Characteristics of a Graphene Nanoplatelet Anode in Advanced Lithium‐Ion Batteries Using Ionic Liquid Added by a Carbonate Electrolyte

A Cu‐supported, graphene nanoplatelet (GNP) electrodes are reported a as high performance anode in lithium ion battery. The electrode precursor is an easy‐to‐handle aqueous ink cast on cupper foil and following dried in air. The scanning electron microscopy evidences homogeneous, micrometric flakes‐like morphology. Electrochemical tests in conventional electrolyte reveal a capacity of about 450 mAh g⁻¹ over 300 cycles, delivered at a current rate as high as 740 mA g⁻¹. The graphene‐based electrode is characterized using a N‐butyl‐N‐methyl‐pyrrolidiniumbis (trifluoromethanesulfonyl) imide, lithium‐bis(trifluoromethanesulfonyl)imide (Py_1,4TFSI–LiTFSI) ionic liquid‐based solution added by ethylene carbonate (EC): dimethyl carbonate (DMC). The Li‐electrolyte interface is investigated by galvanostatic and potentiostatic techniques as well as by electrochemical impedance spectroscopy, in order to allow the use of the graphene‐nanoplatelets as anode in advanced lithium‐ion battery. Indeed, the electrode is coupled with a LiFePO₄ cathode in a battery having a relevant safety content, due to the ionic liquid‐based electrolyte that is characterized by an ionic conductivity of the order of 10⁻² S cm⁻¹, a transference number of 0.38 and a high electrochemical stability. The lithium ion battery delivers a capacity of the order of 150 mAh g⁻¹ with an efficiency approaching 100%, thus suggesting the suitability of GNPs anode for application in advanced configuration energy storage systems.     

Air‐Stable and High‐Performance Solution‐Processed Organic Light‐Emitting Devices Based on Hydrophobic Polymeric Ionic Liquid Carrier‐Injection Layers

A lot of research, mostly using electron‐injection layers (EILs) composed of alkali‐metal compounds has been reported with a view to increase the efficiency of solution‐processed organic light‐emitting devices (OLEDs). However, these materials have intractable properties, such as a strong affinity for moisture, which cause the degradation of OLEDs. Consequently, optimal EIL materials should exhibit high electron‐injection efficiency as well as be stable in air. In this study, polymer light‐emitting devices (PLEDs) based on the commonly used yellow‐fluorescence‐emitting polymer F8BT, which utilize poly(diallyldimethylammonium)‐based polymeric ionic liquids, are experimentally and analytically investigated. As a result, the optimized PLED employing an EIL comprising poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (poly(DDA)TFSI), which is expected to display good moisture resistance because of water repellency of fluorocarbon groups, exhibits excellent storage stability in air and electroluminescence performance with a low turn‐on voltage of 2.01 V, maximum external quantum efficiency of 9.00%, current efficiency of 30.1 cd A^?1, and power efficiency of 32.4 lm W^?1. The devices with poly(DDA)TFSI show one of the highest efficiencies as compared to the reported standard PLEDs. Moreover, poly(DDA)TFSI is applied as a hole‐injection layer (HIL). The optimized PLED using poly(DDA)TFSI as the HIL exhibits performances comparable to those of a device that uses a conventional poly(3,4‐ethylenedioxy‐thiophene):poly(4‐styrenesulfonate) HIL.     

Quantitative Determination on Ionic‐Liquid‐Gating Control of Interfacial Magnetism

Ionic‐liquid gating on a functional thin film with a low voltage has drawn a lot of attention due to rich chemical, electronic, and magnetic phenomena at the interface. Here, a key challenge in quantitative determination of voltage‐controlled magnetic anisotropy (VCMA) in Au/[DEME]⁺[TFSI]^?/Co field‐effect transistor heterostructures is addressed. The magnetic anisotropy change as response to the gating voltage is precisely detected by in situ electron spin resonance measurements. A reversible change of magnetic anisotropy up to 219 Oe is achieved with a low gating voltage of 1.5 V at room temperature, corresponding to a record high VCMA coefficient of ≈146 Oe V^?1. Two gating effects, the electrostatic doping and electrochemical reaction, are distinguished at various gating voltage regions, as confirmed by X‐ray photoelectron spectroscopy and atomic force microscopy experiments. This work shows a unique ionic‐liquid‐gating system for strong interfacial magnetoelectric coupling with many practical advantages, paving the way toward ion‐liquid‐gating spintronic/electronic devices.     

