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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Triggering Anionic Redox Activity in Li 3 NbS 4 Through Cationic Disordering or Substitution

Extensive utilization of Li-ion batteries for varieties of applications necessitates ceaseless improvements of electrode materials for achieving higher energy density. Towards this goal, Li-rich layered oxides exhibiting high capacity due to cumulated cationic and anionic redox activities are under study for nearly a decade. Still, several unanswered questions remain with respect to these Li-driven anionic redox reactions in terms of the activation process and long-term consequences upon cycling. Here, the Li-rich Li 3 NbS 4 phase is focused, and synthesized as two different polymorphs, namely ordered and disordered phases. From analyses of their chemical and electrochemical properties, a crystal-electronic structure relationship is unraveled that triggers the anionic redox activity in these compounds. Moreover, through complementary theoretical calculations, the capability of cationic disorder to trigger anionic redox activity via the hybridization of cationic and non-bonding anionic energy levels is shown. This finding is further supported by the appearance of anionic redox activity by introducing the disorder through cationic substitution. Altogether, the insights derived here can help in designing new anionic redox materials with optimum performances for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Unusual water-assisted NO adsorption over Pd/FER calcined at high temperatures: The effect of cation migration

Moisture contained in vehicle exhaust gas normally degrades the capacity and efficiency of Pd ion-exchanged zeolites as NO x adsorbents by competitive adsorption on active sites. Here, we report a counterexample to this general proposition, in which moisture facilitates the storage of NO as a nitrosyl complex on hydrated Pd ions in high temperature calcined FER-type zeolites. The divalent Pd 2+ cations upon elevated temperature (>800 °C) calcination occupy cationic position that render them fully coordinated by oxygen ions of the zeolite framework, and become inactive for the adsorption of probe molecules such as NO or CO. These ‘hidden’ Pd ions, however, are accessible by NO when the zeolite is hydrated, but readily release NO at around 200°C as dehydration proceeds. Herein, by combining systematic in situ infra-red data with X-ray diffraction Rietveld analyses, we revealed that the high temperature-induced relocation of Pd ions to more stable cationic positions located near 6-membered ring of the ferrierite cage is responsible for this anomalous behavior. This discovery constitutes a notable advance in understanding coordination chemistry of cations in zeolites.

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

Tuning spin-orbit coupling towards enhancing photocurrent in hybrid organic-inorganic perovskites by using mixed organic cations

The presence of the heavy elements leads to strong spin-orbit coupling (SOC) in hybrid organic-inorganic perovskites (HOIPs), which plays an important role in the photovoltaic performance of HOIPs by changing the populations between bright and dark states. The organic cation is a critical composition and affects SOC via the interaction with the inorganic cage. In this work, we use magneto-photocurrent measurement to explore the SOC effect upon using mixed organic cations (methylammonium (MA) and formamidinium (FA)) with different dipole moments in Pb based perovskites. Magneto-photocurrent measurements showed that the internal magnetic parameter B0 is decreased from 402.41 mT to 180.18 mT and 104.58 mT with decreasing the MA/FA ratio. This provides evidence that changing the internal dipole moment by using mixed organic cations can essentially change the SOC in HOIPs. Simultaneously, the photocurrent is increased from 21.46 mA/cm 2 to 22.60 mA/cm 2 and 23.08 mA/cm 2 when the MA/FA ratio is changed from 1:0 to 0.9:0.1 and 0.7:0.3. Above all, our results indicate that the change in SOC by different organic cations can also be a factor affecting the performance of perovskite solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Alkali Metal Cation Effects on Dinitrogen Complexes and Organometallic Compounds

Alkali metal (AM) cations are often taken for granted as counterions in coordination chemistry and organometallic reactions. However, the AM cation can be more than a bystander in inorganic transformations. This Account focuses on research that has elucidated several types of AM cation effects and how these can be exploited to achieve novel structures and reactivity pathways. Here, a particular focus is on AM cation effects in low-coordinate iron β-diketiminate complexes, though we address general trends and potential applications in systems with other supporting ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solvent and A-Site Cation Control Preferred Crystallographic Orientation in Bromine-Based Perovskite Thin Films

