Colossal Reversible Barocaloric Effects in a Plastic Crystal Mediated by Lattice Vibrations and Ion Diffusion.

Solid-state methods for cooling and heating promise a sustainable alternative to current compression cycles of greenhouse gases and inefficient fuel-burning heaters. Barocaloric effects (BCE) driven by hydrostatic pressure (p) are especially encouraging in terms of large adiabatic temperature changes (|ΔT| ≈ 10 K) and isothermal entropy changes (|ΔS| ≈ 100 J K-1 kg-1). However, BCE typically require large pressure shifts due to irreversibility issues, and sizeable |ΔT| and |ΔS| seldom are realized in a same material. Here, the existence of colossal and reversible BCE in LiCB11H12 is demonstrated near its order-disorder phase transition at ≈380 K. Specifically, for Δp ≈ 0.23 (0.10) GPa, |ΔSrev| = 280 (200) J K-1 kg-1 and |ΔTrev| = 32 (10) K are measured, which individually rival with state-of-the-art BCE figures. Furthermore, pressure shifts of the order of 0.1 GPa yield huge reversible barocaloric strengths of ≈2 J K-1 kg-1 MPa-1. Molecular dynamics simulations are performed to quantify the role of lattice vibrations, molecular reorientations, and ion diffusion on the disclosed BCE. Interestingly, lattice vibrations are found to contribute the most to |ΔS| while the diffusion of lithium ions, despite adding up only slightly to the entropy change, is crucial in enabling the molecular order-disorder phase transition.

Light-driven dynamical tuning of the thermal conductivity in ferroelectrics.

Dynamical tuning of the thermal conductivity in crystals, κ, is critical for thermal management applications, as well as for energy harvesting and the development of novel phononic devices able to perform logic operations with phonons. Such a desired κ control can be achieved in functional materials that experience large structural and phonon variations as a result of field-induced phase transformations. However, this approach is only practical within reduced temperature intervals containing zero-bias phase transition points, since otherwise the necessary driving fields become excessively large and the materials' performances are detrimentally affected. Here, based on first-principles calculations, we propose an alternative strategy for dynamically tuning κ that is operative over broad temperature conditions and realizable in a wide class of materials. By shining light on the archetypal perovskite oxide KNbO3, we predict that ultrafast and reversible ferroelectric-to-paraelectric phase transitions are induced, yielding large and anisotropic κ variations (up to ≈30% at T = 300 K). These light-induced thermal transport shifts can take place at temperatures spanning several hundreds of kelvin and are essentially the result of anharmonic effects affecting the phonon lifetimes.

How Concerted Are Ionic Hops in Inorganic Solid-State Electrolytes?

Despite being fundamental to the understanding of solid-state electrolytes (SSEs), little is known on the degree of coordination between mobile ions in diffusive events, thus hindering a detailed comprehension and possible rational design of SSEs. Here, we introduce an unsupervised k-means clustering approach that is able to identify ion-hopping events and correlations between many mobile ions and apply it to a comprehensive ab initio MD database comprising several families of inorganic SSEs and millions of ionic configurations. It is found that despite two-body interactions between mobile ions being the largest, higher-order n-ion (2 < n) correlations are most frequent. Specifically, we prove a general exponential decaying law for the probability density function governing the number of concerted mobile ions. For the particular case of Li-based SSEs, it is shown that the average number of correlated mobile ions amounts to 10 ± 5 and that this result is practically independent of the temperature. Interestingly, our data-driven analysis reveals that fast-ionic diffusion strongly and positively correlates with ample hopping lengths and long hopping spans but not with high hopping frequencies and short interstitial residence times. Finally, it is shown that neglection of many-ion correlations generally leads to a modest overestimation of the hopping frequency that roughly is proportional to the average number of correlated mobile ions.

Fast Organic Cation Exchange in Colloidal Perovskite Quantum Dots toward Functional Optoelectronic Applications.

