Superacid-doped polyaniline as a soluble polymeric active electrolyte for supercapacitors.

Using polyaniline as a soluble electrochemically active additive in an electrolyte has the advantages of high pseudocapacitance and good cycle stability of polyaniline, however, the challenge is how to make polyaniline soluble in the electrolyte. In this study, we prepare a solution of polyaniline in N-methylpyrrolidone by protonating polyaniline with trifluoromethyl sulfonic acid. Spectroscopic and electrochemical results indicate that the weak binding interaction, between trifloromethyl sulfonate ions and protonated polyaniline chains, increases the solubility of trifloromethyl sulfonic acid doped polyaniline. An active electrolyte system composed of 15 mg mL-1 polyaniline and 0.4 M trifluoromethyl sulfonic acid in N-methylpyrrolidone is developed. With the active electrolyte and reduced graphene oxide as the electrodes, the fabricated supercapacitor shows a higher specific capacitance than the corresponding electric double-layer supercapacitors. Because the volume change and hydrolyzation of polyaniline, which are the main causes of the performance degradation in polyaniline-based supercapacitors, are avoided, the present supercapacitor exhibits an excellent cycle stability of 100% capacitance retention after 10 000 cycles. This work demonstrates the possibility of directly using a conductive polymer as an active electrolyte in supercapacitors with high cycle stability.

Nanowire-Seeded Growth of Single-Crystalline (010) ß-Ga2 O3 Nanosheets with High Field-Effect Electron Mobility and On/Off Current Ratio.

2D ß-Ga2 O3 nanosheets, as fundamental materials, have great potential in next generations of ultraviolet transparent electrodes, high-temperature gas sensors, solar-blind photodetectors, and power devices, while their synthesis and growth with high crystalline quality and well-controlled orientation have not been reported yet. The present study demonstrates how to grow single-crystalline ultrathin quasi-hexagonal ß-Ga2 O3 nanosheets with nanowire seeds and proposes a hierarchy-oriented growth mechanism. The hierarchy-oriented growth is initiated by epitaxial growth of a single-crystalline ( 2 - 01 ) ß-Ga2 O3 nanowire on a GaN nanocrystal and followed by homoepitaxial growth of quasi-hexagonal (010) ß-Ga2 O3 nanosheets. The undoped 2D (010) ß-Ga2 O3 nanosheet field effect transistor has a field-effect electron mobility of 38 cm2 V-1 s-1 and an on/off current ratio of 107 with an average subthreshold swing of 150 mV dec-1 . The from-nanowires-to-nanosheets technique paves a novel way to fabricate nanosheets, which has great impact on the field of nanomaterial synthesis and growth and the area of nanoelectronics as well.

Enhancing sodium ionic conductivity in tetragonal-Na3PS4 by halogen doping: a first principles investigation.

Tetragonal Na3PS4 (t-Na3PS4) has been demonstrated as a very promising candidate for a solid-state sodium-ion electrolyte with high Na ionic conductivity at ambient temperature. In this paper, we systematically investigated the Na ionic conductivity in pristine and halogen (F, Cl, Br, and I) doped tetragonal-Na3PS4 superionic conductors using first-principles calculations. The Na ionic conductivity of pristine t-Na3PS4 is calculated to be about 0.01 mS cm-1, while much higher Na ionic conductivities could be achieved by introducing Na ion vacancies via a halogen doping strategy. The calculated Na ionic conductivity of t-Na3PS4 doped with 1.56% Cl is 1.07 mS cm-1 at ambient temperature. Among different halogen-doped t-Na3PS4, Br-doped t-Na3PS4 shows the lowest activation energy and the highest Na ionic conductivity, which reaches 2.37 mS cm-1 at 300 K. The low activation energy and high Na ionic conductivity in Br-doped t-Na3PS4 are due to a relatively lower defect binding energy of the defect pair of halogen substitution and a Na ion vacancy. Our results suggest Br-doped t-Na3PS4 may serve as a very promising Na-ion solid-state superionic conductor.

Stress-Induced Cubic-to-Hexagonal Phase Transformation in Perovskite Nanothin Films.

