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At least 199 records · Page 11

Hydrogen in energy and information sciences

Beyond its fascinating chemistry as the first element in the Periodic Table, hydrogen is of high societal importance in energy technologies and of growing importance in energy-efficient computing. In energy, hydrogen has reemerged as a potential solution to long-term energy storage and as a carbon-free input for materials manufacturing. Its utilization and production rely on the availability of proton-conducting electrolytes and mixed proton–electron conductors for the components in fuel cells and electrolyzers. In computing, proton mediation of electronic properties has garnered attention for electrochemically controlled energy-efficient neuromorphic computing. Incorporation of substitutional and interstitial hydride ions in oxides, though only recently established, enables tuning of electronic and magnetic properties, inviting a range of possible exotic applications. This article addresses common themes in the fundamental science of hydrogen incorporation and transport in oxides as relevant to pressing technological needs. The content covers (1) lattice (or bulk) mechanisms of hydrogen transport, primarily addressing proton transport, but also touching on hydride ion transport; (2) interfacial transport; (3) exploitation of extreme external drivers to achieve unusual response; and (4) advances in methods to probe the hydrogen environment and transport pathway. The snapshot of research activities in the field of hydrogen-laden materials described here underscores exciting recent breakthroughs, remaining open questions, and breathtaking experimental tools now available for unveiling the nature of hydrogen in solid-state matter.

08 HYDROGEN↗

Surface Amorphization of Vanadium Dioxide (B) for K-ion Battery

Given the merits of low cost, fast ionic transport in electrolyte, and high operating voltage, potassium ion batteries (PIBs) are promising alternatives to lithium-ion batteries. However, developing suitable electrode materials that can reversibly accommodate large potassium ions is a great challenge. In this paper, guided by density functional theory (DFT) calculations, it is demonstrated that the strategy of interfacial engineering via surface amorphization of VO 2 (B) nanorods (SA-VO 2 ), which results in the formation of a crystalline core/amorphous shell heterostructure, enables superior K + storage performance in terms of large capacity, outstanding rate capability, and long cycle stability working as an anode for PIBs. DFT calculations reveal that the created crystalline/amorphous heterointerface in SA-VO 2 can substantially lower the surface energy, narrow the band gap, and reduce the K + diffusion barrier of VO 2 (B). These conditions enable enhanced K + storage capacity and rapid K + /electron transfer, which result in large capacity and outstanding rate capability. Using in situ X-ray diffraction and in situ transmission electron microscopy complemented by ex situ microscopic and spectroscopic techniques, it is unveiled that the superior cycling stability originates from the excellent phase reversibility with negligible strain response and robust mechanical behavior of SA-VO 2 upon (de)potassiation.

25 ENERGY STORAGE↗

NiFeCo-based catalysts in high current zero-gap anion exchange membrane water electrolyzers

Understanding degradation mechanisms in pure water anion exchange membrane water electrolyzers is essential for developing durable and precious metal-free hydrogen production systems, yet electronic, chemical, and transport-driven pathways often occur simultaneously at the anode. To separate these effects, we establish a morphology invariant Ni/Fe/Co thin film model catalyst platform using physical vapor deposition and systematically compare composition-dependent behavior under both pure water and 0.1 M KOH feeds. Devices were operated under industrially relevant current density conditions, galvanostatically at 1 A cm −2 for 24 hours; metal dissolution, ionomer oxidation, and resistance growth were quantified using inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy. Under pure-water operation, Ni-rich films showed voltage increases that correlated with rising total cell resistance (ΔV ≈ 243 mV, ΔR ≈ 0.17 Ω cm 2 ). Co-rich films maintained near constant voltages with minimal resistance change (ΔV < 10 mV, ΔR ≈ 0.03 Ω cm 2 ) but induced pronounced ionomer oxidation observed by XPS. In 0.1 M KOH, ionomer oxidation is suppressed, and impedance growth is minimized (<0.08 Ω cm 2 ) across all compositions, consistent with reduced transport limitations and improved ionic conduction relative to pure-water feeds. These results demonstrate how a controlled thin film model platform can isolate composition electrolyte relationships and provide mechanistic design principles for stable pure water anion exchange membrane electrolyzers.