Preferred crystallographic orientation in polycrystalline films is desirable for efficient charge carrier transport in metal halide perovskites and semiconductors. However, the mechanisms that determine the preferred orientation of halide perovskites are still not well understood. In this work, we investigate crystallographic orientation in lead bromide perovskites. We show that the solvent of the precursor solution and organic A-site cation strongly affect the preferred orientation of the deposited perovskite thin films. Specifically, we show that the solvent, dimethylsulfoxide, influences the early stages of crystallization and induces preferred orientation in the deposited films by preventing colloidal particle interactions. Additionally, the methylammonium A-site cation induces a higher degree of preferred orientation than the formamidinium counterpart. We use density functional theory to show that the lower surface energy of the (100) plane facets in methylammonium-based perovskites, compared to the (110) planes, is the reason for the higher degree of preferred orientation. In contrast, the surface energy of the (100) and (110) facets is similar for formamidinium-based perovskites, leading to lower degree of preferred orientation. Furthermore, we show that different A-site cations do not significantly affect ion diffusion in bromine-based perovskite solar cells but impact ion density and accumulation, leading to increased hysteresis. Our work highlights the interplay between the solvent and organic A-site cation which determine crystallographic orientation and plays a critical role in the electronic properties and ionic migration of solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Layered and Low-Dimensional Lead, Silver, and Bismuth Halide Perovskites Directed by Halogen-Substituted Spacer Cations

Hybrid organic–inorganic metal halides provide a diverse parameter space in which the optoelectronic properties can be tuned through the composition. The compositional tunability extends to the metal site, which can be expanded from single valent metals (e.g., Pb 2+ ) to multivalent metals (e.g., Ag + and Bi 3+ ), and the dimension (2D, 1D, or 0D). However, a deeper understanding of how the organic cations template these metal halide structures is needed. Here, we synthesize and study the structures of a series of new layered and low-dimensional metal (Pb, Ag, and Bi) halides templated by the halogenated aryl spacer cations 2-chlorobenzylammonium (2ClBZ) and 3-chloro-2-fluorobenzylammonium (3Cl2FBZ). We report new lead perovskites, (3Cl2FBZ) 2 PbBr 4 , (2ClBZ) 3 PbI 5 , and (3Cl2FBZ) 2 PbI 4 , and compare them to their silver and/or bismuth analogs (2ClBZ) 4 AgBiBr 8 , (3Cl2FBZ) 4 AgBiBr 8 , (2ClBZ) 3 Bi 2 I 9 , and (3Cl2FBZ) 4 Bi 2 I 10 . In all structures, the halogen-substituted cations result in 2D or “pseudo-2D” layering, but the different halogen substituents introduce different distortions (tilting, octahedral distortion) and dimensional reduction to 1D or 0D depending on the metal and halide compositions. Optical absorption measurements reveal the bandgaps are tunable through metal sites, dimension, and cations to different extents. Furthermore, the 1D (3Cl2FBZ) 4 Bi 2 I 10 crystallizes in the noncentrosymmetric space group Cmc2 1 and exhibits second-harmonic generation (SHG). Furthermore, the organic–inorganic interactions and resultant structural distortions examined here provide insights toward the engineering of noncentrosymmetry and dimensional control in hybrid metal halide perovskites.

Cations↗
DOE OSTI2025

Anion and Cation Size Effects on Viscoelasticity and Ion Transport of Imine Vitrimer Electrolytes

Vitrimers are a subclass of covalent adaptable networks where bond exchange occurs without breaking, thereby offering polymer materials with enhanced mechanical strength, thermal stability, and reprocessability compared to conventional electrolytes. Despite recent progress, we lack a complete understanding of the role of ions in controlling the physical and chemical properties of vitrimers. In this work, we study how different salts affect the viscoelasticity, morphology, and ionic conductivity of imine vitrimers. Our results show that addition of salt decreases relaxation times at elevated temperatures due to the catalytic effect of the cations, with smaller cations leading to faster relaxation. However, the activation energy for terminal relaxation increases with smaller cation size. This apparent discrepancy is attributed to the complex interplay among bond exchange kinetics, chain diffusion, and salt dissociation. Anions act as plasticizers by reducing the shear modulus, except lithium bromide. Ionic conductivity increases with larger anions due to smaller salt dissociation energies, whereas the cation type has a minor impact as polymer segmental dynamics dominate ionic transport. Imine-based vitrimers are reprocessable and recyclable, maintaining original mechanical properties and ionic conductivity after recovery. Mixed salt vitrimers exhibited tunable viscoelasticity and ionic conductivity intermediate to the analogous pure salt systems. Altogether, this work highlights the role of salt in the dynamic and conductive properties of imine vitrimers.