Multimodal Wearable Ionoskins Enabling Independent Recognition of External Stimuli Without Crosstalk

Wearable ionoskins are one of the representative examples of the many useful applications offered by deformable stimuli-responsive sensory platforms. Herein, ionotronic thermo-mechano-multimodal response sensors are proposed, which can independently detect changes in temperature and mechanical stimuli without crosstalk. For this purpose, mechanically robust, thermo-responsive ion gels composed of poly(styrene-ran-n-butyl methacrylate) (PS-r-PnBMA, copolymer gelator) and 1-butyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([BMI][TFSI], ionic liquid) are prepared. The optical transmittance change arising from the lower critical solution temperature (LCST) phenomenon between PnBMA and [BMI][TFSI] is exploited to track the external temperature, creating a new concept of the temperature coefficient of transmittance (TCT). The TCT of this system (-11.5% °C^-1) is observed to be more sensitive to temperature fluctuations than the conventional metric of temperature coefficient of resistance. The tailoring molecular characteristics of gelators selectively improved the mechanical robustness of the gel, providing an additional application opportunity for strain sensors. This functional sensory platform, which is attached to a robot finger, can successfully detect thermal and mechanical environmental changes through variations in the optical (transmittance) and electrical (resistance) properties of the ion gel, respectively, indicating the high practicality of on-skin multimodal wearable sensors.     

Analysis of electromigration phenomenon in thick-film and LTCC structures at elevated temperature

Studies on electromigration phenomenon in thick-film structures on alumina and LTCC substrates are presented in this paper. The effects of storage of Au and Ag electrode patterns in temperature range up to 300 °C under voltage bias were examined. The leakage characteristics of electrodes with 100 μm spacing at 50 V dc bias as a function of time and temperature are presented and analyzed. Scanning electron microscope (SEM) equipped with the energy-dispersive X-ray spectroscopy (EDX) detector was applied for determination of metal ions transport. Test structures with Au-based conductive material are much more resistant to electromigration than Ag-based layers.     

聚氧化乙烯-聚硅氧烷基离子液体复合聚合物电解质的研究

通过对不同聚硅氧烷(PDMS)含量的聚氧化乙烯-聚硅氧烷(PEO-PDMS)聚合物电解质电化学性能的测试,确定出PDMS最佳添加量,并以此聚合物配比为基体,通过复合不同质量分数的离子液体1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐([BMIM]TF-SI)或N-甲基、丙基哌啶双三氟甲磺酰亚胺盐(PP13TFSI),制备得到不同体系的离子液体复合聚合物电解质膜。离子液体的加入可显著提高聚合物电解质的室温电导率,样品PPP-100%室温电导率达到5.6×10-4S/cm。同时,样品均具有良好的热学和电化学稳定性。通过两种体系聚合物电解质性能对比得知,PP13TFSI离子液体复合聚合物电解质具有更优性能,有望作为新型电解质材料应用在锂离子电池中。     

Overcoming the Interfacial Limitations Imposed by the Solid–Solid Interface in Solid‐State Batteries Using Ionic Liquid‐Based Interlayers

Li‐garnets are promising inorganic ceramic solid electrolytes for lithium metal batteries, showing good electrochemical stability with Li anode. However, their brittle and stiff nature restricts their intimate contact with both the electrodes, hence presenting high interfacial resistance to the ionic mobility. To address this issue, a strategy employing ionic liquid electrolyte (ILE) thin interlayers at the electrodes/electrolyte interfaces is adopted, which helps overcome the barrier for ion transport. The chemically stable ILE improves the electrodes‐solid electrolyte contact, significantly reducing the interfacial resistance at both the positive and negative electrodes interfaces. This results in the more homogeneous deposition of metallic lithium at the negative electrode, suppressing the dendrite growth across the solid electrolyte even at high current densities of 0.3 mA cm^?2. Further, the improved interface Li/electrolyte interface results in decreasing the overpotential of symmetric Li/Li cells from 1.35 to 0.35 V. The ILE modified Li/LLZO/LFP cells stacked either in monopolar or bipolar configurations show excellent electrochemical performance. In particular, the bipolar cell operates at a high voltage (≈8 V) and delivers specific capacity as high as 145 mAh g^?1 with a coulombic efficiency greater than 99%.     

