes that would have low resistance, high selectivity, and physical and chemical stability when used in acidic media in a redox energy storage system. Of the twelve systems selected for study, only the system that was based on crosslinked poly-4-vinylpyridinium chloride produced physically strong membranes when equilibrated in l M HCl. The resistivity of the best membrane was 12 ohm-cm, and the transference number for chloride ions was 0.81.

Lacey, R. E.↗
DOE OSTI2020

EFRC Accomplishments 2014-2020: NorthEast Center for Chemical Energy Storage (NECCES)

The mission of NECCES is to develop an understanding of how key electrode reactions occur in cathode materials for Li based batteries, and how they can be controlled to improve electrochemical performance, from the atomistic level to the macroscopic level through the life-time of the operating battery. This mission will allow the determination of the ultimate limits of intercalation reactions for chemical energy storage. The approach and specific research goals of NECCES are to: 1. Attain reversible multi-electron transfer in a cathode material using lithium, using the model compound ε -VOPO 4 ; 2. Close the gap between the theoretical and practical energy density for intercalation compounds, using the model compound LiNi 0.85 Co 0 .10Al 0.05 O 2 ; 3. Understand the transition from cation redox to anion redox electrochemistry; 4. Understand performance limiting transport in positive electrode structures from the local through the meso to the macroscale.

25 ENERGY STORAGE↗
DOE OSTI2020

Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes

Owing to the capacity boost from oxygen redox activities, Li-rich cation-disordered rocksalts (LRCDRS) represent a new class of promising high-energy Li-ion battery cathode materials. Redox-inactive transition-metal (TM) cations, typically d 0 TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d 0 TM (Nb 5+ and Ti 4+ ) is systematically compared on the redox chemistry of Mn-based model LRCDRS cathodes, namely Li 1.3 Nb 0.3 Mn 0.4 O 2 (LNMO), Li 1.25 Nb 0.15 Ti 0.2 Mn 0.4 O 2 (LNTMO), and Li 1.2 Ti 0.4 Mn 0.4 O 2 (LTMO). Although electrochemically inactive, d 0 TM serves as a modulator for oxygen redox, with Nb 5+ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X-ray scattering reveal that Ti 4+ is better in stabilizing the oxidized oxygen anions (O n- , 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d 0 TM on degradation mechanism further suggests that proper design of redox-inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

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↗
DOE OSTI2020

Designing a hybrid electrode toward high energy density with a staged Li + and PF 6 - deintercalation/intercalation mechanism

Existing lithium-ion battery technology is struggling to meet our increasing requirements for high energy density, long lifetime, and low-cost energy storage. Here, a hybrid electrode design is developed by a straightforward reengineering of commercial electrode materials, which has revolutionized the “rocking chair” mechanism by unlocking the role of anions in the electrolyte. Our proof-of-concept hybrid LiFePO 4 (LFP)/graphite electrode works with a staged deintercalation/intercalation mechanism of Li + cations and PF 6 - anions in a broadened voltage range, which was thoroughly studied by ex situ X-ray diffraction, ex situ Raman spectroscopy, and operando neutron powder diffraction. Introducing graphite into the hybrid electrode accelerates its conductivity, facilitating the rapid extraction/insertion of Li + from/into the LFP phase in 2.5 to 4.0 V. This charge/discharge process, in turn, triggers the in situ formation of the cathode/electrolyte interphase (CEI) layer, reinforcing the structural integrity of the whole electrode at high voltage. Consequently, this hybrid LFP/graphite-20% electrode displays a high capacity and long-term cycling stability over 3,500 cycles at 10 C, superior to LFP and graphite cathodes. Importantly, the broadened voltage range and high capacity of the hybrid electrode enhance its energy density, which is leveraged further in a full-cell configuration.