The strong coupling between crystal structure and mechanical deformation can stabilize low-symmetry phases from high-symmetry phases or induce novel phase transformation in oxide thin films. Stress-induced structural phase transformation in oxide thin films has drawn more and more attention due to its significant influence on the functionalities of the materials. Here, we discovered experimentally a novel stress-induced cubic-to-hexagonal phase transformation in the perovskite nanothin films of barium titanate (BaTiO3) with a special thermomechanical treatment (TMT), where BaTiO3 nanothin films under various stresses are annealed at temperature of 575 °C. Both high-resolution transmission electron microscopy and Raman spectroscopy show a higher density of hexagonal phase in the perovskite thin film under higher tensile stress. Both X-ray photoelectron spectroscopy and electron energy loss spectroscopy does not detect any change in the valence state of Ti atoms, thereby excluding the mechanism of oxygen vacancy induced cubic-to-hexagonal (c-to-h) phase transformation. First-principles calculations show that the c-to-h phase transformation can be completed by lattice shear at elevated temperature, which is consistent with the experimental observation. The applied bending plus the residual tensile stress produces shear stress in the nanothin film. The thermal energy at the elevated temperature assists the shear stress to overcome the energy barriers during the c-to-h phase transformation. The stress-induced phase transformation in perovskite nanothin films with TMT provides materials scientists and engineers a novel approach to tailor nano/microstructures and properties of ferroelectric materials.

Discovering a First-Order Phase Transition in the Li-CeO2 System.

An in-depth understanding of (de)lithiation induced phase transition in electrode materials is crucial to grasp their structure-property relationships and provide guidance to the design of more desirable electrodes. By operando synchrotron XRD (SXRD) measurement and Density Functional Theory (DFT) based calculations, we discover a reversible first-order phase transition for the first time during (de)lithiation of CeO2 nanoparticles. The LixCeO2 compound phase is identified to possess the same fluorite crystal structure with FM3M space group as that of the pristine CeO2 nanoparticles. The SXRD determined lattice constant of the LixCeO2 compound phase is 0.551 nm, larger than that of 0.541 nm of the pristine CeO2 phase. The DFT calculations further reveal that the Li induced redistribution of electrons causes the increase in the Ce-O covalent bonding, the shuffling of Ce and O atoms, and the jump expansion of lattice constant, thereby resulting in the first-order phase transition. Discovering the new phase transition throws light upon the reaction between lithium and CeO2, and provides opportunities to the further investigation of properties and potential applications of LixCeO2.

Charge- and thickness-dependent inplane deformation of multilayer graphene thin films.

The charge- and thickness-dependent inplane deformation of multilayer graphene thin films in an electrolyte was studied by joint first-principles/continuum calculations (JFPCC) and the surface eigenstress model. At thermodynamic equilibrium, a multilayer graphene film exhibits initial deformation, which is asymmetric with respect to negative and positive charges, and the thickness-dependent minimal inplane C-C bond length occurs at the same positive charge of about 0.0381 × 10(20) |e| m(-2) for all studied films. The surface eigenstress model was further developed to take the charge-induced deformation into account, which yields analytical formulas. The analytical formulas describe the JFPCC results well for multilayer graphene thin films with a layer number larger than two, and are powerful and user friendly for understanding the charge and thickness dependent deformation in atomistic calculations and sophisticated experiments with multilayer graphene thin films.

Size- and temperature-dependent Young's modulus and size-dependent thermal expansion coefficient of thin films.

Nanomaterials possess a high surface/volume ratio and surfaces play an essential role in size-dependent material properties. In the present study, nanometer-thick thin films were taken as an ideal system to investigate the surface-induced size- and temperature-dependent Young's modulus and size-dependent thermal expansion coefficient. The surface eigenstress model was further developed with the consideration of thermal expansion, leading to analytic formulas of size- and temperature-dependent Young's modulus, and size-dependent thermal expansion coefficient of thin films. Molecular dynamics (MD) simulations on face-centered cubic (fcc) Ag, Cu, and Ni(001) thin films were conducted at temperatures ranging from 300 K to 600 K. The MD simulation results are perfectly consistent with the theoretical predictions, thereby verifying the theoretical approach. The newly developed surface eigenstress model will be able to attack similar problems in other types of nanomaterials.

Periodically Modulated Size-Dependent Elastic Properties of Armchair Graphene Nanoribbons.

