Strong Local Polarization Fluctuations Enabled High Electrostatic Energy Storage in Pb-Free Relaxors.

Electrostatic energy-storage ceramic capacitors are essential components of modern electrified power systems. However, improving their energy-storage density while maintaining high efficiency to facilitate cutting-edge miniaturized and integrated applications remains an ongoing challenge. Herein, we report a record-high energy-storage density of 20.3 J cm-3 together with a high efficiency of 89.3% achieved by constructing a relaxor ferroelectric state with strongly enhanced local polarization fluctuations. This is realized by incorporating highly polarizable, heterovalent, and large-sized Zn and Nb ions into a Bi0.5Na0.5TiO3-BaTiO3 ferroelectric matrix with very strong tetragonal distortion. Element-specific local structure analysis revealed that the foreign ions strengthen the magnitude of the unit-cell polarization vectors while simultaneously reducing their orientation anisotropy and forming strong fluctuations in both magnitude and orientation within 1-3 nm polar clusters. This leads to a particularly high polarization variation (ΔP) of 72 µC cm-2, low hysteresis, and a high effective polarization coefficient at a high breakdown strength of 80 kV mm-1. This work has surpassed the current energy density limit of 20 J cm-3 in bulk Pb-free ceramics and has demonstrated that controlling the local structure via the chemical composition design can open up new possibilities for exploring relaxors with high energy-storage performance.

Chemical Framework to Design Linear-like Relaxors toward Capacitive Energy Storage.

ABO3-type perovskite relaxor ferroelectrics (RFEs) have emerged as the preferred option for dielectric capacitive energy storage. However, the compositional design of RFEs with high energy density and efficiency poses significant challenges owing to the vast compositional space and the absence of general rules. Here, we present an atomic-level chemical framework that captures inherent characteristics in terms of radius and ferroelectric activity of ions. By categorizing A/B-site ions as host framework, rattling, ferroelectrically active, and blocking ions and assembling these four types of ions with specific criteria, linear-like relaxors with weak locally correlated and highly extendable unit-cell polarization vectors can be constructed. As example, we demonstrate two new compositions of Bi0.5K0.5TiO3-based and BaTiO3-based relaxors, showing extremely high recoverable energy densities of 17.3 and 12.1 J cm-3, respectively, both with a high efficiency of about 90%. Further, the role of different types of ions in forming heterogeneous polar structures is identified through element-specific local structure analysis using neutron total scattering combined with reverse Monte Carlo modeling. Our work not only opens up new avenues toward rational compositional design of high energy storage performance lead-free RFEs but also sheds light on atomic-level manipulation of functional properties in compositionally complex ferroelectrics.

Outstanding Energy-Storage Density Together with Efficiency of above 90% via Local Structure Design.

Dielectric ceramic capacitors with high recoverable energy density (Wrec) and efficiency (η) are of great significance in advanced electronic devices. However, it remains a challenge to achieve high Wrec and η parameters simultaneously. Herein, based on density functional theory calculations and local structure analysis, the feasibility of developing the aforementioned capacitors is demonstrated by considering Bi0.25Na0.25Ba0.5TiO3 (BNT-50BT) as a matrix material with large local polarization and structural distortion. Remarkable Wrec and η of 16.21 J/cm3 and 90.5% have been achieved in Bi0.25Na0.25Ba0.5Ti0.92Hf0.08O3 via simple chemical modification, which is the highest Wrec value among reported bulk ceramics with η greater than 90%. The examination results of local structures at lattice and atomic scales indicate that the disorderly polarization distribution and small nanoregion (∼3 nm) lead to low hysteresis and high efficiency. In turn, the drastic increase in local polarization activated via the ultrahigh electric field (80 kV/mm) leads to large polarization and superior energy storage density. Therefore, this study emphasizes that chemical design should be established on a clear understanding of the performance-related local structure to enable a targeted regulation of high-performance systems.

Local Chemical Clustering Enabled Ultrahigh Capacitive Energy Storage in Pb-Free Relaxors.