Colloidal quantum dots with lower surface ligand density are desired for preparing the active layer for photovoltaic, lighting, and other potential optoelectronic applications. In emerging perovskite quantum dots (PQDs), the diffusion of cations is thought to have a high energy barrier, relative to that of halide anions. Herein, we investigate the fast cross cation exchange approach in colloidal lead triiodide PQDs containing methylammonium (MA+) and formamidinium (FA+) organic cations, which exhibits a significantly lower exchange barrier than inorganic cesium (Cs+)-FA+ and Cs+-MA+ systems. First-principles calculations further suggest that the fast internal cation diffusion arises due to a lowering in structural distortions and the consequent decline in attractive cation-cation and cation-anion interactions in the presence of organic cation vacancies in mixed MA+-FA+ PQDs. Combining both experimental and theoretical evidence, we propose a vacancy-assisted exchange model to understand the impact of structural features and intermolecular interaction in PQDs with fewer surface ligands. Finally, for a realistic outcome, the as-prepared mixed-cation PQDs display better photostability and can be directly applied for one-step coated photovoltaic and photodetector devices, achieving a high photovoltaic efficiency of 15.05% using MA0.5FA0.5PbI3 PQDs and more precisely tunable detective spectral response from visible to near-infrared regions.

First-Principles Study on the Interplay of Strain and State-of-Charge with Li-Ion Diffusion in the Battery Cathode Material LiCoO2.

Cathode degradation of Li-ion batteries (Li+) continues to be a crucial issue for higher energy density. A main cause of this degradation is strain due to stress induced by structural changes according to the state-of-charge (SOC). Moreover, in solid-state batteries, a mismatch between incompatible cathode/electrolyte interfaces also generates a strain effect. In this respect, understanding the effects of the mechanical/elastic phenomena associated with SOC on the cathode performance, such as voltage and Li+ diffusion, is essential. In this work, we focused on LiCoO2 (LCO), a representative LIB cathode material, and investigated the effects of biaxial strain and hydrostatic pressure on its layered structure and Li+ transport properties through first-principles calculations. With the nudged elastic band technique and molecular dynamics, we demonstrated that in Li-deficient LCO, compressive biaxial strain increases the Li+ diffusivity, whereas tensile biaxial strain and hydrostatic pressure tend to suppress it. Structural parameter analysis revealed the key correlation of "Co layer distances" with Li+ diffusion instead of "Li layer distances", as ordinarily expected. Structural analysis further revealed the interplay between the Li-Li Coulomb interaction, SOC, and Li+ diffusion in LCO. The activation volume of LCO under hydrostatic pressure was reported for the first time. Moreover, vacancy formation energy calculations showed that the Li intercalation potential could be decreased under compressive biaxial strain due to the weakening of the Li-O bond interaction. The present findings may serve to improve the control of the energy density performance of layered cathode materials.

Facet-engineered TiO2 drives photocatalytic activity and stability of supported noble metal clusters during H2 evolution.

Metal clusters supported on TiO2 are widely used in many photocatalytic applications, including pollution control and production of solar fuels. Besides high photoactivity, stability during the photoreaction is another essential quality of high-performance photocatalysts, however systematic studies on this attribute are absent for metal clusters supported on TiO2. Here we have studied, both experimentally and with first-principles simulation methods, the stability of Pt, Pd and Au clusters prepared by ball milling on nanoshaped anatase nanoparticles preferentially exposing {001} (plates) and {101} (bipyramids) facets during the photogeneration of hydrogen. It is found that Pt/TiO2 exhibits superior stability than Pd/TiO2 and Au/TiO2, and that {001} facet-based photocatalysts always are more stable than their {101} analogous regardless of the considered metal species. The loss of stability associated with cluster sintering, which is facilitated by the transfer of photoexcited carriers from the metal species to the neighbouring Ti and O atoms, most significantly and detrimentally affects the H2-evolution photoactivity.

