Lithium ion transport in a model of amorphous polyethylene oxide

Summary We have made a molecular dynamics study of transport of a single lithium ion in a previously reported model of amorphous polyethylene oxide. New ab initio calculations of the interaction of the lithium ion with 1,2-dimethoxyethane and with dimethyl ether are reported which are used to determine force fields for the simulation. We report preliminary calculations of solvation energies and hopping barriers and a calculation of the ionic conductivity which is independent of any assumptions about the mechanism of ion transport. We also report some details of a study of transport of the trapped lithium ion on intermediate time and length scales.     

Electronic transport properties of individual chemically reduced graphene oxide sheets

Individual graphene oxide sheets subjected to chemical reduction were electrically characterized as a function of temperature and external electric fields. The fully reduced monolayers exhibited conductivities ranging between 0.05 and 2 S/cm and field effect mobilities of 2-200 cm2/Vs at room temperature. Temperature-dependent electrical measurements and Raman spectroscopic investigations suggest that charge transport occurs via variable range hopping between intact graphene islands with sizes on the order of several nanometers. Furthermore, the comparative study of multilayered sheets revealed that the conductivity of the undermost layer is reduced by a factor of more than 2 as a consequence of the interaction with the Si/SiO2 substrate.     

Electrochemical properties of solid polymer electrolytes prepared by the hard/soft acid base principle

In order to improve the electrochemical properties including ionic conductivity of SPEs (solid polymer electrolytes), understanding of the interaction between the polymer and salt in the SPE is important. In this study, four types of polymer matrices and four types of salts were used according to the hard/soft acid base (HSAB) principle. The results of impedance measurement reveal that the ionic conductivities are affected by the HSAB principle at low salt concentration. With increasing salt content, however, the SPEs are influenced by the ion hopping property of salt rather than by the solubility of the polymer with salt. In contrast, the PPS-based SPE shows different characteristics because it is prepared as a slurry phase at high salt content.     

Two semi-empirical approaches for the prediction of oxide ionic conductivities in ABO3 perovskites

Atomic properties and ionic conductivity data of perovskite-type oxides were collected from literatures and experiments. The relationship between the electrical conductivity and the atomic property was examined. The oxide ionic conductivities were predicted by using two semi-empirical approaches based on first-principles calculations and three machine learning methods, such as partial least squares (PLS), back propagation artificial neural network (BP-ANN), and support vector regression (SVR). It was found that P/L (the ratio of O–O charge population to the O–O band length) has a quadratic curving relationship with Lnσ (logarithm of oxide ion conductivity) in some undoped perovskite-type oxides. The results of machine learning indicate that the generalization ability of SVR is better than those of BP-ANN and PLS models for predicting Lnσ.     

Ionic transport in P(VdF-HFP)-PEO based novel microporous polymer electrolytes

A novel microporous polymer electrolyte (MPE) comprising blends of poly(vinylidene fluoride-cohexafluoropropylene) [P(VdF-HFP)] and polyethylene oxide (PEO) was prepared by phase inversion technique. It was observed that addition of PEO improved the pore configuration, such as pore size, pore connectivity and porosity of P(VdF-HFP) based membranes. The room temperature ionic conductivity was significantly enhanced. The highest porosity of about 65% and ionic conductivity of about 7 × 10⁻⁴ S cm⁻¹ was obtained when the weight ratio of PEO was 40%. The liquid electrolyte uptake was found to increase with increase in porosity and pore size. However, at higher weight ratio of PEO (> 40%) porosity, pore size and ionic conductivity was decreased. This descending trend with further increase of PEO weight ratio was attributed to conglomeration effect of PEO at the pores.     

Direct‐Write Formation and Dissolution of Silver Nanofilaments in Ionic Liquid‐Polymer Electrolyte Composites

Materials with reconfigurable optical properties are candidates for applications such as optical cloaking and wearable sensors. One approach to fabricate these materials is to use external fields to form and dissolve nanoscale conductive channels in well‐defined locations within a polymer. In this study, conductive atomic force microscopy is used to electrochemically form and dissolve nanoscale conductive filaments at spatially distinct points in a polyethylene glycol diacrylate (PEGDA)‐based electrolyte blended with varying amounts of ionic liquid (IL) and silver salt. The fastest filament formation and dissolution times are detected in a PEGDA/IL composite that has the largest modulus (several GPa) and the highest polymer crystal fraction. This is unexpected because filament formation and dissolution events are controlled by ion transport, which is typically faster within amorphous regions where polymer mobility is high. Filament kinetics in primarily amorphous and crystalline regions are measured, and two different mechanisms are observed. The formation time distributions show a power‐law dependence in the crystalline regions, attributable to hopping‐based ion transport, while amorphous regions show a normal distribution. The results indicate that the timescale of filament formation/dissolution is determined by local structure, and suggest that structure could be used to tune the optical properties of the film.     