25 ENERGY STORAGE↗
DOE OSTI2021

High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells

Low-temperature direct ammonia fuel cells (DAFCs) use carbon-neutral ammonia as a fuel, which has attracted increasing attention recently due to ammonia's low source-to-tank energy cost, easy transport and storage, and wide availability. However, current DAFC technologies are greatly limited by the kinetically sluggish ammonia oxidation reaction (AOR) at the anode. Herein, we report an AOR catalyst, in which ternary PtIrZn nanoparticles with an average size of 2.3 ± 0.2 nm were highly dispersed on a binary composite support comprising cerium oxide (CeO 2 ) and zeolitic imidazolate framework-8 (ZIF-8)-derived carbon (PtIrZn/CeO 2 -ZIF-8) through a sonochemical-assisted synthesis method. Additionally, the PtIrZn alloy, with the aid of abundant OH ad provided by CeO 2 and uniform particle dispersibility contributed by porous ZIF-8 carbon (surface area: ~600 m 2 g -1 ), has shown highly efficient catalytic activity for the AOR in alkaline media, superior to that of commercial PtIr/C. The rotating disk electrode (RDE) results indicate a lower onset potential (0.35 vs. 0.43 V), relative to the reversible hydrogen electrode at room temperature, and a decreased activation energy (~36.7 vs. 50.8 kJ mol -1 ) relative to the PtIr/C catalyst. Notably, the PtIrZn/CeO 2 -ZIF-8 catalyst was assembled with a high-performance hydroxide anion-exchange membrane to fabricate an alkaline DAFC, reaching a peak power density of 91 mW cm -2 . Unlike in aqueous electrolytes, supports play a critical role in improving uniform ionomer distribution and mass transport in the anode. PtIrZn nanoparticles on silicon dioxide (SiO 2 ) integrated with carboxyl-functionalized carbon nanotubes (CNT–COOH) were further studied as the anode in a DAFC. A significantly enhanced peak power density of 314 mW cm -2 was achieved. Density functional theory calculations elucidated that Zn atoms in the PtIr alloy can reduce the theoretical limiting potential of *NH 2 dehydrogenation to *NH by ~0.1 V, which can be attributed to a Zn-modulated upshift of the Pt–Ir d-band that facilitates the N–H bond breakage.

25 ENERGY STORAGE↗
DOE OSTI2024

High–Energy Earth–Abundant Cathodes with Enhanced Cationic/Anionic Redox for Sustainable and Long–Lasting Na–Ion Batteries

Layered iron/manganese-based oxides are a class of promising cathode materials for sustainable batteries due to their high energy densities and earth abundance. However, the stabilization of cationic and anionic redox reactions in these cathodes during cycling at high voltage remain elusive. Here, an electrochemically/thermally stable P2-Na 0.67 Fe 0.3 Mn 0.5 Mg 0.1 Ti 0.1 O 2 cathode material with zero critical elements is designed for sodium-ion batteries (NIBs) to realize a highly reversible capacity of ≈210 mAh g –1 at 20 mA g –1 and good cycling stability with a capacity retention of 74% after 300 cycles at 200 mA g –1 , even when operated with a high charge cut-off voltage of 4.5 V versus sodium metal. Combining a suite of cutting-edge characterizations and computational modeling, it is shown that Mg/Ti co-doping leads to stabilized surface/bulk structure at high voltage and high temperature, and more importantly, enhances cationic/anionic redox reaction reversibility over extended cycles with the suppression of other undesired oxygen activities. This work fundamentally deepens the failure mechanism of Fe/Mn-based layered cathodes and highlights the importance of dopant engineering to achieve high-energy and earth-abundant cathode material for sustainable and long-lasting NIBs.

25 ENERGY STORAGE↗
DOE OSTI2019

Krypton storage capacity of the Earth's lower mantle

Noble gases are important geochemical tracers allowing reconstructing global volatile cycles in Earth's reservoirs. To constrain these fundamental processes, precise data on their partitioning behavior at deep Earth conditions are needed. Such data are only available at moderate pressures up to 25 GPa due to experimental challenges. We have investigated the possibility of noble gas storage in the Earth's lower mantle up to 115 GPa. We studied the incorporation of krypton in the second most abundant lower mantle mineral (Mg 1-x ,Fe x )O (ferropericlase) as well as in liquid metal-alloys by performing experiments up to 115 GPa and 3700 K using the laser-heated diamond anvil cell coupled to post-mortem EMPA analysis and X-ray absorption spectroscopy. The results reveal that, at these extreme conditions, up to 3 wt.% of krypton can be stored in (Mg 1-x ,Fe x )O and 3000 ppm in the Fe-rich liquid metal. For both phases the storage capacities increase with pressure (between 40 GPa and 60 GPa) at a constant high temperature of 2300 K. Fpc has never been considered as a NG host, despite being the second most abundant mineral in the Earth's LM. Using recent accurate compressibility data, we demonstrate that a substitution of krypton into the anion site of (Mg 1-x ,Fe x )O in form of neutral oxygen Schottky defects at diluted lower mantle conditions is possible. This noble gas incorporation mechanism is in agreement with a previous study on bridgmanite. We show that (Mg 1-x ,Fe x )O exhibits higher noble gas storage capacities than bridgmanite through the lower mantle using lattice strain modeling and including experimental solubility and thermoelastic data for neon, argon, krypton and xenon. We also demonstrate that both phases exhibit the highest solubilities for argon and krypton. We used the solubility data from lattice strain modeling to predict noble gas abundances stored in the solid lower mantle after magma ocean crystallization. The modeled abundances show apparent similarities with estimates for the deep noble gas reservoir that are based on either 3He abundances in ocean island basalts or radiogenic 40Ar abundances in the bulk Earth. This strongly indicates that the crystalline lower mantle may play an important role as deep noble gas storage reservoir. We propose, based on considerations on noble gas replenishment from the lower mantle to the atmosphere, that the lower mantle can only contribute to a small fraction of the present-day atmospheric noble gases. This suggests that the lower mantle is an un-degassed reservoir.