Designing Pb-free relaxors with both a high capacitive energy density (Wrec) and high storage efficiency (η) remains a remarkable challenge for cutting-edge pulsed power technologies. Local compositional heterogeneity is crucial for achieving complex polar structure in solid solution relaxors, but its role in optimizing energy storage properties is often overlooked. Here, we report that an exceptionally high Wrec of 15.2 J cm-3 along with an ultrahigh η of 91% can be achieved through designing local chemical clustering in Bi0.5Na0.5TiO3-BaTiO3-based relaxors. A three-dimensional atomistic model derived from neutron/X-ray total scattering combined with reverse Monte Carlo method reveals the presence of subnanometer scale clustering of Bi, Na, and Ba, which host differentiated polar displacements, and confirming the prediction by density functional theory calculations. This leads to a polar state with small polar clusters and strong length and direction fluctuations in unit-cell polar vectors, thus manifesting improved high-field polarizability, steadily reduced hysteresis, and high breakdown strength macroscopically. The favorable polar structure features also result in a unique field-increased η, excellent stability, and superior discharge capacity. Our work demonstrates that the hidden local chemical order exerts a significant impact on the polarization characteristic of relaxors, and can be exploited for accessing superior energy storage performance.

Chemical Design of Pb-Free Relaxors for Giant Capacitive Energy Storage.

Dielectric capacitors have captured substantial attention for advanced electrical and electronic systems. Developing dielectrics with high energy density and high storage efficiency is challenging owing to the high compositional diversity and the lack of general guidelines. Herein, we propose a map that captures the structural distortion (δ) and tolerance factor (t) of perovskites to design Pb-free relaxors with extremely high capacitive energy storage. Our map shows how to select ferroelectric with large δ and paraelectric components to form relaxors with a t value close to 1 and thus obtaining eliminated hysteresis and large polarization under a high electric breakdown. Taking the Bi0.5Na0.5TiO3-based solid solution as an example, we demonstrate that composition-driven predominant order-disorder characteristic of local atomic polar displacements endows the relaxor with a slushlike structure and strong local polar fluctuations at several nanoscale. This leads to a giant recoverable energy density of 13.6 J cm-3, along with an ultrahigh efficiency of 94%, which is far beyond the current performance boundary reported in Pb-free bulk ceramics. Our work provides a solution through rational chemical design for obtaining Pb-free relaxors with outstanding energy-storage properties.

Superior Capacitive Energy-Storage Performance in Pb-Free Relaxors with a Simple Chemical Composition.

Chemical design of lead-free relaxors with simultaneously high energy density (Wrec) and high efficiency (η) for capacitive energy-storage has been a big challenge for advanced electronic systems. The current situation indicates that realizing such superior energy-storage properties requires highly complex chemical components. Herein, we demonstrate that, via local structure design, an ultrahigh Wrec of 10.1 J/cm3, concurrent with a high η of 90%, as well as excellent thermal and frequency stabilities can be achieved in a relaxor with a very simple chemical composition. By introducing 6s2 lone pair stereochemical active Bi into the classical BaTiO3 ferroelectric to generate a mismatch between A- and B-site polar displacements, a relaxor state with strong local polar fluctuations can be formed. Through advanced atomic-resolution displacement mapping and 3D reconstructing the nanoscale structure from neutron/X-ray total scattering, it is revealed that the localized Bi enhances the polar length largely at several perovskite unit cells and disrupts the long-range coherent Ti polar displacements, resulting in a slush-like structure with extremely small size polar clusters and strong local polar fluctuations. This favorable relaxor state exhibits substantially enhanced polarization, and minimized hysteresis at a high breakdown strength. This work offers a feasible avenue to chemically design new relaxors with a simple composition for high-performance capacitive energy-storage.

Emergence of high piezoelectricity from competing local polar order-disorder in relaxor ferroelectrics.

Relaxor ferroelectrics are known for outstanding piezoelectric properties, finding a broad range of applications in advanced electromechanical devices. Decoding the origins of the enhanced properties, however, have long been complicated by the heterogeneous local structures. Here, we employ the advanced big-box refinement method by fitting neutron-, X-ray-based total scattering, and X-ray absorption spectrum simultaneously, to extract local atomic polar displacements and construct 3D polar configurations in the classical relaxor ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3. Our results demonstrate that prevailing order-disorder character accompanied by the continuous rotation of local polar displacements commands the composition-driven global structure evolution. The omnidirectional local polar disordering appears as an indication of macroscopic relaxor characteristics. Combined with phase-field simulations, it demonstrates that the competing local polar order-disorder between different states with balanced local polar length and direction randomness leads to a flattening free-energy profile over a wide polar length, thus giving rise to high piezoelectricity. Our work clarifies that the critical structural feature required for high piezoelectricity is the competition states of local polar rather than relaxor.

Cation Short-Range Ordering of MgAl2O4 and NiAl2O4 Spinel Oxides at High Temperatures via In Situ Neutron Total Scattering.