Excitonic insulator to superconductor phase transition in ultra-compressed helium.

Helium, the second most abundant element in the universe, exhibits an extremely large electronic band gap of about 20 eV at ambient pressures. While the metallization pressure of helium has been accurately determined, thus far little attention has been paid to the specific mechanisms driving the band-gap closure and electronic properties of this quantum crystal in the terapascal regime (1 TPa = 10 Mbar). Here, we employ density functional theory and many-body perturbation calculations to fill up this knowledge gap. It is found that prior to reaching metallicity helium becomes an excitonic insulator (EI), an exotic state of matter in which electrostatically bound electron-hole pairs may form spontaneously. Furthermore, we predict metallic helium to be a superconductor with a critical temperature of ≈ 20 K just above its metallization pressure and of ≈ 70 K at 100 TPa. These unforeseen phenomena may be critical for improving our fundamental understanding and modeling of celestial bodies.

Colossal room-temperature electrocaloric strength aided by hydrostatic pressure in lead-free multiferroic solid solutions.

Solid-state cooling applications based on electrocaloric (EC) effects are particularly promising from a technological point of view due to their downsize scalability and natural implementation in circuitry. However, EC effects typically involve materials that contain toxic substances and require relatively large electric fields (∼100-1000 kV cm-1) that cause fateful leakage current and dielectric loss problems. Here, we propose a possible solution to these practical issues that consists of concertedly applying hydrostatic pressure and electric fields on lead-free multiferroic materials. We theoretically demonstrate this strategy by performing first-principles simulations on supertetragonal BiFe1-xCoxO3 solid solutions (BFCO). It is shown that hydrostatic pressure, besides adjusting the occurrence of EC effects to near room temperature, can reduce enormously the intensity of driving electric fields. For pressurized BFCO, we estimate a colossal room-temperature EC strength, defined as the ratio of the adiabatic EC temperature change by an applied electric field, of ∼1 K cm kV-1, a value that is several orders of magnitude larger than those routinely measured in uncompressed ferroelectrics.

Universal ion-transport descriptors and classes of inorganic solid-state electrolytes.

Solid-state electrolytes (SSEs) with high ion conductivity are pivotal for the development and large-scale adoption of green-energy conversion and storage technologies such as fuel cells, electrocatalysts and solid-state batteries. Yet, SSEs are extremely complex materials for which general rational design principles remain indeterminate. Here, we combine first-principles materials modelling, computational power and modern data analysis techniques to advance towards the solution of such a fundamental and technologically pressing problem. Our data-driven survey reveals that the correlations between ion diffusivity and other materials descriptors in general are monotonic, although not necessarily linear, and largest when the latter are of vibrational nature and explicitly incorporate anharmonic effects. Surprisingly, principal component and k-means clustering analyses show that elastic and vibrational descriptors, rather than the usual ones related to chemical composition and ion mobility, are best suited for reducing the high complexity of SSEs and classifying them into universal classes. Our findings highlight the need for considering databases that incorporate temperature effects to improve our understanding of SSEs and point towards a generalized approach to the design of energy materials.

Eutectic Mixture Formation and Relaxation Dynamics of Coamorphous Mixtures of Two Benzodiazepine Drugs.