Internal ion transport in ionic 2D CuInP2S6 enabling multi-state neuromorphic computing with low operation current

Memristor-based neuromorphic computing is promising for artificial intelligence. However, most of the reported memristors have limited linear computing states and consume large operation energy which hinder their applications. Herein, we report a memristor based on ionic two-dimensional CuInP₂S₆ (2D CIPS), in which up to 1350 linear conductance states are achieved by controlling the migration of internal Cu ions in CIPS. In addition, the device shows a low operation current of ∼100 pA. Cu ions are proven to move along the electric field by in-situ scanning electron microscopy and energy dispersive spectroscopy measurements. Furthermore, complex signal transport among multiple neurons in the brain is imitated by 2D CIPS-based memristor arrays. Our results offer a new platform to fabricate high-performance memristors based on ion transport in 2D materials for neuromorphic computing.     

Low-frequency dispersion in hopping electronic systems

We present the results of frequency- and time-domain measurements of Low-Frequency Dispersion on organic charge transfer complexes in which charge transport is due to hopping electrons. To our knowledge, this is the first convincing result establishing specifically that LFD can be observed in electronic conductors and this has consequences for the interpretation of these phenomena, which tended to be observed mainly in ionic conductors.     

The zwitterion effect in high-conductivity polyelectrolyte materials

The future of lithium metal batteries as a widespread, safe and reliable form of high-energy-density rechargeable battery depends on a significant advancement in the electrolyte material used in these devices. Molecular solvent-based electrolytes have been superceded by polymer electrolytes in some prototype devices, primarily in a drive to overcome leakage and flammability problems, but these often exhibit low ionic conductivity and prohibitively poor lithium-ion transport. To overcome this, it is necessary to encourage dissociation of the lithium ion from the anionic polymer backbone, ideally without the introduction of competing, mobile ionic species. Here we demonstrate the effect of zwitterionic compounds, where the cationic and anionic charges are immobilized on the same molecule, as extremely effective lithium ion 'dissociation enhancers'. The zwitterion produces electrolyte materials with conductivities up to seven times larger than the pure polyelectrolyte gels, a phenomenon that appears to be common to a number of different copolymer and solvent systems.     

Analyzing the frequency and temperature dependences of the ac conductivity and dielectric analysis of reduced graphene oxide/epoxy polymer nanocomposites

A series of composite materials was fabricated by mixing reduced graphene oxide (rGO) powder particles in an epoxy resin. In this paper, we analyze impedance measurements on these materials over broad frequency and temperature ranges. The real and imaginary parts of the effective complex impedance are well fitted to the Cole–Cole equation. The frequency dependence of the ac conductivity follows Jonscher’s law with relaxation processes characterized by a broad distribution of relaxation times. The imaginary part of the effective electric impedance collapses onto a single master curve using a single characteristic frequency as a scaling parameter. We find that the electrical properties of the samples are strongly influenced by graphene oxide content. Below percolation threshold, the ac transport can be interpreted as due to electron hopping. Further, we find that the frequency-dependent effective impedance measurements overlap on a single master curve in the range of temperatures explored, showing that a single electrical conduction mechanism is operative. Close and above percolation threshold, the ac conduction originates from both electron tunneling and capacitive paths among the rGO nanoparticles in the polymer bulk.     

Ce0.8Sm0.2O1.9基纳米复合材料的共沉淀合成与氧离子导电性

用化学共沉淀法制备了Ce_0.8Sm_0.2O_1.9-La_9.33Si₆O₂₆纳米复合氧离子导电材料,通过X射线衍射和透射电子显微镜对合成材料的相结构进行了分析,利用交流阻抗分析测试研究了材料的离子导电性. 结果表明,纳米复合材料的煅烧粉末的平均晶粒尺寸为20nm、烧结陶瓷体的平均晶粒尺寸为44nm;700℃时,纳米复合导电体的离子导电率为0.25Ω/cm;在整个测试温度范围内,纳米复合导电体比纯La_9.33Si₆O₂₆提高了3个以上数量级,并高于纯相Ce_0.8Sm_0.2O_1.9的导电性.     