Anions↗
DOE OSTI2020

Redox Behaviors in Li-Excess Cation-Disordered Mn-Nb-O-F Rocksalt Cathode

Lithium-excess cation-disordered rocksalt oxide (DRX) is a new choice of high energy Li-ion cathode materials. DRX cathode can deliver an exceptionally high capacity of >250 mAh/g, implying the participation of cationic transition metal and anionic oxygen redox in the electrochemistry. Understanding the explicit roles of both redox reactions in the newly developed cathode is of critical importance to further development of these materials. Herein, we synthesize a representative Mn-redox-based fluorinated DRX material, Li1.2Mn0.625Nb0.175O1.95F0.05 (LMNOF). Using a comprehensive suite of electroanalytical methods, we probe the cationic and anionic redox processes and their evolution upon cycling exclusively from the electrochemical point of view. This work sheds light on understanding of cationic and anionic redox and their roles in the capacity loss for high-capacity fluorinated DRX cathode, meanwhile, showcases an explicit approach to study the electrochemistry of novel electrode materials using such non-disruptive electroanalytical methods.

Li-ion battery, high-capacity cathode, Li-excess m↗
DOE OSTI2024

From +I to +IV, Alkalis to Actinides: Capturing Cations across the Periodic Table with Keggin Polyoxometalate Ligands

Coordination chemistry trends across the periodic table are often difficult to probe experimentally due to limitations in finding a versatile but consistent chelating platform that can accommodate various elements without changing its coordination mode. Herein, we present new metal/ligand systems covering a wide range of ionic radii, charges, and elements. Five different ligands derived from the Keggin structure (HBW 11 O 39 8– , PW 11 O 39 7– , SiW 11 O 39 8– , GeW 11 O 39 8– , and GaW 11 O 39 9– ) were successfully crystallized with six different cations (Na + , Sr 2+ , Ba 2+ , La 3+ , Ce 4+ , and Th 4+ ) and characterized by single-crystal X-ray diffraction. Twenty-five new compounds were obtained by using Cs + as the counterion, yielding a consistent base formula of Cs x [M(XW 11 O 39 ) 2 ]·nH 2 O. Despite having a similar first-coordination sphere geometry (i.e., 8-coordinated), the nature of the central cation was found to impact the long-range geometry of the complexes. This unique crystallographic data set shows that, despite the traditional consensus, the local geometry of the cation (i.e., metal–oxygen bond distance) is not enough to depict the full impact of the complexed metal ion. The bending and twisting of the complexes, as well as ligand–ligand distances, were all impacted by the nature of the central cation. We also observed that counterions play a critical role by stabilizing the geometry of the M(XW 11 ) 2 complex and directing complex–complex interactions in the lattice. We also define certain structural limits for this type of complex, with the large Ba 2+ ion seemingly approaching those limits. Finally, this study thus lays the foundation for capturing the coordination chemistry of other rarer elements across the periodic table such as Ra 2+ , Ac 3+ , Bk 4+ , Cf 3+ , etc.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Quantifying the Lewis Acidity of Mono-, Di-, and Trivalent Cations in Anhydrous Bis(trifluoromethylsulfonyl)imide Salts

While the bis(trifluoromethylsulfonyl)imide anion (TFSI – ; formula [N(SO 2 CF 3 ) 2 ] – ) has been noted for its practical utility, the use of TFSI – salts as sources of Lewis acidic metal cations for studies of cation-driven tuning effects has not been reported. Here, the effective Lewis acidity of mono-, di-, and trivalent cations (namely, K + , Na + , Li + , Ba 2+ , Ca 2+ , Mg 2+ , Zn 2+ , La 3+ , Y 3+ , Lu 3+ , and Sc 3+ ) in the form of their TFSI – salts is described, along with quantitative comparisons to salts of several other weakly coordinating anions (namely, SO 3 CF 3 – , PF 6 – , and BArF 24 – ). Triphenylphosphine oxide (TPPO) was used as a 31 P NMR probe in titration experiments for quantification of key parameters describing the effective Lewis acidity of the salts in acetonitrile (CH 3 CN) solutions. Notably, the TFSI – salts of di- and trivalent cations were found to display strong binding to TPPO with significant speciation and were found to be quite hygroscopic. Taken together, the measurements demonstrate that TFSI – salts are systematically better/stronger effective Lewis acids than their triflate analogues. And, considering the excellent solubility of TFSI – salts, these materials appear attractive for further use and development in Lewis-acidity-dependent applications, including catalysis and tuning of multimetallic materials.