First-principles calculations were conducted on armchair graphene nanoribbons (AGNRs) to simulate the elastic behavior of AGNRs with hydrogen-terminated and bare edges. The results show width-dependent elastic properties with a periodicity of three, which depends on the nature of edge. The edge eigenstress and eigendisplacement models are able to predict the width-dependent nominal Young's modulus and Poisson's ratio, while the Clar structure explains the crucial role of edges in the periodically modulated size-dependent elastic properties.

Double hysteresis loops and large negative and positive electrocaloric effects in tetragonal ferroelectrics.

Phase field modelling and thermodynamic analysis are employed to investigate depolarization and compression induced large negative and positive electrocaloric effects (ECEs) in ferroelectric tetragonal crystalline nanoparticles. The results show that double-hysteresis loops of polarization versus electric field dominate at temperatures below the Curie temperature of the ferroelectric material, when the mechanical compression exceeds a critical value. In addition to the mechanism of pseudo-first-order phase transition (PFOPT), the double-hysteresis loops are also caused by the abrupt rise of macroscopic polarization from the abc phase to the c phase or the sudden fall of macroscopic polarization from the c phase to the abc phase when the temperature increases. This phenomenon is called the electric-field-induced-pseudo-phase transition (EFIPPT) in the present study. Similar to the two types of PFOPTs, the two types of EFIPPTs cause large negative and positive ECEs, respectively, and give the maximum absolute values of negative and positive adiabatic temperature change (ATC ΔT). The temperature associated with the maximum absolute value of negative ATC ΔT is lower than that associated with the maximum positive ATC ΔT. Both maximum absolute values of ATC ΔTs change with the variation in the magnitude of an applied electric field and depend greatly on the compression intensity.

Performance analysis of compressive ghost imaging based on different signal reconstruction techniques.

We present different signal reconstruction techniques for implementation of compressive ghost imaging (CGI). The different techniques are validated on the data collected from ghost imaging with the pseudothermal light experimental system. Experiment results show that the technique based on total variance minimization gives high-quality reconstruction of the imaging object with less time consumption. The different performances among these reconstruction techniques and their parameter settings are also analyzed. The conclusion thus offers valuable information to promote the implementation of CGI in real applications.

Standoff two-color quantum ghost imaging through turbulence.

Recently, a two-color quantum ghost imaging configuration was proposed by Karmakar et al. [Phys. Rev. A81, 033845 (2010)]. By illuminating an object located far away from the source and detector, with a signal beam of long wavelength to avoid absorption of short wavelengths in the atmosphere while a reference beam of short wavelength is detected locally, this imaging configuration can be appropriate for standoff sensing. In practice, the signal beam must propagate through atmosphere in the presence of serious turbulence. We analyzed theoretically the performance of this ghost imaging configuration through turbulence. Based on the Gaussian state source model and extended Huygens-Fresnel integral, a formula is derived to depict the ghost image formed through turbulence of a standoff reflective object. Numerical calculations are also given according to the formula. The results show that the image quality will be degraded by the turbulence, but the resolution can be improved by means of optimizing the wavelengths of the reference and signal beams even when the turbulence is very serious.

Crystallographic phase identifier of a convolutional self-attention neural network (CPICANN) on powder diffraction patterns.

Spectroscopic data, particularly diffraction data, are essential for materials characterization due to their comprehensive crystallographic information. The current crystallographic phase identification, however, is very time consuming. To address this challenge, we have developed a real-time crystallographic phase identifier based on a convolutional self-attention neural network (CPICANN). Trained on 692 190 simulated powder X-ray diffraction (XRD) patterns from 23 073 distinct inorganic crystallographic information files, CPICANN demonstrates superior phase-identification power. Single-phase identification on simulated XRD patterns yields 98.5 and 87.5% accuracies with and without elemental information, respectively, outperforming JADE software (68.2 and 38.7%, respectively). Bi-phase identification on simulated XRD patterns achieves 84.2 and 51.5% accuracies, respectively. In experimental settings, CPICANN achieves an 80% identification accuracy, surpassing JADE software (61%). Integration of CPICANN into XRD refinement software will significantly advance the cutting-edge technology in XRD materials characterization.

A Novel Cargo Delivery System-AnCar-ExoLaIMTS Ameliorates Arthritis via Specifically Targeting Pro-Inflammatory Macrophages.