Carbon Nanotube and Graphene‐based Bioinspired Electrochemical Actuators

Bio‐inspired actuation materials, also called artificial muscles, have attracted great attention in recent decades for their potential application in intelligent robots, biomedical devices, and micro‐electro‐mechanical systems. Among them, ionic polymer metal composite (IPMC) actuator has been intensively studied for their impressive high‐strain under low voltage stimulation and air‐working capability. A typical IPMC actuator is composed of one ion‐conductive electrolyte membrane laminated by two electron‐conductive metal electrode membranes, which can bend back and forth due to the electrode expansion and contraction induced by ion motion under alternating applied voltage. As its actuation performance is mainly dominated by electrochemical and electromechanical process of the electrode layer, the electrode material and structure become to be more crucial to higher performance. The recent discovery of one dimensional carbon nanotube and two dimensional graphene has created a revolution in functional nanomaterials. Their unique structures render them intriguing electrical and mechanical properties, which makes them ideal flexible electrode materials for IPMC actuators in stead of conventional metal electrodes. Currently although the detailed effect caused by those carbon nanomaterial electrodes is not very clear, the presented outstanding actuation performance gives us tremendous motivation to meet the challenge in understanding the mechanism and thus developing more advanced actuator materials. Therefore, in this review IPMC actuators prepared with different kinds of carbon nanomaterials based electrodes or electrolytes are addressed. Key parameters which may generate important influence on actuation process are discussed in order to shed light on possible future research and application of the novel carbon nanomateials based bio‐inspired electrochemical actuators.     

Radiative ion-ion neutralization: a new gas-phase atmospheric pressure ion transduction mechanism

All atmospheric pressure ion detectors, including photo ionization detectors, flame ionization detectors, electron capture detectors, and ion mobility spectrometers, utilize Faraday plate designs in which ionic charge is collected and amplified. The sensitivity of these Faraday plate ion detectors are limited by thermal (Johnson) noise in the associated electronics. Thus approximately 10(6) ions per second are required for a minimal detection. This is not the case for ion detection under vacuum conditions where secondary electron multipliers (SEMs) can be used. SEMs produce a cascade of approximately 10(6) electrons per ion impinging on the conversion dynode. Similarly, photomultiplier tubes (PMTs) can generate approximately 10(6) electrons per photon. Unlike SEMs, however, PMTs are evacuated and sealed so that they are commonly used under atmospheric pressure conditions. This paper describes an atmospheric pressure ion detector based on coupling a PMT with light emitted from ion-ion neutralization reactions. The normal Faraday plate collector electrode was replaced with an electrode "needle" used to concentrate the anions as they were drawn to the tip of the needle by a strong focusing electric field. Light was emitted near the surface of the electrode when analyte ions were neutralized with cations produced from the anode. Although radiative-ion-ion recombination has been previously reported, this is the first time ions from separate ionization sources have been combined to produce light. The light from this radiative-ion-ion-neutralization (RIIN) was detected using a photon multiplier such that an ion mobility spectrum was obtained by monitoring the light emitted from mobility separated ions. An IMS spectrum of nitroglycerin (NG) was obtained utilizing RIIN for tranducing the mobility separated ions into an analytical signal. The implications of this novel ion transduction method are the potential for counting ions at atmospheric pressure and for obtaining ion specific emission spectra for mobility separated ions.     

