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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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Prediction of structure and cation ordering in an ordered normal-inverse double spinel

Abstract Spinels represent an important class of technologically relevant materials, used in diverse applications ranging from dielectrics, sensors and energy materials. While solid solutions combining two “single spinels” have been explored in a number of past studies, no ordered “double” spinels have been reported. Based on our first principles computations, here we predict the existence of such a double spinel compound MgAlGaO 4 , formed by an equimolar mixing of MgAl 2 O 4 normal and MgGa 2 O 4 inverse spinels. After studying the details of its atomic and electronic structure, we use a cluster expansion based effective Hamiltonian approach with Monte Carlo simulations to study the thermodynamic behavior and cation distribution as a function of temperature. Our simulations provide strong evidence for short-ranged cation order in the double spinel structure, even at significantly elevated temperatures. Finally, an attempt was made to synthesize the predicted double spinel compound. Energy Dispersive X-ray Spectrometry and X-ray diffraction Rietveld refinements were performed to characterize the single-phase chemical composition and local configurational environments, which showed a favorable agreement with the theoretical predictions. These findings suggest that a much larger number of compounds can potentially be realized within this chemical space, opening new avenues for the design of spinel-structured materials with tailored functionality.

36 MATERIALS SCIENCE↗
DOE OSTI2024

N-type molecular doping of a semicrystalline conjugated polymer through cation exchange

Control of electrical doping is indispensable in any semiconductor device, and both efficient hole and electron doping are required for many devices. In organic semiconductors, however, electron doping has been essentially more problematic compared to hole doping because in general organic semiconductors have low electron affinities and require dopants with low ionization potentials that are often air-sensitive. Here, we adapt an efficient molecular doping method, so-called ion-exchange doping, to dope electrons in a polymeric semiconductor. We initially reduce the polymeric semiconductor using one electron transfer from molecular dopants, and then the ionized dopants in the resulting air-unstable films are replaced with secondary ions via cation exchange. Improved ambient stability and crystallinity of the doped polymeric semiconductors are achieved when a specific bulky molecular cation was chosen as the secondary ion, compared to conventional methods. The presented strategy can overcome the trade-off relationship between reducing capability and ambient stability in molecular dopants, and a wider selection of dopant ions will help to realize ambient-stable electron conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Elucidating the mechanism behind the stabilization of multi-charged metal cations in water: A case study of the electronic states of microhydrated Mg2+, Ca2+ and Al3+”

Metal atoms typically have second and higher ionization potentials (IPs) that are larger than the IP of water, resulting in the Coulombic explosion of the first few [M(H2O)n]+q (q ≥ 2) clusters as the M+ + (H2O)n + or MOH+ + H3O+(H2O)n energy levels are energetically more stable than the M2+ + (H2O)n ones for small n. We present a theoretical analysis of the various electronic states correlating with the above channels that are involved in the sequential hydration of the Ca2+, Mg2+ and Al3+ cations with up to six water molecules that, for the first time, quantifies their relative shift with the degree of solvation accounting for the observed stabilization of those multi-charged metal cations in an aqueous solution. *

Miliordos, Evangelos↗
DOE OSTI2013

Influence of cationic substitutions on the first charge and reversible capacities of lithium-rich layered oxide cathodes

The reversible capacity values of lithium-rich layered oxide cathodes depend on the length (capacity) of the plateau region during the first charge. With an aim to understand the factors that control the length of the plateau region and thereby enhance the reversible capacity, the effects of various cationic substitutions in Li 1.2 Mn 0.6 Ni 0.2 O 2 have been investigated systematically. Specifically, substitutions of (i) M 3+ = Al 3+ , Cr 3+ , Fe 3+ , Co 3+ , and Ga 3+ for equal amounts of Mn 4+ and Ni 2+ in Li 1.2 Mn 0.6-0.5x Ni 0.2-0.5x M x O 2 with x = 0.06, 0.13, and 0.2, (ii) Ti 4+ for Mn 4+ in Li 1.2 Mn 0.6-x Ti x Ni 0.2 O 2 with x = 0.025, 0.05, and 0.1, and (iii) Mg 2+ for Ni 2+ in Li 1.2 Mn 0.6 Ni 0.2-x Mg x O 2 with x = 0.025, 0.05, and 0.1 have been investigated. The cationic substitutions affect the first charge capacity values both in the sloping region corresponding to the oxidation of the transition-metal ions to the 4+ state and in the plateau region corresponding to the oxidation of O 2- ions to O 2 and/or transition-metal ions beyond 4+, which control the reversible capacity values in subsequent cycles. While the changes in the sloping-region capacity could be readily understood by considering the redox activities of the transition-metal ions, the plateau-region capacity is found to depend sensitively on the metal–oxygen covalence, which is dictated by the relative positions of the metal:3d band with respect to the top of the O 2- :2p band, and electron delocalization. For instance, an overlap of the Co 3+/4+ :t 2g band with the top of the O 2- :2p band along with a partially filled t 2g band across the shared octahedral edges makes the oxygen loss from the lattice and/or oxidation beyond 4+ much more facile.