Complex oxides that adopt the isometric spinel structure (AB2O4) are important for numerous technological applications and are relevant for certain geological processes, which involve exposure to extreme environments such as high pressures and temperatures. Recent studies have shown that the changes to the spinel structure caused by these environments are complex and depend on the material length scale under consideration. In this study, we have expanded this approach to the behavior of spinels under high temperatures. In situ neutron total scattering experiments, coupled with pair distribution function analysis, performed on two spinel compositions with various levels of pre-existing disorder (MgAl2O4 and NiAl2O4) revealed that both compositions trend to a state of maximum disorder where the A and B cations are randomly distributed among the two available sites. Temperature-induced cation inversion, conventionally understood as an exchange of cations on the A and B sites, is locally expressed as an atomic rearrangement to a tetragonal symmetry, a correlation that is retained up to the maximum temperature studied (1000 °C). A complex thermal expansion behavior is revealed wherein the oxide materials expand heterogeneously at the level of coordination polyhedra with an apparent dependence on bond strength.

Understanding the Re-entrant Phase Transition in a Non-magnetic Scheelite.

The stereochemical activity of lone pair electrons plays a central role in determining the structural and electronic properties of both chemically simple materials such as H2O, as well as more complex condensed phases such as photocatalysts or thermoelectrics. TlReO4 is a rare example of a non-magnetic material exhibiting a re-entrant phase transition and emphanitic behavior in the long-range structure. Here, we describe the role of the Tl+ 6s2 lone pair electrons in these unusual phase transitions and illustrate its tunability by chemical doping, which has broad implications for functional materials containing lone pair bearing cations. First-principles density functional calculations clearly show the contribution of the Tl+ 6s2 in the valence band region. Local structure analysis, via neutron total scattering, revealed that changes in the long-range structure of TlReO4 occur due to changes in the correlation length of the Tl+ lone pairs. This has a significant effect on the anion interactions, with long-range ordered lone pairs creating a more densely packed structure. This resulted in a trade-off between anionic repulsions and lone pair correlations that lead to symmetry lowering upon heating in the long-range structure, whereby lattice expansion was necessary for the Tl+ lone pairs to become highly correlated. Similarly, introducing lattice expansion through chemical pressure allowed long-range lone pair correlations to occur over a wider temperature range, demonstrating a method for tuning the energy landscape of lone pair containing functional materials.

The "good," the "bad," and the "hidden" in neutron scattering and molecular dynamics of ionic aqueous solutions.

We characterize a concentrated 7.3 m CaCl2 solution, combining neutron diffraction with chloride isotopic substitution (Cl-NDIS) in null water and molecular dynamics (MD) simulations. We elucidate the solution structure, thermodynamic properties, and extent of ion pairing previously suggested as concentration-dependent and often not observed at lower concentrations. Our Cl-NDIS measurements designate the solvent-shared ion pairing as dominant and the contact ion pairing (CIP) as insignificant even under conditions close to the solubility limit. The MD models parameterized against neutron diffraction with calcium isotopic substitution (Ca-NDIS) overestimate CIP despite successfully reproducing most of the Cl-NDIS signal. This drawback originates from the fact that Ca2+-Cl- interactions were primarily "hidden" in the Ca-NDIS signal due to overlapping with Ca2+-Ow and Ca2+-Hw contributions to the total scattering. Contrary, MD models with moderate CIP and possessing generally good performance at high concentrations fail to reproduce the NDIS measurements accurately. Therefore, the electronic polarization, introduced in most of the recent MD models via scaling ionic charges, resolves some but not all parameterization drawbacks. We conclude that despite improving the quality of MD models "on average," the question "which model is the best" has not been answered but replaced by the question "which model is better for a given research." An overall "good" model can still be inappropriate or, in some instances, "bad" and, unfortunately, produce erroneous results. The accurate interpretation of several NDIS datasets, complemented by MD simulations, can prevent such mistakes and help identify the strengths, weaknesses, and convenient applications for corresponding computational models.

The nano- and meso-scale structure of amorphous calcium carbonate.