Local ionic and electron heating in single-molecule junctions

A basic aim in molecular electronics is to understand transport through a single molecule connected to two electrodes. Substantial progress towards this goal has been made over the past decade as a result of advances in both experimental techniques and theoretical methods. Nonetheless, a fundamental and technologically important issue, current-induced local heating of molecules, has received much less attention. Here, we report on a combined experimental and theoretical study of local heating in single molecules (6-, 8- and 10-alkanedithiol) covalently attached to two gold electrodes as a function of applied bias and molecular length. We find that the effective local temperature of the molecular junction first increases with applied bias, and then decreases after reaching a maximum. At fixed bias, the effective temperature decreases with increasing molecular length. These experimental findings are in agreement with hydrodynamic predictions, which include both electron-phonon and electron-electron interactions.     

Ionic selectivity of single nanochannels

There has been an increasing interest in single nanochannel ionic devices, such as ionic filters that control the type of transported ions and ionic diodes that rectify the ionic flow. In this article, we theoretically investigate the importance of the dimensions, surface charge, electrolyte concentration, and applied bias on nanopore performance. We compare numerical solutions of the Poisson, Nernst-Planck (PNP), and Navier-Stokes (NS) equations with their one-dimensional, analytical approximations. We show that by decreasing the length of the nanopore, the ionic current and ionic selectivity become affected by processes outside the nanochannel. The contribution of electroosmosis is noticeable, especially for highly charged nanochannels, but is insignificant, justifying the use of the simple one-dimensional approximation in many cases. Estimates for the critical electric field at which the nanopore selectivity decreases and the ion current starts to saturate are provided.     

Local electron heating in nanoscale conductors

The electron current density in nanoscale junctions is typically several orders of magnitude larger than the corresponding one in bulk electrodes. Consequently, the electron-electron scattering rate increases substantially in the junction. This leads to local electron heating of the underlying Fermi sea in analogy to the local ionic heating that is due to the increased electron-phonon scattering rates. We predict the bias dependence of local electron heating in quasi-ballistic nanoscale conductors and its effect on ionic heating and discuss possible experimental tests of our results.     

Flexible Zinc‐Ion Hybrid Fiber Capacitors with Ultrahigh Energy Density and Long Cycling Life for Wearable Electronics

Emerging wearable electronics require flexible energy storage devices with high volumetric energy and power densities. Fiber‐shaped capacitors (FCs) offer high power densities and excellent flexibility but low energy densities. Zn‐ion capacitors have high energy density and other advantages, such as low cost, nontoxicity, reversible Faradaic reaction, and broad operating voltage windows. However, Zn‐ion capacitors have not been applied in wearable electronics due to the use of liquid electrolytes. Here, the first quasisolid‐state Zn‐ion hybrid FC (ZnFC) based on three rationally designed components is demonstrated. First, hydrothermally assembled high surface area and conductive reduced graphene oxide/carbon nanotube composite fibers serve as capacitor‐type positive electrodes. Second, graphite fibers coated with a uniform Zn layer work as battery‐type negative electrodes. Third, a new neutral ZnSO₄‐filled polyacrylic acid hydrogel act as the quasisolid‐state electrolyte, which offers high ionic conductivity and excellent stretchability. The assembled ZnFC delivers a high energy density of 48.5 mWh cm^?3 at a power density of 179.9 mW cm^?3. Further, Zn dendrite formation that commonly happens under high current density is efficiently suppressed on the fiber electrode, leading to superior cycling stability. Multiple ZnFCs are integrated as flexible energy storage units to power wearable devices under different deformation conditions.     

Synthesis and electrochemical performances of LiNiCuZn oxides as anode and cathode catalyst for low temperature solid oxide fuel cell

Low temperature solid oxide fuel cell (LTSOFC, 300-600 degrees C) is developed with advantages compared to conventional SOFC (800-1000 degrees C). The electrodes with good catalytic activity, high electronic and ionic conductivity are required to achieve high power output. In this work, a LiNiCuZn oxides as anode and cathode catalyst is prepared by slurry method. The structure and morphology of the prepared LiNiCuZn oxides are characterized by X-ray diffraction and field emission scanning electron microscopy. The LiNiCuZn oxides prepared by slurry method are nano Li0.28Ni0.72O, ZnO and CuO compound. The nano-crystallites are congregated to form ball-shape particles with diameter of 800-1000 nm. The LiNiCuZn oxides electrodes exhibits high ion conductivity and low polarization resistance to hydrogen oxidation reaction and oxygen reduction reaction at low temperature. The LTSOFC using the LiNiCuZn oxides electrodes demonstrates good cell performance of 1000 mW cm(-2) when it operates at 470 degrees C. It is considered that nano-composite would be an effective way to develop catalyst for LTSOFC.     