solar (photovoltaic), phonons, energy storage (inc↗
DOE OSTI2014

Hydrophenylation of ethylene using a cationic Ru( ii ) catalyst: comparison to a neutral Ru( ii ) catalyst

Charge neutral Ru(II) complexes of the type TpRu(L)(NCMe)Ph [Tp = hydridotris(pyrazolyl)borate; L = CO, PMe 3 , P(OCH 2 ) 3 CEt] have been previously reported to catalyze the hydrophenylation of ethylene (Organometallics 2012, 31, 6851-6860). Yet, catalyst longevity for the TpRu(L)(NCMe)Ph complexes is inhibited by competitive ethylene C–H activation. For example, ethylene C–H activation limits catalysis using TpRu(P(OCH 2 ) 3 CEt)(NCMe)Ph to a maximum of 20 turnover numbers for conversion of benzene and ethylene to ethylbenzene. In contrast, reaction of the cationic Ru(II) complex [(HC(pz 5 ) 3 )Ru(P(OCH 2 ) 3 CEt)(NCMe)Ph][BAr' 4 ] [HC(pz 5 ) 3 = tris(5-methyl-pyrazolyl)methane; BAr' 4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate] (0.025 mol% relative to benzene) in benzene with C 2 H 4 (15 psi) at 90 °C gives 565 turnover numbers of ethylbenzene after 131 hours. The production of 565 turnovers of ethylbenzene corresponds to an approximate one-pass 95% yield with ethylene is the limiting reagent and is a 28-fold improvement compared to the charge neutral catalyst TpRu(P(OCH 2 ) 3 CEt)(NCMe)Ph. Under identical conditions, the activity of [(HC(pz 5 ) 3 )Ru(P(OCH 2 ) 3 CEt)(NCMe)Ph][BAr' 4 ] is only 1.3 times less than TpRu(P(OCH 2 ) 3 CEt)(NCMe)Ph, but the increased stability of the cationic Ru(II) catalyst allows reactivity at much higher temperatures (up to 175 °C) and significantly enhanced rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Highly Active Electrolytes for Rechargeable Mg Batteries Based on [Mg2(μ-Cl)2]2+ Cation Complex in Dimethoxyethane

Highly active electrolytes based on a novel [Mg2(μ-Cl)2]2+ cation complex for reversible Mg deposition were developed and analyzed in this work. These electrolytes were formulated in dimethoxyethane through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI= bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The cation complex was identified for the first time as [Mg2(μ-Cl)2(DME)4]2+ (DME=dimethoxyethane) and its molecular structure was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with efficiency close to 100%, wide electrochemical window (up to 3.5V) and high ionic conductivity (> 6 mS/cm) were obtained. The electrolyte synthesis and understandings developed in this work could bring significant opportunities for rational formulation of electrolytes with the general formula [Mg2(μ-Cl)2(DME)4][anion]x for practical Mg batteries.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2016

Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations

Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4] – was investigated using inelastic neutron scattering viewed from vibrational dynamics. Here, the hydrogen release followed the softening of translational and [AlH4] – librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations

Here, photo-generated charge carrier dynamics in Ruddlesden–Popper 2D perovskites with linear ( n -BA) and branched (iso-BA) butylamine as spacing cations have been studied by using transient absorption and time-resolved photoluminescence spectroscopies. Both n -BA and iso-BA perovskites consist of mixed-phase 2D quantum wells with various layer thicknesses, where the photo-generated charges undergo inter-phase charge transfer from thinner quantum wells to thicker ones. By shortening the spacer from n -BA to iso-BA, the transfer rates are significantly increased, which can also diminish the charge accumulation in thin quantum wells induced by the unbalanced electron and hole charge transfer rates. Under high excitation intensity, the shorter spacing cation is found to further facilitate the energy transfer, which can compete with fast high-order carrier recombination and consequently improve the charge transfer efficiency. Intriguingly, we observe the existence of extra bulk 3D phases embedded within iso-BA perovskites, which can efficiently collect the confined charges within 2D phases and then transport them with faster carrier mobility and slower recombination rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Mn 2 CoReO 6 : a robust multisublattice antiferromagnetic perovskite with small A-site cations