Understanding the underlying processes of biomineralization is crucial to a range of disciplines allowing us to quantify the effects of climate change on marine organisms, decipher the details of paleoclimate records and advance the development of biomimetic materials. Many biological minerals form via intermediate amorphous phases, which are hard to characterize due to their transient nature and a lack of long-range order. Here, using Monte Carlo simulations constrained by X-ray and neutron scattering data together with model building, we demonstrate a method for determining the structure of these intermediates with a study of amorphous calcium carbonate (ACC) which is a precursor in the bio-formation of crystalline calcium carbonates. We find that ACC consists of highly ordered anhydrous nano-domains of approx. 2 nm that can be described as nanocrystalline. These nano-domains are held together by an interstitial net-like matrix of water molecules which generate, on the mesoscale, a heterogeneous and gel-like structure of ACC. We probed the structural stability and dynamics of our model on the nanosecond timescale by molecular dynamics simulations. These simulations revealed a gel-like and glassy nature of ACC due to the water molecules and carbonate ions in the interstitial matrix featuring pronounced orientational and translational flexibility. This allows for viscous mobility with diffusion constants four to five orders of magnitude lower than those observed in solutions. Small and ultra-small angle neutron scattering indicates a hierarchically-ordered organization of ACC across length scales that allow us, based on our nano-domain model, to build a comprehensive picture of ACC formation by cluster assembly from solution. This contribution provides a new atomic-scale understanding of ACC and provides a framework for the general exploration of biomineralization and biomimetic processes.

Superior High-Temperature Strength in a Supersaturated Refractory High-Entropy Alloy.

Refractory high-entropy alloys (RHEAs) show promising applications at high temperatures. However, achieving high strengths at elevated temperatures above 1173K is still challenging due to heat softening. Using intrinsic material characteristics as the alloy-design principles, a single-phase body-centered-cubic (BCC) CrMoNbV RHEA with high-temperature strengths (beyond 1000 MPa at 1273 K) is designed, superior to other reported RHEAs as well as conventional superalloys. The origin of the high-temperature strength is revealed by in situ neutron scattering, transmission-electron microscopy, and first-principles calculations. The CrMoNbV's elevated-temperature strength retention up to 1273 K arises from its large atomic-size and elastic-modulus mismatches, the insensitive temperature dependence of elastic constants, and the dominance of non-screw character dislocations caused by the strong solute pinning, which makes the solid-solution strengthening pronounced. The alloy-design principles and the insights in this study pave the way to design RHEAs with outstanding high-temperature strength.

Predicting short-range order and correlated phenomena in disordered crystalline materials.

Disordered crystalline materials are used in a wide variety of energy-related technologies. Recent results from neutron total scattering experiments have shown that the atomic arrangements of many disordered crystalline materials are not random nor are they represented by the long-range structure observed from diffraction experiments. Despite the importance of disordered materials and the impact of disorder on the expression of physical properties, the underlying fundamental atomic-scale rules of disordering are not currently well understood. Here, we report that heterogeneous disordering (and associated structural distortions) can be understood by the straightforward application of Pauling's rules (1929). This insight, corroborated by first principles calculations, can be used to predict the short-range, atomic-scale changes that result from structural disordering induced by extreme conditions associated with energy-related applications, such as high temperature, high pressure, and intense radiation fields.

Unprecedented lattice volume expansion on doping stereochemically active Pb2+ into uniaxially strained structure of CaBa1-xPbxZn2Ga2O7.

Lone pair cations like Pb2+ are extensively utilized to modify and tune physical properties, such as nonlinear optical property and ferroelectricity, of some specific structures owing to their preference to adopt a local distorted coordination environment. Here we report that the incorporation of Pb2+ into the polar "114"-type structure of CaBaZn2Ga2O7 leads to an unexpected cell volume expansion of CaBa1-xPbxZn2Ga2O7 (0 ≤ x ≤ 1), which is a unique structural phenomenon in solid state chemistry. Structure refinements against neutron diffraction and total scattering data and theoretical calculations demonstrate that the unusual evolution of the unit cell for CaBa1-xPbxZn2Ga2O7 is due to the combination of the high stereochemical activity of Pb2+ with the extremely strained [Zn2Ga2O7]4- framework along the c-axis. The unprecedented cell volume expansion of the CaBa1-xPbxZn2Ga2O7 solid solution in fact is a macroscopic performance of the release of uniaxial strain along c-axis when Ba2+ is replaced with smaller Pb2+.

Disorder in Ho2Ti2-x Zr x O7: pyrochlore to defect fluorite solid solution series.