Particle size-dependent electrical properties of nanocrystalline NiO

Nickel oxide nanoparticles are formed by chemical precipitation and subsequent drying and calcinations at temperatures ≥523 K. Samples are characterized using X-ray diffraction and BET surface area measurements indicating the formation of a single NiO phase whose crystallite size increases with increasing calcination temperature. The electrical properties are examined by measuring DC and AC conductivities and dielectric properties as functions of temperature. Electrical conductivities first slightly increases with increasing particle size up to 7–10 nm and are about 8 orders of magnitude higher than that of NiO single crystals. Further increasing the particle size above 10 nm, leads to a monotonic decrease of conductivity. The data are discussed in view of variations of grain boundary as well as triple junction volume fractions as the particle size varies. At temperatures above θ_D/2 (θ_D is the Debye temperature), the conductivity is ascribed to a band-like conduction due to the large polaron. The activation energy of conduction was found to be minimal for the highly conducting samples of 7–10 nm, and gradually increases to ~0.5 eV with increasing the particle size above 10 nm. For T < θ_D/2, the conductivity is best described by variable–range–hopping models. Model parameters are thus estimated and presented as functions of particle size. Frequency as well as temperature dependencies of the AC conductivity and dielectric constant exhibit trends usually observed in carrier dominated dielectrics.     

Ionic conductivity and hopping rate data for some NASICON analogues

The a.c. conductivity of ionic materials shows two regions of frequency-dependent conductivity over a wide range of frequencies. Jonscher’s law of dielectric response for ionic conductors enables us to characterize the conductivities. The region of low frequency dispersion approximates to a frequency-independent plateau enabling us to obtain the d.c. conductivity. In some other conductors, the presence of low-frequency dispersion cannot be neglected while determining the effective d.c. conductivity. We have used this method to extract the d.c. conductivity and hopping rate as well as to estimate concentrations of the mobile ions (carriers) in some NASICON analogues.     

Light‐Powered Directional Nanofluidic Ion Transport in Kirigami‐Made Asymmetric Photonic‐Ionic Devices

Nacre‐mimetic 2D nanofluidic materials with densely packed sub‐nanometer‐height lamellar channels find widespread applications in water‐, energy‐, and environment‐related aspects by virtue of their scalable fabrication methods and exceptional transport properties. Recently, light‐powered nanofluidic ion transport in synthetic materials gained considerable attention for its remote, noninvasive, and active control of the membrane transport property using the energy of light. Toward practical application, a critical challenge is to overcome the dependence on inhomogeneous or site‐specific light illumination. Here, asymmetric photonic‐ionic devices based on kirigami‐tailored graphene oxide paper are fabricated, and directional nanofluidic ion transport properties therein powered by full‐area light illumination are demonstrated. The in‐plane asymmetry of the graphene oxide paper is essential to the generation of photoelectric driving force under homogeneous illumination. This light‐powered ion transport phenomenon is explained based on a modified carrier diffusion model. In asymmetric nanofluidic structures, enhanced recombination of photoexcited charge carriers at the membrane boundary breaks the electric potential balance in the horizontal direction, and thus drives the ion transport in that direction under symmetric illumination. The kirigami‐based strategy provides a facile and scalable way to fabricate paper‐like photonic‐ionic devices with arbitrary shapes, working as fundamental elements for large‐scale light‐harvesting nanofluidic circuits.     

The superionic Agl-Ag2O-V2O5 system: Electrical conductivity studies on glass and polycrystalline forms

Superionic conducting glasses in the Agl-Ag₂O-V₂O₅ system were prepared by heating the appropriate amounts of raw materials at 723 K and quenching in liquid nitrogen. The polycrystalline materials were prepared by slowly cooling the melt to room temperature. X-ray diffraction was used for material characterization. The electrical conductivity of the pulverized samples, pressed together with an electrode mixture of silver and electrolyte (1:2 by weight) under 5000 kg cm^–2 pressure to form pellets 10 mm in diameter and 2 to 3 mm in thickness, was measured in the temperature range 300 to 365 K at 1 kHz. The ionic conductivities of the glasses were always higher than those of their polycrystalline counterparts, while their activation energies were also slightly higher. Conductivity measurements on annealed glassy samples indicated that the conductivity decreases with the time of annealing, and reaches a constant value which is nearly the same as that of the polycrystalline sample. Electronic conductivities of both types of sample were obtained by using Wagner's polarization cell technique, which showed that the electronic conductivity for both types was five orders of magnitude less than the total conductivity. Typical galvanic cells having the configuration Ag,electrolyte/electrolyte/C,electrolyte,I₂ were constructed and the silver ion transport number was calculated by the e.m.f. method.     

Interstitial oxide ion conductivity in the layered tetrahedral network melilite structure

High-conductivity oxide ion electrolytes are needed to reduce the operating temperature of solid-oxide fuel cells. Oxide mobility in solids is associated with defects. Although anion vacancies are the charge carriers in most cases, excess (interstitial) oxide anions give high conductivities in isolated polyhedral anion structures such as the apatites. The development of new families of interstitial oxide conductors with less restrictive structural constraints requires an understanding of the mechanisms enabling both incorporation and mobility of the excess oxide. Here, we show how the two-dimensionally connected tetrahedral gallium oxide network in the melilite structure La(1.54)Sr(0.46)Ga(3)O(7.27) stabilizes oxygen interstitials by local relaxation around them, affording an oxide ion conductivity of 0.02-0.1 S cm(-1) over the 600-900 degrees C temperature range. Polyhedral frameworks with central elements exhibiting variable coordination number can have the flexibility needed to accommodate mobile interstitial oxide ions if non-bridging oxides are present to favour cooperative network distortions.     