The formation of coamorphous mixtures of pharmaceuticals is an interesting strategy to improve the solubility and bioavailability of drugs, while at the same time enhancing the kinetic stability of the resulting binary glass and allowing the simultaneous administration of two active principles. In this contribution, we describe kinetically stable amorphous binary mixtures of two commercial active pharmaceutical ingredients, diazepam and nordazepam, of which the latter, besides being administered as a drug on its own, is also the main active metabolite of the other in the human body. We report the eutectic equilibrium-phase diagram of the binary mixture, which is found to be characterized by an experimental eutectic composition of 0.18 molar fraction of nordazepam, with a eutectic melting point of Te = 395.4 ± 1.2 K. The two compounds are barely miscible in the crystalline phase. The mechanically obtained mixtures were melted and supercooled to study the glass-transition and molecular-relaxation dynamics of amorphous mixtures at the corresponding concentration. The glass-transition temperature was always higher than room temperature and varied linearly with composition. The Te was lower than the onset of thermal decomposition of either compound (pure nordazepam decomposes upon melting and pure diazepam well above its melting point), thus implying that the eutectic liquid and glass can be obtained without any degradation of the drugs. The eutectic glass was kinetically stable against crystallization for at least a few months. The relaxation processes of the amorphous mixtures were studied by dielectric spectroscopy, which provided evidence for a single structural (α) relaxation, a single Johari-Goldstein (ß) relaxation, and a ring-inversion conformational relaxation of the diazepinic ring, occurring on the same timescale in both drugs. We further characterized both the binary mixtures and pure compounds by FTIR spectroscopy and first-principles density functional theory (DFT) simulations to analyze intermolecular interactions. The DFT calculations confirm the presence of strong attractive forces within the heteromolecular dimer, leading to large dimer interaction energies of the order of -0.1 eV.

Absence of Off-Diagonal Long-Range Order in hcp

The mass transport properties along dislocation cores in hcp ^{4}He are revisited by considering two types of edge dislocations as well as a screw dislocation, using a fully correlated quantum simulation approach. Specifically, we employ the zero-temperature path-integral ground state (PIGS) method together with ergodic sampling of the permutation space to investigate the fundamental dislocation core structures and their off-diagonal long-range order properties. It is found that the Bose-Einstein condensate fraction of such defective ^{4}He systems is practically null (≤10^{-6}), just as in the bulk defect-free crystal. These results provide compelling evidence for the absence of intrinsic superfluidity in dislocation cores in hcp ^{4}He and challenge the superfluid dislocation-network interpretation of the mass-flux-experiment observations, calling for further experimental investigation.

Effects of Multiple Local Environments on Electron Energy Loss Spectra of Epitaxial Perovskite Interfaces.

The role of local chemical environments in the electron energy loss spectra of complex multiferroic oxides was studied using computational and experimental techniques. The evolution of the O K-edge across an interface between bismuth ferrite (BFO) and lanthanum strontium manganate (LSMO) was considered through spectral averaging over crystallographically equivalent positions to capture the periodicity of the local O environments. Computational techniques were used to investigate the contribution of individual atomic environments to the overall spectrum, and the role of doping and strain was considered. Chemical variation, even at the low level, was found to have a major impact on the spectral features, whereas strain only induced a small chemical shift to the edge onset energy. Through a combination of these methods, it was possible to explain experimentally observed effects such as spectral flattening near the interface as the combination of spectral responses from multiple local atomic environments.

Tuning the Electronic, Ion Transport, and Stability Properties of Li-rich Manganese-based Oxide Materials with Oxide Perovskite Coatings: A First-Principles Computational Study.

Lithium-rich manganese-based oxides (LRMO) are regarded as promising cathode materials for powering electric applications due to their high capacity (250 mAh g-1) and energy density (∼900 Wh kg-1). However, poor cycle stability and capacity fading have impeded the commercialization of this family of materials as battery components. Surface modification based on coating has proven successful in mitigating some of these problems, but a microscopic understanding of how such improvements are attained is still lacking, thus impeding systematic and rational design of LRMO-based cathodes. In this work, first-principles density functional theory (DFT) calculations are carried out to fill out such a knowledge gap and to propose a promising LRMO-coating material. It is found that SrTiO3 (STO), an archetypal and highly stable oxide perovskite, represents an excellent coating material for Li1.2Ni0.2Mn0.6O2 (LNMO), a prototypical member of the LRMO family. An accomplished atomistic model is constructed to theoretically estimate the structural, electronic, oxygen vacancy formation energy, and lithium-transport properties of the LNMO/STO interface system, thus providing insightful comparisons with the two integrating bulk materials. It is found that (i) electronic transport in the LNMO cathode is enhanced due to partial closure of the LNMO band gap (∼0.4 eV) and (ii) the lithium ions can easily diffuse near the LNMO/STO interface and within STO due to the small size of the involved ion-hopping energy barriers. Furthermore, the formation energy of oxygen vacancies notably increases close to the LNMO/STO interface, thus indicating a reduction in oxygen loss at the cathode surface and a potential inhibition of undesirable structural phase transitions. This theoretical work therefore opens up new routes for the practical improvement of cost-affordable lithium-rich cathode materials based on highly stable oxide perovskite coatings.