Milenia Rojas Mendoza, B. [Stanford Univ., CA (Uni↗

Fast and Scalable Synthesis of LiNi 0.5 Mn 1.5 O 4 Cathode by Sol–Gel-Assisted Microwave Sintering

High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is a promising cathode material for high-energy-density and high-power-density lithium-ion batteries (LIBs). The high cost of the currently available LIBs needs to be addressed urgently for wide application in the transport sector (electric vehicles, buses) and large-scale energy storage systems (ESS). Of significance, herein, novel fast and scalable microwave-assisted synthesis of LNMO is reported, which leads to a production cost cut. X-ray diffraction (XRD) analysis confirms the formation of the desired phase with high crystallinity. Field emission scanning (FE-SEM) and transmission electron microscopy (TEM) analyses indicate that the synthesized phase is of nanometric size (50–150 nm) due to an extremely short sintering time (20 min). The material synthesized at 750 °C shows a higher initial discharge capacity (130 mA h g -1 ) than that synthesized at 650 °C (115 mA h g -1 ). The materials heat treated at higher temperatures show better electrochemical performance in terms of initial capacity, rate capability, and improved cycling. The improved electrochemical performance of LNMO at 750 °C is attributed to the formation of a stable crystal structure, low charge transfer resistance at the electrode/electrolyte interface, high electrical conductivity due to the presence of a disorder structure, and improved ionic diffusivity.

25 ENERGY STORAGE↗

Engineered MXene quantum dots for micro-supercapacitors with excellent capacitive behaviors

Micro-supercapacitors (MSCs) have drawn tremendous attention as promising candidates to power miniaturized portable/wearable electronics, but they still suffer from unsatisfactory electrochemical performance (e.g., insufficient energy density, mediocre rate capability), thus impeding their widespread applications. Here, a synergistic surface and structure engineering strategy achieved by downsizing to quantum dot scale, doping of heteroatoms, and introducing defects and functional groups is proposed to regulate the physicochemical properties of Ti 3 C 2 T x MXene. Encouragingly, the resulting MSCs based on defect-rich nitrogen-doped Ti 3 C 2 T x quantum dots (QDs) possess excellent electrochemical performance as demonstrated by large operating voltage (3.0 V in ionic liquid and 1.0 V in aqueous electrolyte), perfect rectangular CV shape even at 1000 V·s -1 , high volumetric capacitance of 33.1 F·cm -3 , and superior cycling stability after 10000 cycles. By employing experimental characterizations and density functional theory calculations, the remarkable performance of the MSCs is mainly due to the special chemical states as well as the unique surface and structural features of Ti 3 C 2 T x QDs, which offer abundant active sites, shorten ion diffusion pathways, promote ion/electron transports, and provide enhanced capacitance. Finally, this work provides a new strategy for the design of high-performance MSCs and a reference for the applications of MXene QDs in other energy-related fields.

42 ENGINEERING↗

Understanding and design of interstitial oxygen conductors

Highly efficient oxygen-active materials that react with, absorb, and transport oxygen is essential for fuel cells, electrolyzers and related applications. While vacancy-mediated oxygen-ion conductors have long been the focus of research, they are limited by high migration barriers at intermediate temperatures (400–600 °C), which hinder their practical applications. In contrast, interstitial oxygen conductors exhibit significantly lower migration barriers enabling higher ionic conductivity at lower temperatures. This review systematically examines both well-established and recently identified families of interstitial oxygen-ion conductors, focusing on how their unique structural motifs such as corner-sharing polyhedral frameworks, isolated polyhedral, and cage-like architectures, facilitate low migration barriers through interstitial and/or interstitialcy diffusion mechanisms. A central discussion of this review focuses on the evolution of design strategies, from targeted donor doping, element screening, to physical-intuition descriptor material screening and machine learning approach, which leverage computational tools to explore vast chemical spaces in search for new interstitial conductors. The success of these strategies demonstrates that a significant, largely unexplored space remains for discovering high-performing interstitial oxygen conductors. Crucial features enabling high-performance interstitial oxygen diffusion include the availability of electrons for oxygen reduction and sufficient structural flexibility with accessible volume for interstitial accommodation and migration. This review concludes with a forward-looking perspective, proposing a knowledge-driven methodology that integrates current understanding with data-centric approaches to identify promising interstitial oxygen conductors outside traditional search paradigms. These approaches are expected to significantly accelerate the development of high-performance interstitial oxygen conductors for a variety of oxygen-active applications, ultimately paving the way for more efficient and sustainable energy technologies.