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

Table-Top X-ray Spectroscopy of Benzene Radical Cation

Herein, ultrafast table-top X-ray spectroscopy at the carbon K-edge is used to measure the X-ray spectral features of benzene radical cations (Bz + ). The ground state of the cation is prepared selectively by two-photon ionization of neutral benzene, and the X-ray spectra are probed at early times after the ionization by transient absorption using X-rays produced by high harmonic generation (HHG). Bz + is well-known to undergo Jahn-Teller distortion, leading to a lower symmetry and splitting of the π orbitals. Comparison of the X-ray absorption spectra of the neutral and the cation reveals a splitting of the two degenerate π* orbitals as well as an appearance of a new peak due to excitation to the partially occupied π-subshell. The π* orbital splitting of the cation, elucidated on the basis of high-level calculations in a companion theoretical paper, is discovered to be due to both the symmetry distortion and even more dominant spin coupling of the unpaired electron in the partially vacant π orbital (from ionization) with the unpaired electrons resulting from the transition from the 1s C core orbital to the fully vacant π* orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Polarizability Plays a Decisive Role in Modulating Association between Molecular Cations and Anions

Electrostatic interactions involving proteins depend on not only the ionic charges involved but also their chemical identities. Here we examine the origins of incompletely understood differences in the strength of association of different pairs of monovalent molecular ions that are relevant to protein–protein and protein–ligand interactions. Cationic analogues of the basic amino acid side chains are simulated, along with oxyanionic analogues of cation-exchange ligands and acidic amino acids. Experimentally observed association trends with respect to the cations, but not anions, are captured by a nonpolarizable model. An effective continuum correction to account for electronic polarizability can capture both trends better but at the expense of fidelity to the underlying free energy landscape for ion-pair association. Finally, a polarizable model proves decisive in capturing experimentally suggested trends with respect to both cations and anions; critically, the free energy landscape for ion-pair association is itself altered, thus altering configurational sampling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Diffusion-Limited Kinetics of Isovalent Cation Exchange in III–V Nanocrystals Dispersed in Molten Salt Reaction Media

The goal of this work is to determine the kinetic factors that govern isovalent cation exchange in III–V colloidal quantum dots using molten salts as the solvent and cation source. We focus on the reactions of InP + GaI 3 → In 1 – x Ga x P and InAs + GaI 3 → In 1–x Ga x As to create technologically important ternary III–V phases. We find that the molten salt reaction medium causes the transformation of nearly spherical InP nanocrystals to tetrahedron-shaped In 1–x Ga x P nanocrystals. Furthermore, we determine that the activation energy for the cation exchange reaction is 0.9 eV for incorporation of Ga into InP and 1.2 eV for incorporation of Ga into InAs, both much lower than the measured values in bulk semiconductors. Next, we use powder XRD simulations to constrain our understanding of the structure of the In 1–x Ga x P nanocrystals. Together our results reveal several important features of molten salt-mediated cation exchange and provide guidance for future development of these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

How Cation Migration across a 2D/3D Interface Dictates Perovskite Solar Cell Efficiency

Perovskite solar cells with 2D/3D architecture are claimed to exhibit better stability compared to pristine 3D films at room temperature. However, under illumination and/or heat, cation migration causes the exchange of the bulky spacer cations (2D phase) with the smaller A-site cations (3D phase), creating a gradient heterostructure at the 2D/3D interface. We have evaluated the performance of BA 2 MAPb 2 I 7 /MAPbI 3 (2D/3D) and MAPbI 3 (3D) solar cells at different temperatures, while simultaneously probing the absorption changes of the 2D/3D perovskite layer and the photovoltaic performance of solar cell devices. The 2D/3D solar cells were more stable at room temperature but exhibited deterioration of photovoltaic performance at high temperatures. Here, by employing in situ measurements of operating solar cells to track both the photoconversion efficiency and absorption changes at different temperatures, we show that the cation exchange at the 2D/3D interface contributes to the efficiency losses.