高银离子浓度非晶质快离子导体的合成

高能球磨技术是一种有效的合成非晶质材料、纳米材料的方法,本研究利用高能球磨技术制备了Ag₂S含量为80％的非晶质快离子导电材料,研究表明:当研磨时间为12～20h可导致非晶质相的形成.这种非晶质材料具有很高的电导率,其中20h研磨样品的室温电导率最高,为296×10⁰Sm^-1.进一步研磨致使部分Ag₈SiS₆晶体相析出,材料的电导率有所下降.利用直流极化技术对这些样品电子电导率测定结果表明:非晶质样品、(研磨时间长于27h的)复相样品以及Ag₈SiS₆晶体的银离子迁移率为1.     

Thermoelectricity in Heterogeneous Nanofluidic Channels

Ionic fluids are essential to energy conversion, water desalination, drug delivery, and lab‐on‐a‐chip devices. Ionic transport in nanoscale confinements and complex physical fields still remain elusive. Here, a nanofluidic system is developed using nanochannels of heterogeneous surface properties to investigate transport properties of ions under different temperatures. Steady ionic currents are observed under symmetric temperature gradients, which is equivalent to generating electricity using waste heat (e.g., electronic chips and solar panels). The currents increase linearly with temperature gradient and nonlinearly with channel size. Contributions to ion motion from temperatures and channel properties are evaluated for this phenomenon. The findings provide insights into the study of confined ionic fluids in multiphysical fields, and suggest applications in thermal energy conversion, temperature sensors, and chip‐level thermal management.     

Exploring water and ion transport process at silicone/copper interfaces using in-situ electrochemical and Kelvin probe approaches

In general,packaging materials which encapsulate light emitting diodes(LEDs)and microelectronic devices offer barrier protection against several environmental hazards such as water and ionic contaminants.However,these encapsulants may provide pathways for water and ionic contaminants to reach the metal/polymer interfaces and provoke local corrosion of electronics,which is a major reliability concern for polymer encapsulated LEDs and microelectronics.As the water and corrosive constituents play a crucial role in their reliability,water uptake kinetics,interfacial ion transport and delamination behaviour of silicone coated copper model system,mimicking a typical microelectronics packaging system,is explored in the present work.Electrochemical impedance spectroscopy(EIS)integrated with attenuated total reflection Fourier transform infrared(ATR-FTIR)spectroscopy studies revealed that water diffusion inside the silicone network is Fickian in nature and the evolution of the observed time constants are related to the diffusion and interfacial reactions.A decrease of impedance magnitude with time was observed in EIS measurements concurrently with water absorption bands shifting towards lower wavenumber in ATR-FTIR measurements,implying the growth of strong hydrogen bonding between water molecules and the silicone network.The estimated diffusion constant of water using the capacitance method was in the order of 7×10^-12m²s^-1and the water absorption volume fraction was in the range of 0%to 0.30%.Scanning Kelvin probe studies elucidated the ion transport process occurring at the silicone/copper interface in a humid atmosphere.The interfacial ion transport process is controlled by the interfacial electrochemical reactions at the cathodic delamination front and the estimated average delamination rate is 0.43 mm h^-1/2.This work demonstrates that exploring ion and water transport in the silicone coating and along the silicone/copper interface is of pivotal importance as part of a detailed reliability assessment of the polymer encapsulated LEDs and microelectronics.     

A study of CdS as a solid electrolyte for a thin film galvanic cell

This work is a continuation of our previous work in which it was reported that vacuum-evaporated CdS, when sandwiched between an aluminium electrode and a catalytic electrode such as silver, shows a galvanic effect. Cells of the type Al/CdS/M (where M  Ag, Cu or Au) were made by vacuum evaporation. The ionic conductivity of the CdS films was determined using the d.c. polarization technique. The ratio of ionic to electronic conductivity was calculated and was observed to have a minimum value of 1:1. The increase in the cell voltage and the decrease in its internal resistance with increasing temperature were studied. An Arrhenius plot of cell resistance gave an activation energy of 0.82 eV for sulphur ion hopping. A possible reaction mechanism of voltage generation is described in terms of the ionic conductivity of CdS films and the electrochemical effects at the interface between the CdS and the electrode materials. The decrease in the cell voltage with ambient air pressure is compared with the theory. The photoeffect suggest that CdS is behaving partially as an electronic photoresistor.