Interstitial oxygen conductors↗

Synthetic Nuances to Maximize n-Type Organic Electrochemical Transistor and Thermoelectric Performance in Fused Lactam Polymers

A series of fully fused n-type mixed conduction lactam polymers p(g 7 NC n N), systematically increasing the alkyl side chain content, are synthesized via an inexpensive, nontoxic, precious-metal-free aldol polycondensation. Employing these polymers as channel materials in organic electrochemical transistors (OECTs) affords state-of-the-art n-type performance with p(g 7 NC 10 N) recording an OECT electron mobility of 1.20 x 10 -2 cm 2 V -1 s -1 and a μC* figure of merit of 1.83 F cm -1 V -1 s -1. In parallel to high OECT performance, upon solution doping with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl)dimethylamine (N-DMBI), the highest thermoelectric performance is observed for p(g 7 NC 4 N), with a maximum electrical conductivity of 7.67 S cm -1 and a power factor of 10.4 μWm -1 K -2 . These results are among the highest reported for n-type polymers. Importantly, while this series of fused polylactam organic mixed ionic-electronic conductors (OMIECs) highlights that synthetic molecular design strategies to bolster OECT performance can be translated to also achieve high organic thermoelectric (OTE) performance, a nuanced synthetic approach must be used to optimize performance. Herein, we outline the performance metrics and provide new insights into the molecular design guidelines for the next generation of high-performance n-type materials for mixed conduction applications, presenting for the first time the results of a single polymer series within both OECT and OTE applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering of Lead Selenide Quantum Dot Based Devices and Core/Shell Heterostructures

Near infrared (NIR) emitting colloidal quantum dots (QDs) such as PbSe are interesting materials for implementation in various optoelectronic devices such as solar cells, photodetectors, and radiation detectors. Material properties like size tunable emission wavelengths, facile solution processability, the possibility of carrier multiplication and Auger assisted up-conversion, and high Z number provide PbSe QDs with unique advantages over many currently available commercial materials used in these devices. In this dissertation, after an introduction to QDs in general, we first focus on synthesis of PbSe-based heterostructured QDs for study via optical spectroscopy. PbSe/CdSe QDs synthesized via cation exchange reaction were used as seeds to study the proper conditions for further CdSe or CdS shell growth. Optical spectroscopy studies show that growth of thicker CdSe shells leads to tunable visible emission, while growth of thick CdS shells can greatly increase the photoluminescence quantum yield (PLQY) observed from the intermediate CdSe shell. NIR PL lifetimes can be greatly enhanced by the growth of CdS shells, due to strong delocalization of the hole wavefunction within the PbSe core, while the electron is delocalized throughout the QD including in the CdS shell, resulting in radiative lifetimes in the tens of microseconds. Two pulse delay measurements show that Auger assisted up conversion is also taking place in these engineered QD dot heterostructures. In the sections that follow, we look at QD devices, first with a focus on novel devices fabricated from PbSe QDs, using an amine synthesis method that allows for facile in-solution ligand exchange. QD film mobilities are measured for PbSe QDs capped with various short ionic ligands. Carrier densities in PbSe QD films are calculated from C-V measurements, showing for the first time that carrier densities can be modulated by simply changing the capping ligand. vii Radiation detectors utilizing PbSe QDs capped with KI and NH4I ligands show tangible response to incident alpha radiation. Current output response to alpha radiation is dependent on strength of radiation source and amount of bias voltage applied. In the final section a critical review of hybrid layered 2D-QD photodetectors is presented. In a typical example, PbSe and PbS QDs act as the absorbing layer in phototransistor devices which utilize layered 2D materials such as graphene and transition metal dichalcogenides as transport layers. Resulting devices display high gains and improved directivities compared to QD only and 2D only devices.

