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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 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Compositionally complex doping for zero-strain zero-cobalt layered cathodes

We report the high volatility of the price of cobalt and the geopolitical limitations of cobalt mining have made the elimination of Co a pressing need for the automotive industry. Owing to their high energy density and low-cost advantages, high-Ni and low-Co or Co-free (zero-Co) layered cathodes have become the most promising cathodes for next-generation lithium-ion batteries. However, current high-Ni cathode materials, without exception, suffer severely from their intrinsic thermal and chemo-mechanical instabilities and insufficient cycle life. Here, in this paper, by using a new compositionally complex (high-entropy) doping strategy, we successfully fabricate a high-Ni, zero-Co layered cathode that has extremely high thermal and cycling stability. Combining X-ray diffraction, transmission electron microscopy and nanotomography, we find that the cathode exhibits nearly zero volumetric change over a wide electrochemical window, resulting in greatly reduced lattice defects and local strain-induced cracks. In-situ heating experiments reveal that the thermal stability of the new cathode is significantly improved, reaching the level of the ultra-stable NMC-532. Owing to the considerably increased thermal stability and the zero volumetric change, it exhibits greatly improved capacity retention. This work, by resolving the long-standing safety and stability concerns for high-Ni, zero-Co cathode materials, offers a commercially viable cathode for safe, long-life lithium-ion batteries and a universal strategy for suppressing strain and phase transformation in intercalation electrodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Effect of heat treatments on superconducting properties and connectivity in K-doped BaFe2As2

Abstract Fe-based superconductors and in particular K-doped BaFe 2 As 2 (K-Ba122) are materials of interest for possible future high-field applications. However the critical current density ( J c ) in polycrystalline Ba122 is still quite low and connectivity issues are suspected to be responsible. In this work we investigated the properties of high-purity, carefully processed, K-Ba122 samples synthesized with two separate heat treatments at various temperatures between 600 and 825 °C. We performed specific heat characterization and T c -distribution analysis up to 16 T and we compared them with magnetic T c and J c characterizations, and transmission-electron-microscopy (TEM) microstructures. We found no direct correlation between the magnetic T c and J c , whereas the specific heat T c -distributions did provide valuable insights. In fact the best J c -performing sample, heat treated first at 750 °C and then at 600 °C, has the peak of the T c -distributions at the highest temperatures and the least field sensitivity, thus maximizing H c2 . We also observed that the magnetic T c onset was always significantly lower than the specific heat T c : although we partially ascribe the lower magnetization T c to the small grain size (< λ , the penetration depth) of the K-Ba122 phase, this behaviour also implies the presence of some grain-boundary barriers to current flow. Comparing the T c -distribution with J c , our systematic synthesis study reveals that increasing the first heat treatment above 750 °C or the second one above 600 °C significantly compromises the connectivity and suppresses the vortex pinning properties. We conclude that high-purity precursors and clean processing are not yet enough to overcome all J c limitations. However, our study suggests that a higher temperature T c -distribution, a larger H c2 and a better connectivity could be achieved by lowering the second heat treatment temperature below 600 °C thus enhancing, as a consequence, J c .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

A negative piezo-conductive effect from doped semiconducting polymer thin films

In the past years, piezo-conductive sensors have drawn great attention in both academic and industrial sectors. The piezo-conductive sensors made by inorganic semiconductors exhibited poor mechanical flexibility, restricting their further practical applications. In this study, we report the piezo-conductive sensors by a semiconducting polymer, poly(3,4-ethylenedioxythiophene) doped with tosylate ions (PEDOT:Tos) thin films. Systemically studies indicate that the piezo-conductive response of the PEDOT:Tos thin films is originated from the deformation of the PEDOT crystal cells and the stretched π–π distances induced by Tos. Moreover, the negative piezo-conductive effect, for the first time, is observed from PEDOT:Tos thin film under the pressure. A working mechanism is further proposed to interpret the transient from a positive to a negative piezo-conductive response within the PEDOT:Tos thin films. Our studies offer a facile route to approach effective piezo-conductive sensors based on conjugated polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Emergence of low-energy spin waves in superconducting electron-doped cuprates