Macrophages are heterogenic phagocytic cells that play distinct roles in physiological and pathological processes. Targeting different types of macrophages has shown potent therapeutic effects in many diseases. Although many approaches are developed to target anti-inflammatory macrophages, there are few researches on targeting pro-inflammatory macrophages, which is partially attributed to their non-s pecificity phagocytosis of extracellular substances. In this study, a novel recombinant protein is constructed that can be anchored on an exosome membrane with the purpose of targeting pro-inflammatory macrophages via antigen recognition, which is named AnCar-ExoLaIMTS . The data indicate that the phagocytosis efficiencies of pro-inflammatory macrophages for different AnCar-ExoLaIMTS show obvious differences. The AnCar-ExoLaIMTS3 has the best targeting ability for pro-inflammatory macrophages in vitro and in vivo. Mechanically, AnCar-ExoLaIMTS3 can specifically recognize the leucine-rich repeat domain of the TLR4 receptor, and then enter into pro-inflammatory macrophages via the TLR4-mediated receptor endocytosis pathway. Moreover, AnCar-ExoLaIMTS3 can efficiently deliver therapeutic cargo to pro-inflammatory macrophages and inhibit the synovial inflammatory response via downregulation of HIF-1α level, thus ameliorating the severity of arthritis in vivo. Collectively, the work established a novel gene/drug delivery system that can specifically target pro-inflammatory macrophages, which may be beneficial for the treatments of arthritis and other inflammatory diseases.

A Thermo-Electro-Viscoelastic Model for Dielectric Elastomers.

Dielectric elastomers (DEs) are a class of electro-active polymers (EAPs) that can deform under electric stimuli and have great application potential in bionic robots, biomedical devices, energy harvesters, and many other areas due to their outstanding deformation abilities. It has been found that stretching rate, temperature, and electric field have significant effects on the stress-strain relations of DEs, which may result in the failure of DEs in their applications. Thus, this paper aims to develop a thermo-electro-viscoelastic model for DEs at finite deformation and simulate the highly nonlinear stress-strain relations of DEs under various thermo-electro-mechanical loading conditions. To do so, a thermodynamically consistent continuum theoretical framework is developed for thermo-electro-mechanically coupling problems, and then specific constitutive equations are given to describe the thermo-electro-viscoelastic behaviors of DEs. Furthermore, the present model is fitted with the experimental data of VHB4905 to determine a temperature-dependent function of the equilibrium modulus. A comparison of the nonlinear loading-unloading curves between the model prediction and the experimental data of VHB4905 at various thermo-electro-mechanical loading conditions verifies the present model and shows its ability to simulate the thermo-electro-viscoelastic behaviors of DEs. Simultaneously, the results reveal the softening phenomena and the instant pre-stretch induced by temperature and the electric field, respectively. This work is conducive to analyzing the failure of DEs in functionalities and structures from theoretical aspects at various thermo-electro-mechanical conditions.

RuO2 electronic structure and lattice strain dual engineering for enhanced acidic oxygen evolution reaction performance.

Developing highly active and durable electrocatalysts for acidic oxygen evolution reaction remains a great challenge due to the sluggish kinetics of the four-electron transfer reaction and severe catalyst dissolution. Here we report an electrochemical lithium intercalation method to improve both the activity and stability of RuO2 for acidic oxygen evolution reaction. The lithium intercalates into the lattice interstices of RuO2, donates electrons and distorts the local structure. Therefore, the Ru valence state is lowered with formation of stable Li-O-Ru local structure, and the Ru-O covalency is weakened, which suppresses the dissolution of Ru, resulting in greatly enhanced durability. Meanwhile, the inherent lattice strain results in the surface structural distortion of LixRuO2 and activates the dangling O atom near the Ru active site as a proton acceptor, which stabilizes the OOH* and dramatically enhances the activity. This work provides an effective strategy to develop highly efficient catalyst towards water splitting.

Effects of deformability and thermal motion of lipid membrane on electroporation: by molecular dynamics simulations.