36 MATERIALS SCIENCE↗

Functionalization of Electrodes with Tunable [EMIM] x [Cl] x +1 – Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (IL), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. We report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of the IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM] x [Cl] x+1 - (x = 1 – 10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insight into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM] 1 [Cl] 2 - , [EMIM] 3 [Cl] 4 - , and [EMIM] 5 [Cl] 6 - clusters. Kelvin probe microscopy provides insight into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal irreversible adsorption of Fe(CN) 6 4-/3- anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN) 6 4-/3- . Overall, our findings demonstrate that IL clusters with different size and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a High-Rate Lithium-Air Battery Using a Gaseous CO 2 Reactant

Li-air batteries are considered a potential alternative to Li-ion batteries for transportation applications due to their high theoretical specific energy. Most works in this area focus on use of O 2 as the reactant. However, newer concepts for using gaseous reactants (such as CO 2 , which has a theoretical specific energy density of 1,876 Wh/kg) provide opportunities for further exploration. The main objective of this project was the development of a novel strategy that enables operation of Li-CO 2 batteries at high-capacity and high-rate, with a long-cycle-life. The team was able to: (1) Synthesize two novel transition metal chalcogenide (TMC) catalysts that work in synergy with ionic liquid-based electrolytes to enhance the efficiency of reactions during discharge and charge processes; (2) Fabricate high-porosity cathode electrodes with 3D printing to increase electrode surface area and gas permeability; (3) Develop a multiscale modeling framework that integrates Density Functional Theory (DFT), Ab-Initio Molecular Dynamics (AIMD), classical Molecular Dynamics (MD), and Finite Element Analysis (FEA) to investigate atomic and cell-level properties of Li-CO 2 batteries; (4) Assemble a stackable Li-CO 2 pouch-cell able to deliver a capacity of >200 mAh. These achievements were realized through an integrated approach based on materials synthesis, testing, characterization, analysis, and computation. This project produced a thorough understanding of key chemical, electronic, and kinetic parameters that govern the operation of Li- CO 2 batteries in realistic conditions. The methodologies employed, and the insight generated, will be valuable beyond advancing the field of Li-CO 2 batteries

25 ENERGY STORAGE↗

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↗

2024 roadmap on magnetic microscopy techniques and their applications in materials science

Considering the growing interest in magnetic materials for unconventional computing, data storage, and sensor applications, there is active research not only on material synthesis but also characterisation of their properties. In addition to structural and integral magnetic characterisations, imaging of magnetisation patterns, current distributions and magnetic fields at nano- and microscale is of major importance to understand the material responses and qualify them for specific applications. In this roadmap, we aim to cover a broad portfolio of techniques to perform nano- and microscale magnetic imaging using superconducting quantum interference devices, spin centre and Hall effect magnetometries, scanning probe microscopies, x-ray- and electron-based methods as well as magnetooptics and nanoscale magnetic resonance imaging. The roadmap is aimed as a single access point of information for experts in the field as well as the young generation of students outlining prospects of the development of magnetic imaging technologies for the upcoming decade with a focus on physics, materials science, and chemistry of planar, three-dimensional and geometrically curved objects of different material classes including two-dimensional materials, complex oxides, semi-metals, multiferroics, skyrmions, antiferromagnets, frustrated magnets, magnetic molecules/nanoparticles, ionic conductors, superconductors, spintronic and spinorbitronic materials.

2D materials↗

Colossal oxygen vacancy formation at a fluorite-bixbyite interface

Oxygen vacancies in complex oxides are indispensable for information and energy technologies. There are several means to create oxygen vacancies in bulk materials. However, the use of ionic interfaces to create oxygen vacancies has not been fully explored. As such, we report an oxide nanobrush architecture designed to create high-density interfacial oxygen vacancies. An atomically well-defined (111) heterointerface between the fluorite CeO 2 and the bixbyite Y 2 O 3 is found to induce a charge modulation between Y 3+ and Ce 4+ ions enabled by the chemical valence mismatch between the two elements. Local structure and chemical analyses, along with theoretical calculations, suggest that more than 10% of oxygen atoms are spontaneously removed without deteriorating the lattice structure. Our fluorite–bixbyite nanobrush provides an excellent platform for the rational design of interfacial oxide architectures to precisely create, control, and transport oxygen vacancies critical for developing ionotronic and memristive devices for advanced energy and neuromorphic computing technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resonant X-ray Diffraction Reveals the Location of Counterions in Doped Organic Mixed Ionic Conductors