Mn 2 CoReO 6 , the fourth known magnetic transition-metal-only double perovskite oxide (space group P2 1 /n) was synthesized here at high pressure and temperature (8 GPa, 1350 °C). Large structural distortions are induced by the small A-site Mn 2+ cations. Mn 2 CoReO 6 exhibits complex magnetic properties with a robust antiferromagnetic order (T N = 94 K) involving all cation sublattices.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Catalytic activation of ethylene C–H bonds on uniform d 8 Ir( I ) and Ni( II ) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts

The homolytic activation of the strong C–H bonds in ethylene is demonstrated, for the first time, on d 8 Ir(I) and Ni(II) single atoms in the cationic positions of zeolites H-FAU and H-BEA under ambient conditions. The oxidative addition of C 2 H 4 to the metal center occurs with the formation of a d 6 metal vinyl hydride, explaining the initiation of the olefin-polymerization cycle on d 8 M(I/II) sites in the absence of pre-existing M–H bonds. Under mild reaction conditions (80–220 °C, 1 bar), the catalytic dimerization to butenes and dehydrogenative coupling of ethylene to butadiene occurs over these catalysts. 1-Butene is not converted to butadiene under the reaction conditions applied. Post-reaction characterization of the two materials reveals that the active metal cations remain site-isolated whereas deactivation occurs due to the formation of carbonaceous deposits on the zeolites. Here, our findings have significant implications for the molecular level understanding of ethylene conversion and the development of new ways to functionalize C–H bonds under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Influence of organic cation planarity on structural templating in hybrid metal-halides

Controlling the connectivity and topology of solids is a versatile way to target desired physical properties. This is especially relevant in the realm of hybrid halide semiconductors, where the long-range connectivity of the inorganic substructural unit can lead to significant changes in optoelectronic properties such as photoluminescence, charge transport, and absorption. We present a new series of hybrid metal-halide semiconductors, (phenH 2 )BiI 5 ·H 2 O, (2,2-bpyH 2 )BiI 5 , (BrbpyH)BiI 4 ·H 2 O, (phenH 2 ) 2 Pb 3 I 10 ·2H 2 O, and (2,2-bpyH 2 ) 2 Pb 3 I 10 where (phenH 2 ) 2+ = 1,10-phenanthroline-1,10-diium, (2,2-bpyH 2 ) 2+ = 2,2'-bipyridine-1,1'-diium and (BrbpyH) + = 6,6'-dibromo-2,2'-bipyridium. These compounds allow us to observe how the planarity of the cation, induced either through structural modification in the case of (phenH 2 ) 2+ or through non-covalent interactions in (BrbpyH) + , both relative to (2,2-bpyH 2 ) 2+ , modifies the inorganic substructural unit. While the Pb 2+ series of compounds show minimal changes in inorganic connectivity, we observe large differences in the Bi 3+ series, ranging from 0-D dimers to corner- and edge-sharing 1-D chains of octahedra. We find that compounds containing (phenH 2 ) 2+ and (BrbpyH) + pack more efficiently than those with (2,2-bpyH 2 ) 2+ due to their retention of planarity leading to greater inorganic connectivity. Electronic structure calculations and optical diffuse reflectance reveal that the band gaps of these compounds are influenced by the degree of inorganic connectivity and the inorganic substructural unit distances. These results show that the structure and planarity of organic cations can directly influence both the inorganic connectivity and the optical properties that could be tuned for certain optoelectronic applications.

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

Unveiling the mechanisms of lithium dendrite suppression by cationic polymer film induced solid–electrolyte interphase modification

It is crucial to suppress lithium dendrite formation in lithium metal batteries. Formation of a good solid–electrolyte interphase (SEI) has been considered to be effective in limiting lithium dendrite growth. However, how the SEI may be modified during lithium deposition is hard to resolve due to challenges in in situ investigation of the SEI with fine details. Here, we report an in situ study that uncovers the lithium dendrite suppression mechanism arising from SEI modification by a poly(diallyldimethylammonium chloride) (PDDA) cationic polymer film, using electrochemical liquid cell transmission electron microscopy (TEM). Lithium nanogranules are obtained in the presence of the polymer film. Chemical mapping of the deposits provides remarkable details of the SEI on individual nanogranules. It shows that lithium fluorides are uniformly distributed within the inner SEI layer of individual lithium nanogranules, arising from the instantaneous reaction of the deposited lithium with PF 6 – ions accumulated by the cationic polymer film, and thus the dendritic growth of lithium is prohibited. The ability to directly measure SEI chemistry at the nanoscale down to the individual nanograins in situ and unveil its correlation with the lithium deposition behavior opens future opportunities to explore unsolved mechanisms in batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