58 GEOSCIENCES↗
DOE OSTI2022

In Situ Studies of the Swelling by an Electrolyte in Electrochemical Doping of Ethylene Glycol-Substituted Polythiophene

Organic mixed ionic electronic conductors (OMIECs) have the potential to enable diverse new technologies, ranging from biosensors to flexible energy storage devices and neuromorphic computing platforms. However, a study of these materials in their operating state, which convolves both passive and potential-driven solvent, cation, and anion ingress, is extremely difficult, inhibiting rational material design. In this report, we present a novel approach to the in situ studies of the electrochemical switching of a prototypical OMIEC based on oligoethylene glycol (oEG) substitution of semicrystalline regioregular polythiophene via grazing-incidence X-ray scattering. Here by studying the crystal lattice both dry and in contact with the electrolyte while maintaining potential control, we can directly observe the evolution of the crystalline domains and their relationship to film performance in an electrochemically gated transistor. Despite the oEG side-chain enabling bulk electrolyte uptake, we find that the crystalline regions are relatively hydrophobic, exhibiting little (less than one water per thiophene) swelling of the undoped polymer, suggesting that the amorphous regions dominate the reported passive swelling behavior. With applied potential, we observe that the π–π separation in the crystals contracts while the lamella spacing increases in a balanced fashion, resulting in a negligible change in the crystal volume. The potential-induced changes in the crystal structure do not clearly correlate to the electrical performance of the film as an organic electrochemical transistor, suggesting that the transistor performance is strongly influenced by the amorphous regions of the film.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A high-capacity cathode for rechargeable K-metal battery based on reversible superoxide-peroxide conversion

Abstract As a promising low-cost energy storage device, the development of a rechargeable potassium-ion battery (KIB) is severely hindered by the limited capacity of cathode candidates. Regarded as an attractive capacity-boosting strategy, triggering the O-related anionic redox activity has not been achieved within a sealed KIB system. Herein, in contrast to the typical gaseous open K-O2 battery (O2/KO2 redox), we originally realize the reversible superoxide/peroxide (KO2/K2O2) interconversion on a KO2-based cathode. Controlled within a sealed cell environment, the irreversible O2 evolution and electrolyte decomposition (induced by superoxide anion (O2−) formation) are effectively restrained. Rationally controlling the reversible depth-of-charge at 300 mAh/g (based on the mass of KO2), no obvious cell degradation can be observed during 900 cycles. Moreover, benefitting from electrolyte modification, the KO2-based cathode is coupled with a limited amount of K-metal anode (merely 2.5 times excess), harvesting a K-metal full-cell with high energy efficiency (∼90%) and long-term cycling stability (over 300 cycles).

25 ENERGY STORAGE↗
DOE OSTI2022

Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials

Super alkali-rich materials (alkali:transition metal ratio of ≥2:1), such as Li 5 FeO 4 , exhibit the potential to realize anionic redox upon deep delithiation. Li 5 FeO 4 was shown to undergo reversible cycling between Li 4 FeO 3.5 and Li 3 FeO 3.5 with combined cation/anion redox, a remarkable capacity of 189 mAh/g, and no O 2 release. However, the impact of phase transformations on the reaction thermodynamics and the correlation between the structural changes and reaction reversibility remain unclear. In this study, we use first-principles calculations to examine the delithiation and (re)lithiation reactions of Li 5 FeO 4 . We show that the experimentally observed charge and discharge processes go through non-equilibrium pathways. Upon delithiation, the compound undergoes a phase transformation from Li 5 FeO 4 , with tetrahedrally coordinated (T d ) Fe ions, to a delithiated disordered rocksalt structure, with octahedral (O h ) Fe ions. Fe-ion migration has an asymmetric kinetic barrier that makes T d → O h migration facile, whereas the reverse process has a much larger barrier, explaining the difficulties in reaction reversibility. We further elucidate the transition metal and O redox sequences during the charge cycle and identify the complex electrochemistry associated with the dual participation of cationic redox (Fe 3+ /Fe 4+ ) and anionic redox (O 2– /O – /O o ). Armed with this knowledge, we conduct high-throughput screening of known alkali-rich transition metal oxides by evaluating their potential to enable reversible anionic redox, with multiple candidates proposed for further experimental trials. Furthermore, our work provides a useful guide for the further development of super alkali-rich anionic-redox-active electrodes for high-energy-density batteries.

25 ENERGY STORAGE↗