Effects of mechanical properties and thermal motion of POPE lipid membrane on electroporation were studied by molecular dynamics simulations. Among simulations in which specific atoms of lipids were artificially constrained at their equilibrium positions using a spring with force constant of 2.0 kcal/(molŲ) in the external electric field of 1.4 kcal/(molŠe), only constraint on lateral motions of lipid tails prohibited electroporation while non-tail parts had little effects. When force constant decreased to 0.2 kcal/(molŲ) in the position constraints on lipid tails in the external electric field of 2.0 kcal/(molŠe), water molecules began to enter the membrane. Position constraints of lipid tails allow water to penetrate from both sides of membrane. Thermal motion of lipids can induce initial defects in the hydrophobic core of membrane, which are favorable nucleation sites for electroporation. Simulations at different temperatures revealed that as the temperature increases, the time taken to the initial pore formation will decrease.

Two-dimensional sub-half-wavelength atom localization via controlled spontaneous emission.

We propose a scheme for two-dimensional (2D) atom localization based on the controlled spontaneous emission, in which the atom interacts with two orthogonal standing-wave fields. Due to the spatially dependent atom-field interaction, the position probability distribution of the atom can be directly determined by measuring the resulting spontaneously emission spectrum. The phase sensitive property of the atomic system leads to quenching of the spontaneous emission in some regions of the standing-waves, which significantly reduces the uncertainty in the position measurement of the atom. We find that the frequency measurement of the emitted light localizes the atom in half-wavelength domain. Especially the probability of finding the atom at a particular position can reach 100% when a photon with certain frequency is detected. By increasing the Rabi frequencies of the driving fields, such 2D sub-half-wavelength atom localization can acquire high spatial resolution.

Thickness- and temperature-dependent Grüneisen parameter in thin films.

The Grüneisen formula is one of the most important equations of state, in which the Grüneisen parameter plays a key role in the linkage of mechanical and thermal properties of materials. In the present work, for the first time, we investigate the dependence of the Grüneisen parameter on film-thickness and temperature via theoretical modeling and molecular dynamics (MD) simulations. The theoretical analysis gives two analytic expressions of a thickness- and temperature-dependent Grüneisen parameter, and the difference between the two analytic expressions lies in the quadratic or linear dependence on temperature. MD simulations are conducted on face-centered cubic (FCC) Ni, Cu, and Au (001) thin films and their bulk counterparts. The simulation results completely verify the theoretical results and determine the values of parameters involved in the theoretical modeling. The thickness- and temperature-dependent film heat capacity density is also investigated during the course of the Grüneisen parameter study.

Chemical Strain of Graphite-Based Anode during Lithiation and Delithiation at Various Temperatures.

Electrochemical lithiation/delithiation of electrodes induces chemical strain cycling that causes fatigue and other harmful influences on lithium-ion batteries. In this work, a homemade in situ measurement device was used to characterize simultaneously chemical strain and nominal state of charge, especially residual chemical strain and residual nominal state of charge, in graphite-based electrodes at various temperatures. The measurements indicate that raising the testing temperature from 20°C to 60°C decreases the chemical strain at the same nominal state of charge during cycling, while residual chemical strain and residual nominal state of charge increase with the increase of temperature. Furthermore, a novel electrochemical-mechanical model is developed to evaluate quantitatively the chemical strain caused by a solid electrolyte interface (SEI) and the partial molar volume of Li in the SEI at different temperatures. The present study will definitely stimulate future investigations on the electro-chemo-mechanics coupling behaviors in lithium-ion batteries.

Partial sodiation induced laminate structure and high cycling stability of black phosphorous for sodium-ion batteries.

Black phosphorus (BP) is a promising anode material for sodium ion batteries (SIBs) due to its extremely high theoretical capacity. However, the large volume change and breaking of the layered structure result in rapid capacity decay during cycling. Herein, our in situ transmission electron microscopy (TEM) study reveals the highly anisotropic Na diffusion and the formation of alternating layered and amorphous lamellas in BP nanosheets with small volume expansion induced by partial sodiation. Inspired by these results, we investigate systematically the cyclability of BP at controlled discharge capacities using half-cell SIBs, expecting to achieve good cyclability by sacrificing some of the capacity and preserving the layered structure of BP. Our results show that the cycling stability of BP is obviously improved by controlling the capacity appropriately. When the discharge capacity is limited at 400 mA h g-1, the half-cell can sustain more than 100 cycles with an active material mass loading of ∼2 mg cm-2, which is at least 4 times longer than when the capacity is limited at 600 mA h g-1 or above. The in situ TEM and electrochemical tests indicate that maintaining the layered structure by controlling the capacity is key to improve the cyclability of BP as an anode in SIBs.