14 SOLAR ENERGY↗
DOE OSTI2021

Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe 2+/3+ are introduced in the Li-ion conducting phase (Li 2 SnS 3 ). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li + extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen based dual anionic and cationic redox cathode avenue.

25 ENERGY STORAGE↗
DOE OSTI2023

Probing pH-Dependent Dehydration Dynamics of Mg and Ca Cations in Aqueous Solutions with Multi-Level Quantum Mechanics/Molecular Dynamics Simulations

The dehydration of aqueous calcium and magnesium cations is the most fundamental process controlling their reactivity in chemical and biological phenomena, such as the formation of ionic solids or passing through ion channels. It holds particular relevance in light of recent advancements in the development of carbon capture techniques that rely on mineralization for long-term carbon storage. Specifically, dehydration of Ca 2+ and Mg 2+ is a key step in proposed carbon capture processes aiming to exploit the relatively high concentration of dissolved carbon dioxide in seawater via the formation of carbonate minerals from solvated Ca 2+ and Mg 2+ cations for sequestration and storage. Nevertheless, atomic-scale understanding of the dehydration of aqueous Ca 2+ and Mg 2+ cations remains limited. Here, we utilize rare event sampling via density functional theory molecular dynamics and embedded wavefunction theory calculations to elucidate the dehydration dynamics of aqueous Ca 2+ and Mg 2+ . Emphasis is placed on the investigation of the effect pH has on the stability of the different coordination environments. Here, our results reveal significant differences in the dehydration dynamics of the two cations and provide insight into how they may be modulated by pH changes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mechanistic Insights on Permeation of Water over Iron Cations in Nanoporous Silicon Oxide Films for Selective H 2 and O 2 Evolution

Electrocatalysts encapsulated by an ultrathin and semipermeable oxide layer offer a promising avenue for efficient, selective, and cost-effective production of hydrogen through photoelectrochemical water splitting. This architecture is especially attractive for Z-scheme water splitting, for which a nanoporous oxide film can be leveraged to mitigate undesired, yet kinetically facile, reactions involving redox shuttles, such as aqueous iron cations, by limiting transport of these species to catalytically active sites. In this work, molecular dynamics simulations were combined with electrochemical measurements to provide a mechanistic understanding of permeation of water and Fe(III)/Fe(II) redox shuttles through nanoporous SiO 2 films. It is shown that even for SiO 2 pores with a width as small as 0.8 nm, water does not experience any energy barrier for permeating into the pores due to a favorable interaction with hydrophilic silanol groups on the oxide surface. In contrast, permeation of Fe(III) and Fe(II) into microporous SiO 2 pores is limited due to high energy barriers, which stem from a combination of distortion and dehydration of the second and third ion solvation shells. Furthermore, our simulations and experimental results show that SiO 2 coatings can effectively mitigate undesired Fe(III)/Fe(II) redox reactions at underlying electrodes by attenuating permeation of iron cations, while allowing water to permeate and thus participate in water splitting reactions. In a broader context, our study demonstrates that selectivity of solvated cations can be manipulated by controlling the pore size and surface chemistry of oxide films.

14 SOLAR ENERGY↗
DOE OSTI2021

Application of spectroscopic evidence to diffuse layer model (DLM) parameter estimation for cation adsorption onto ferrihydrite in single- and bi-solute systems

The diffuse layer model (DLM) is one of the most frequently used surface complexation models (SCM) for predicting cation adsorption onto ferrihydrite. However, the DLM with its existing database sometimes fails to predict cation adsorption, especially in multi-solute systems. Notably, the failure is often attributed to inaccurate selection of the surface complexes and/or underestimation of the site density for DLM formulation. DLM simulations of batch adsorption data conducted with cadmium, copper, lead, and zinc on ferrihydrite in CO2 free systems demonstrates the ability of the DLM to fit single-solute data reasonably well but highlights its limitations with respect to predicting bi-solute data. Modifications to the DLM were made in two steps. First, spectroscopic evidence was used to guide cation complexation reactions at the ferrihydrite surface. Second, surface characteristics (reactive site density, specific surface area, and acidity constants) of ferrihydrite were updated according to recent literature. The results from this study suggest that when spectroscopic verification is employed and surface site density is increased, a simple two-site DLM can predict cation adsorption on ferrihydrite in single-solute systems for pH data above 3.5 and in most of the bi-solute systems tested.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