In order to fully utilize the technological potential of unconventional superconductors, an enhanced understanding of the superconducting mechanism is necessary. In the best performing superconductors, the cuprates, superconductivity is intimately linked with magnetism, although the details of this coupling remain elusive. Here, we address this gap by studying the electron-doped cuprate Nd 1.85 Ce 0.15 CuO 4−δ that has an antiferromagnetic ground state when synthesized and only becomes superconducting after a reductive annealing process. Using neutron spectroscopy, we show that the as-grown crystal exhibits a large spin pseudogap in the magnetic fluctuation spectrum. Annealing removes defects introduced by the commonly employed synthesis method and significantly reduces the spin pseudogap. While the spin pseudogap in the annealed sample likely arises from superconductivity, in the as-grown sample it results from the absence of long-wavelength spin waves. These results reveal a direct connection between defects, magnetism, and superconductivity, offering new insight into the mechanisms underlying high-temperature superconductivity and guiding the design of improved superconducting materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Predicting the formation of fractionally doped perovskite oxides by a function-confined machine learning method

Abstract Fractionally doped perovskites oxides (FDPOs) have demonstrated ubiquitous applications such as energy conversion, storage and harvesting, catalysis, sensor, superconductor, ferroelectric, piezoelectric, magnetic, and luminescence. Hence, an accurate, cost-effective, and easy-to-use methodology to discover new compositions is much needed. Here, we developed a function-confined machine learning methodology to discover new FDPOs with high prediction accuracy from limited experimental data. By focusing on a specific application, namely solar thermochemical hydrogen production, we collected 632 training data and defined 21 desirable features. Our gradient boosting classifier model achieved a high prediction accuracy of 95.4% and a high F1 score of 0.921. Furthermore, when verified on additional 36 experimental data from existing literature, the model showed a prediction accuracy of 94.4%. With the help of this machine learning approach, we identified and synthesized 11 new FDPO compositions, 7 of which are relevant for solar thermochemical hydrogen production. We believe this confined machine learning methodology can be used to discover, from limited data, FDPOs with other specific application purposes.

08 HYDROGEN↗
DOE OSTI2024

Directing CO 2 electroreduction pathways for selective C 2 product formation using single-site doped copper catalysts

Manipulating the selectivity-determining step in post-C–C coupling is crucial for enhancing C 2 product specificity during electrocatalytic CO 2 reduction, complementing efforts to boost rate-determining step kinetics. Here we highlight the role of single-site noble metal dopants on Cu surfaces in influencing C–O bond dissociation in an oxygen-bound selectivity-determining intermediate, steering post-C–C coupling toward ethylene versus ethanol. Integrating theoretical and experimental analyses, we demonstrate that the oxygen binding strength of the Cu surface controls the favorability of C–O bond scission, thus tuning the selectivity ratio of ethylene-to-ethanol. The Rh-doped Cu catalyst with optimal oxygen binding energy achieves a Faradaic efficiency toward ethylene of 61.2% and an ethylene-to-ethanol Faradaic efficiency ratio of 4.51 at –0.66 V versus RHE (reversible hydrogen electrode). Integrating control of both rate-determining and selectivity-determining steps further raises ethylene Faradaic efficiency to 68.8% at 1.47 A cm -2 in a tandem electrode. Our insights guide the rational design of Cu-based catalysts for selective CO 2 electroreduction to a single C 2 product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Active Learning-driven Quantitative Synthesis-Structure-Property Relations for Improving Performance and Revealing Active Sites of Nitrogen-Doped Carbon for the Hydrogen Evolution Reaction