Enhancing cyclic and in-air stability of Ni-Rich cathodes through perovskite oxide surface coating.

Ni-rich layered oxides, such as LiNi0.8Co0.1Mn0.1O2 (NCM811), are promising cathode materials for high-energy lithium-ion batteries. However, the relatively high reactivity of Ni in NCM811 cathodes results in severe capacity fading originating from the undesired side reactions that occur at the cathode-electrolyte interface during prolonged cycling. Therefore, the trade-off between high capacity and long cycle life can obstruct the commercialization process of Ni-rich cathodes in modern lithium-ion batteries (LIBs). In addition, high sensitivity toward air upon storage greatly limits the commercial application. Herein, a facile surface modification strategy is introduced to enhance the cycling and in-air storage stability of NCM811. The NCM811 with a uniform SrTiO3 (STO) nano-coating layer exhibited outstanding electrochemical performances that could deliver a high discharge capacity of 173.5 mAh⋅g-1 after 200 cycles under 1C with a capacity retention of 90%. In contrast, the uncoated NCM811 only provided 65% capacity retention of 130.8 mAh⋅g-1 under the same conditions. Structural evolution analysis suggested that the STO coating acted as a buffer layer to suppress the dissolution of transition metal ions caused by the HF attack from the electrolyte and promote the lithium diffusion during the charge-discharge process. In addition, the constructed STO layer prevented the exposure of NCM811 to H2O and CO2 and thus effectively improved the in-air storage stability. This work offers an effective way to enhance the performance stability of Ni-rich oxides for high-performance cathodes of lithium-ion batteries.

Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals.

We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (<30 K) specific heat of the molecular crystal benzophenone and those of several of its fully ordered bromine derivatives. Subsequently, by means of theoretical first-principles methods based on density functional theory, we estimate the corresponding phonon dispersions and vibrational density of states. Our results reveal two possible mechanisms for the emergence of the BP-like anomaly: (i) acoustic-optic phonon avoided crossing, which gives rise to a pseudo-van Hove singularity in the acoustic phonon branches, and (ii) piling up of low-frequency optical phonons, which are quasi degenerate with longitudinal acoustic modes and lead to a surge in the vibrational density of states at low energies.

Tailoring Phase Alignment and Interfaces via Polyelectrolyte Anchoring Enables Large-Area 2D Perovskite Solar Cells.

Ruddlesden-Popper phase 2D perovskite solar cells (PSCs) exhibit improved lifetime while still facing challenges such as phase alignment and up-scaling to module-level devices. Herein, polyelectrolytes are explored to tackle this issue. The contact between perovskite and hole-transport layer (HTL) is important for decreasing interfacial non-radiative recombination and scalable fabrication of uniform 2D perovskite films. Through exploring compatible butylamine cations, we first demonstrate poly(3-(4-carboxybutyl)thiophene-2,5-diyl)-butylamine (P3CT-BA) as an efficient HTL for 2D PSCs due to its great hydrophilicity, relatively high hole mobility and uniform surface. More importantly, the tailored P3CT-BA has an anchoring effect and acts as the buried passivator for 2D perovskites. Consequently, a best efficiency approaching 18 % was achieved and we further first report large-area (2×3 cm2 , 5×5 cm2 ) 2D perovskite minimodules with an impressive efficiency of 14.81 % and 11.13 %, respectively.