Organic mixed ionic–electronic conductors (OMIECs) have the potential to enable diverse new technologies, ranging from novel in situ biosensors to flexible energy storage devices and neuromorphic computing platforms. However, their complex behavior in functional films involving electrolyte-induced swelling, ion ingress, and electrochemical doping inhibits rational material design. Of critical importance is an understanding of the specific location of the ions in the volumetrically doped material, yet this information is not readily available. Here, in this report, we present the use of grazing- incidence resonant X-ray diffraction (RXRD, also known as anomalous diffraction) at S and Cl K-edges to determine the structure of a doped, prototypical, semicrystalline polymer OMIEC based on oligo(ethylene glycol) substitution of regioregular polythiophene. The RXRD measurement provides two key insights. Quantitative analysis of the RXRD allows the determination of the position of the ion relative to the polymer backbone in the crystalline regions. We find that the anion is relatively distant from the backbone, nearer to the lamella mid-plane naively in conflict with expected Coulombic attraction between the ion and the doped polymer polaron. Comparison of RXRD to Cl – fluorescence (total Cl – ) allows determination of the relative order of doping between the crystalline and amorphous regions. We find preferential doping of the crystalline regions. Both insights, the preferential doping of crystals at low potential and the specific location of the counterion with respect to the polymer backbone, are critical to developing a microscopic understanding of transport in OMIECs.

36 MATERIALS SCIENCE↗

A -type antiferromagnetic order in the Zintl-phase insulator EuZn 2 P 2

Zintl phases, containing strongly covalently bonded frameworks with separate ionically bonded ions, have emerged as a critical materials family in which to couple magnetism and strong spin-orbit coupling to drive diverse topological phases of matter. Here we report the single-crystal synthesis, magnetic, thermodynamic, transport, and theoretical properties of the Zintl compound EuZn 2 P 2 that crystallizes in the anti-La 2 O 3 (CaAl 2 Si 2 ) P-3m1 structure, containing triangular layers of Eu 2+ ions. In-plane resistivity measurements reveal insulating behavior with an estimated activation energy of E g = 0.11eV. Specific heat and magnetization measurements indicate antiferromagnetic ordering at T N = 23K. Curie-Weiss analysis of in-plane and out of plane magnetic susceptibility from T = 150 to 300 K yields p eff = 8.61 for μ 0 H⊥c and p eff = 7.74 for μ 0 H//c, close to the expected values for the 4f 7 J = S = 7/2 Eu 2+ ion and indicative of weak anisotropy. Below T N , a significant anisotropy of χ ⊥ /χ // ≈ 2.3 develops, consistent with A-type magnetic order as observed in isostructural analogs and as predicted by the density functional theory calculations reported herein. The positive Weiss temperatures of θ W =19.2K for μ 0 H⊥c and θ W =41.9K for μ 0 H//c show a similar anisotropy and suggest competing ferromagnetic and antiferromagnetic interactions. Comparing Eu magnetic ordering temperatures across trigonal EuM 2 X 2 (M= divalent metal, X= pnictide) shows that EuZn 2 P 2 exhibits the highest ordering temperature, with variations in T N correlating with changes in expected dipolar interaction strengths within and between layers and independent of the magnitude of electrical conductivity. These results provide experimental validation of the crystochemical intuition that the cation Eu 2+ layers and the anionic (M 2 X 2 ) 2– framework can be treated as electronically distinct subunits, enabling further predictive materials design.

36 MATERIALS SCIENCE↗

Neutron irradiation induced defects in oxides and their impact on the oxide properties

Understanding the irradiation-induced defects in oxides is of interest for a wide range of applications. ZnO is an interesting oxide with mixed ionic and covalent bonding that contains a variety of point defect structures—making it an excellent model for studying irradiation-induced defects and their impact on properties. Here, we investigate the effects of neutron irradiation on the formation of defects and on the structural, optical, and electrical properties of ZnO single crystals. We observe the formation of vacancies and voids via positron annihilation spectroscopy. Neutron irradiation led to a significant deterioration of the ZnO structure and formed a high concentration of point defects, vacancy clusters, and voids with large disparities in their structure across variable irradiation times. It also led to significant changes in the optical properties and sample color. Irradiation for 444 h induced a high concentration of Cu acceptors as well as a high concentration of Ga donors. Additionally, temperature-dependent Hall effect measurements revealed the competing production of donors and acceptors and showed an increase in the slope of the carrier freeze-out curve with increasing irradiation dose. This work demonstrates the combined effects of neutron irradiation in producing a wide range of structural defects, impurities, and dopants in oxides and their enormous impact on modifying the oxide structure and both the optical and electronic properties. It particularly emphasizes the importance of considering the production of new impurities and dopants during the neutron irradiation of oxides.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