Pyrochlore (A2B2O7) is an important, isometric structure-type because of its large variety of compositions and structural derivatives that are generally related to different disordering mechanisms at various spatial scales. The disordering is key to understanding variations in properties, such as magnetic behavior or ionic conduction. Neutron and X-ray total scattering methods were used to investigate the degree of structural disorder in the Ho2Ti2-x Zr x O7 (x = 0.0-2.0, Δx = 0.25) solid solution series as a function of the Zr-content, x. Ordered pyrochlores (Fd3̄m) disorder to defect fluorite (Fm3̄m) via cation and anion disordering. Total scattering experiments with sensitivity to the cation and anion sublattices provide unique insight into the underlying atomic processes. Using simultaneous Rietveld refinement (long-range structure) and small-box refinement PDF analysis (short-range structure), we show that the series undergoes a rapid transformation from pyrochlore to defect fluorite at x ≈ 1.2, while the short-range structure exhibits a linear increase in a local weberite-type phase, C2221, over the entire composition range. Enthalpies of formation from the oxides determined using high temperature oxide melt solution calorimetry support the structural data and provide insight into the effect of local ordering on the energetics of disorder. The measured enthalpies of mixing are negative and are fit by a regular solution parameter of W = -31.8 ± 3.7 kJ mol-1. However, the extensive short-range ordering determined from the structural analysis strongly suggests that the entropies of mixing must be far less positive than implied by the random mixing of a regular solution. We propose a local disordering scheme involving the pyrochlore 48f to 8a site oxygen Frenkel defect that creates 7-coordinated Zr sites contained within local weberite-type coherent nanodomains. Thus, the solid solution is best described as a mixture of two phases, with the weberite-type nanodomains triggering the long-range structural transformation to defect fluorite after accumulation above a critical concentration (50% Ti replaced by Zr).

Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite.

Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (Na0.27MnO2) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g-1 after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material. Particularly, the co-deintercalation of the hydrated water and sodium-ion during the high potential charging process results in the shrinkage of interlayer distance and thus stabilizes the layered structure. Our results provide a genuine insight into how structural disordering and structural water improve sodium-ion storage in a layered electrode and open up an exciting direction for improving aqueous batteries.

Charge transfer drives anomalous phase transition in ceria.

Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P42/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of -25 °C-75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O2- anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.

Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation.

The ability to probe the structure of a salt solution at the atomic scale is fundamentally important for our understanding of many chemical reactions and their mechanisms. The capability of neutron diffraction to "see" hydrogen (or deuterium) and other light isotopes is exceptional for resolving the structural complexity around the dissolved solutes in aqueous electrolytes. We have made measurements using oxygen isotopes on aqueous nitrate to reveal a small hydrogen-bonded water coordination number (3.9 ± 1.2) around a nitrate oxyanion. This is compared to estimates made using the existing method of nitrogen isotope substitution and those of computational simulations (>5-6 water molecules). The low water coordination number, combined with a comparison to classical molecular dynamics simulations, suggests that ion-pair formation is significant. This insight demonstrates the utility of experimental diffraction data for benchmarking atomistic computer simulations, enabling the development of more accurate intermolecular potentials.

Nanostructured Na2Ti9O19 for Hybrid Sodium-Ion Capacitors with Excellent Rate Capability.

Herein, we report a new Na-insertion electrode material, Na2Ti9O19, as a potential candidate for Na-ion hybrid capacitors. We study the structural properties of nanostructured Na2Ti9O19, synthesized by a hydrothermal technique, upon electrochemical cycling vs Na. Average and local structures of Na2Ti9O19 are elucidated from neutron Rietveld refinement and pair distribution function (PDF), respectively, to investigate the initial discharge and charge events. Rietveld refinement reveals electrochemical cycling of Na2Ti9O19 is driven by single-phase solid solution reaction during (de)sodiation without any major structural deterioration, keeping the average structure intact. Unit cell volume and lattice evolution on discharge process is inherently related to TiO6 distortion and Na ion perturbations, while the PDF reveals the deviation in the local structure after sodiation. Raman spectroscopy and X-ray photoelectron spectroscopy studies further corroborate the average and local structural behavior derived from neutron diffraction measurements. Also, Na2Ti9O19 shows excellent Na-ion kinetics with a capacitve nature of 86% at 1.0 mV s-1, indicating that the material is a good anode candidate for a sodium-ion hybrid capacitor. A full cell hybrid Na-ion capacitor is fabricated by using Na2Ti9O19 as anode and activated porous carbon as cathode, which exhibits excellent electrochemical properties, with a maximum energy density of 54 Wh kg-1 and a maximum power density of 5 kW kg-1. Both structural insights and electrochemical investigation suggest that Na2Ti9O19 is a promising negative electrode for sodium-ion batteries and hybrid capacitors.

The Structure of Liquid and Amorphous Hafnia.

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf-O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that show density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf-Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf-Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO6,7 polyhedra resembling that observed in the monoclinic phase.