Anomalous Structural Evolution and Glassy Lattice in Mixed-Halide Hybrid Perovskites.

Hybrid halide perovskites have emerged as highly promising photovoltaic materials because of their exceptional optoelectronic properties, which are often optimized via compositional engineering like mixing halides. It is well established that hybrid perovskites undergo a series of structural phase transitions as temperature varies. In this work, the authors find that phase transitions are substantially suppressed in mixed-halide hybrid perovskite single crystals of MAPbI3-x Brx (MA = CH3 NH3 + and x = 1 or 2) using a complementary suite of diffraction and spectroscopic techniques. Furthermore, as a general behavior, multiple crystallographic phases coexist in mixed-halide perovskites over a wide temperature range, and a slightly distorted monoclinic phase, hitherto unreported for hybrid perovskites, is dominant at temperatures above 100 K. The anomalous structural evolution is correlated with the glassy behavior of organic cations and optical phonons in mixed-halide perovskites. This work demonstrates the complex interplay between composition engineering and lattice dynamics in hybrid perovskites, shedding new light on their unique properties.

Hydrazine Hydrate Intercalated 1T-Dominant MoS2 with Superior Ambient Stability for Highly Efficient Electrocatalytic Applications.

Metallic 1T-phase MoS2 exhibits superior hydrogen evolution reaction (HER) performance than natural 2H-phase MoS2 owing to its higher electrical conductivity and abundance of active sites. However, the reported 1T-MoS2 catalysts usually suffer from extreme instability, which results in quick phase transformation at ambient conditions. Herein, we present a facile approach to engineer the phase of MoS2 by introducing intercalated hydrazine. Interestingly, the as-synthesized 1T-dominant MoS2 sample demonstrates excellent ambient stability without noticeable degradation for 3 months. Additionally, the 1T-dominant MoS2 exhibits superior electrical conductivity (∼700 times higher than that of 2H-MoS2) and improved electrochemical catalytic performance (current density ∼12 times larger than that of 2H-MoS2 at an overpotential of 300 mV vs the reversible hydrogen electrode, RHE). Through experimental characterizations and density functional theory (DFT) calculation, we conclude that the stabilization of the metallic phase could be attributed to the electron donation from hydrazine molecules to the adjacent Mo atoms. The phase control strategy in this work provides a guideline to develop other highly efficient and stable two-dimensional (2D) electrocatalysts.

Quantum Dot Passivation of Halide Perovskite Films with Reduced Defects, Suppressed Phase Segregation, and Enhanced Stability.

Structural defects are ubiquitous for polycrystalline perovskite films, compromising device performance and stability. Herein, a universal method is developed to overcome this issue by incorporating halide perovskite quantum dots (QDs) into perovskite polycrystalline films. CsPbBr3 QDs are deposited on four types of halide perovskite films (CsPbBr3 , CsPbIBr2 , CsPbBrI2 , and MAPbI3 ) and the interactions are triggered by annealing. The ions in the CsPbBr3 QDs are released into the thin films to passivate defects, and concurrently the hydrophobic ligands of QDs self-assemble on the film surfaces and grain boundaries to reduce the defect density and enhance the film stability. For all QD-treated films, PL emission intensity and carrier lifetime are significantly improved, and surface morphology and composition uniformity are also optimized. Furthermore, after the QD treatment, light-induced phase segregation and degradation in mixed-halide perovskite films are suppressed, and the efficiency of mixed-halide CsPbIBr2 solar cells is remarkably improved to over 11% from 8.7%. Overall, this work provides a general approach to achieving high-quality halide perovskite films with suppressed phase segregation, reduced defects, and enhanced stability for optoelectronic applications.