While quantitative structure-properties relations (QSPRs) have been developed successfully in multiple fields, catalyst synthesis affects structure and in turn performance, making simple QSPRs inadequate. Furthermore, catalysts often have multiple active sites preventing one from obtaining insights into structure-property relations. Here, we develop a data-driven quantitative synthesis-structure-property relation (QS2PRs) methodology to elucidate correlations between catalyst synthesis conditions, structural properties as well as observed performance and to provide fundamental insights into active sites and a systematic way to optimize practical catalysts. Here, we demonstrate the approach to the synthesis of nitrogen-doped catalysts (NDC) made via pyrolysis for the performance of the electrochemical hydrogen evolution reaction (HER), quantified by the onset potential and the current density. We determine crystallinity, nitrogen species type and fraction, surface area, and pore structure of the NDC’s using XRD, XPS, and BET characterization. We demonstrated that an active learning-based optimization combined with various elementary machine learning tools (regression, principal component analysis, partial least squares) can efficiently identify optimum pyrolysis conditions to tune structural characteristics and performance with concomitant savings in materials and experimental time. Unlike previous reports on the importance of pyridinic or graphitic nitrogen, we discover that the electrochemical performance is not driven by a single catalyst property; rather, it arises from a multivariate influence of nitrogen dopants, pore structure and disorder in the NDC materials. Identification of active sites can help mechanistic understanding and further catalyst improvement.

42 ENGINEERING↗
DOE OSTI2020

Engineering efficient bifunctional electrocatalysts for rechargeable zinc–air batteries by confining Fe–Co–Ni nanoalloys in nitrogen-doped carbon nanotube@nanosheet frameworks

Developing precious-metal-free bifunctional oxygen reduction and evolution reaction (ORR/OER) electrocatalysts is of great significance for several key energy conversion and storage systems, yet remains a formidable challenge. In this work, we systematically designed Fe–Co–Ni trimetallic nanoalloys encapsulated in nitrogen-doped carbon nanotube@nanosheet frameworks (FeCoNi-NC) for application as effective bifunctional ORR/OER electrocatalysts. The rational structural design of FeCoNi-NC provides hierarchical porosity coupled with greatly increased effective electrochemical specific area for exposing abundant active sites and enhanced mass-transfer capability toward the ORR/OER. Experimental observations and theoretical calculations confirmed that Fe–Co–Ni nanoalloys interacting with pyridinic nitrogen-rich carbon synergistically optimized the adsorption/desorption free energies of oxygen intermediates, thus significantly enhancing the intrinsic ORR/OER activity. Consequently, FeCoNi-NC exhibits remarkable bifunctionality for the ORR (half-wave potential of 0.89 V) and OER (1.54 V at 10 mA cm –2 ) with ΔE = 0.65 V, and even outperforms Pt/C–RuO 2 benchmarks. Moreover, the corresponding zinc–air battery shows large power density (315.2 mW cm –2 ), high capacity (803.78 mA h g –1 at 100 mA cm –2 ) and excellent cycling durability (over 100 hours at 50 mA cm –2 ), further testifying its practical applications. This work demonstrates an effective pathway to highly active non-precious-metal bifunctional catalysts toward sustainable energy technologies.

25 ENERGY STORAGE↗
DOE OSTI2021

Bandgap recovery of monolayer MoS 2 using defect engineering and chemical doping

Two-dimensional transition metal dichalcogenide materials have created avenues for exciting physics with unique electronic and photonic applications. Among these materials, molybdenum disulfide is the most known due to extensive research in understanding its electronic and optical properties. In this paper, we report on the successful growth and modification of monolayer MoS 2 (1L MoS 2 ) by controlling carrier concentration and manipulating bandgap in order to improve the efficiency of light emission. Atomic size MoS 2 vacancies were created using a Helium Ion Microscope, then the defect sites were doped with 2,3,5,6-tetrafluro7,7,8,8-tetracyanoquinodimethane (F4TCNQ). The carrier concentration in intrinsic (as-grown) and engineered 1L MoS 2 was calculated using Mass Action model. The results are in a good agreement with Raman and photoluminescence spectroscopy as well as Kelvin probe force microscopy characterizations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