A redox-active organic cation for safer high energy density Li-ion batteries

Ni-rich layered cathode materials are at the forefront to be deployed in high energy density Li-ion batteries for the automotive market. However, the intrinsic poor structural and interfacial stability during overcharging could trigger violent thermal failure, which severely limits their wide application. To protect the Ni-rich cathode from overcharging, we firstly report a redox-active cation, thioether-substituted diaminocyclopropenium, as an electrolyte additive to limit the cell voltage within the safe value during overcharging. The organic cation demonstrates a record-breaking electrochemical reversibility at ~4.55 V versus Li + /Li and solubility (0.5 M) in carbonate-based electrolyte. The protection capability of the additive was explored in two cell chemistries: a LiNi 0.8 Co 0.15 Al 0.05 O 2 /graphite cell and a LiNi 0.8 Co 0.15 Al 0.05 O 2 /silicon–graphene cell with areal capacities of ~2.2 mA h cm -2 and ~3 mA h cm -2 , respectively. With 0.2 M addition, the LiNi 0.8 Co 0.15 Al 0.05 O 2 /graphite cell survived 54 cycles at 0.2C with 100% overcharge. Moreover, the cell can carry an utmost 4.4 mA cm -2 (2C) with 100% overcharge and a maximum capacity of 7540% SOC at 0.2C.

25 ENERGY STORAGE↗
DOE OSTI2020

Effects of surface chemical potentials on cation segregation

Surface cation segregation on perovskite-type electrodes is one of the major issues limiting the durability of high-temperature solid-oxide electrochemical cells, and this process is strongly dependent on temperature, the external gas-environment, and impurities in air, such as CO 2 . Here cation segregation on La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) is systematically evaluated under a set of chemical potentials to determine the origin of surface segregation and the dominant factors that govern the segregation process. Temperature is the main driving force for surface strontium segregation as the thermodynamic stability of each phase varies, and the SrO particles appear primarily in a specific operating window. In addition to the required thermal energy, the presence of gaseous oxygen-containing molecules as reactants help drive the precipitation of SrO. Oxygen partial pressure (pO 2 ) controls the defect chemistry of LSCF, leading to promotion or suppression of surface segregation. The presence of CO 2 promotes the nucleation process and suppresses the surface migration step, significantly altering the surface morphology. We also show that A-site deficiency can limit the SrO segregation in certain conditions but shows no effect in others. This study reveals the impact of gas–solid interactions on surface segregation and highlights the subtle relationship between multiple segregation driving forces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Understanding cation-disordered rocksalt oxyfluoride cathodes

Partial fluorine (F) substitution into the oxygen (O) sublattice has been shown to improve cycling stability of cation-disordered Li-excess rocksalt oxide (DRX) cathodes. Detailed understanding on failure mechanisms and key optimization knowledge of fluorinated-DRX (F-DRX), however, are lacking. In the present study, we incorporate different amounts of F into a baseline DRX system, Li 1.2 Ti 0.4 Mn 0.4 O 2 (LTMO3.0, 3.0 denotes nominal Li/Mn ratio), and synthesize two oxyfluoride compounds, Li-rich Li 1.3 Ti 0.3 Mn 0.4 O 1.7 F 0.3 (LTMOF3.25) and Mn-rich Li 1.2 Ti 0.2 Mn 0.6 O 1.8 F 0.2 (LTMOF2.0) with an increased and reduced Li/Mn ratio of 3.25 and 2.0, respectively. Through careful monitoring of chemical and structural evolution, we show that cycling-induced changes are manifested not only by Mn reduction and degradation of its local coordination environment, but also by F enrichment and formation of LiF-type of domains on the surface. A “concerted-densification” based failure mechanism, involving atomic-level changes in both transition-metal cationic sublattice and oxygen/fluorine anionic sublattice, is proposed for the degradation in F-DRX cathode materials. The study reveals that increasing F content accompanied by reduced Li/Mn ratio mitigates the degradation process, offering key design strategies in achieving balanced cathode capacity and stability.

25 ENERGY STORAGE↗
DOE OSTI2022

Revealing uncommon transport in the previously unascertained very low cation clathrate-I Eu 2 Ga 11 Sn 35

In this study, high occupancy of cation sites is typical for clathrate-I compositions allowing limited tunability of the electrical properties beyond doping and elemental substitution. Herein, we report on the structure and electrical transport of single-crystal Eu 2 Ga 11 Sn 35 , the sole example of a very low (25%) cation concentration clathrate-I material with atypical transport directly attributable to the structure and stoichiometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