Nanoscale memory elements based on solid-state electrolytes

We report on the fabrication and characterization of nanoscale memory elements based on solid electrolytes. When combined with silver, chalcogenide glasses such as Se-rich Ge-Se are good solid electrolytes, exhibiting high Ag ion mobility and availability. By placing an anode that has oxidizable Ag and an inert cathode (e.g., Ni) in contact with a thin layer of such a material, a device is formed that has an intrinsically high resistance, but which can be switched to a low-resistance state at small voltage via reduction of the silver ions. An opposite bias will return the device to a high-resistance state, and this reversible switching effect is the basis of programmable metallization cell technology. In this paper, electron beam lithography was used to make sub-100-nm openings in polymethylmethacrylate layers used as the dielectric between the device electrodes. The solid electrolyte film was formed in these via-holes so that their small diameter defined the active switching area between the electrodes. The Ag-Ge-Se electrolyte was created by the photodiffusion, with or without thermal assistance, of an Ag layer into the Ge-Se base glass. Combined thermal and photodiffusion leads to a nanophase separated material with a dispersed Ag ion-rich material with an average crystallite size of 7.5 nm in a glassy insulating Ge-rich continuous phase. The nanoscale devices write at an applied bias as low as 0.2 V, erase by -0.5 V, and fall from over 10/sup 7/ /spl Omega/ to a low-resistance state (e.g., 10/sup 4/ /spl Omega/ for a 10-/spl mu/A programming current) in less than 100 ns. Cycling appears excellent with projected endurance well beyond 10/sup 11/ cycles.     

Millivolt Modulation of Plasmonic Metasurface Optical Response via Ionic Conductance

A plasmonic metasurface with an electrically tunable optical response that operates at strikingly low modulation voltages is experimentally demonstrated. The fabricated metasurface shows up to 30% relative change in reflectance in the visible spectral range upon application of 5 mV and 78% absolute change in reflectance upon application of 100 mV of bias. The designed metasurface consists of nanostructured silver and indium tin oxide (ITO) electrodes which are separated by 5 nm thick alumina. The millivolt‐scale optical modulation is attributed to a new modulation mechanism, in which transport of silver ions through alumina dielectric leads to bias‐induced nucleation and growth of silver nanoparticles in the ITO counter‐electrode, altering the optical extinction response. This transport mechanism, which occurs at applied electric fields of 1 mV nm^?1, provides a new approach to use of ionic transport for electrical control over light–matter interactions.     

Impedance Spectroscopy of Ionic Ligand‐Modulated Charge Transport of Gold Nanoparticle Films

Assembled monolayer‐protected nanoparticles (NPs) possess unique electrical properties that are determined by the coupled effects of their nano‐sized electroactive inorganic cores that are capable of donating and accepting electrons and the organic shells. Core and ligand engineering for NP conductance modulation has been extensively explored; however, most studies focus on electron transport and not the interplay between the ion and electron transport processes. It is demonstrated here that electronic‐ and ionic‐conducting properties of nanoparticle assemblies can be controlled by engineering the charge and flexibility of the ligand shell. By using impedance spectroscopy, the electronic, mixed ionic and electronic, and responsive conductance of the nanoparticle film and structure‐function correlation are systematically investigated, and this correlation is used to provide a prototype volatile gas sensor based on the combined ionic and electronic conductance behavior of ionic ligand‐functionalized gold NPs.     

Nanoscale Energy Storage Materials Produced by Hydrogen‐Driven Metallurgical Reactions

Nanoscale energy storage materials offer enhanced kinetics, material stability and gravimetric capacity, with respect to their bulk counterparts. Hydrogen‐driven metallurgical reactions (HDMR) represent a novel method for synthesis of these nanomaterials. Nanoscale and nanocomposite electrodes for Li‐ion batteries synthesized by HDMR demonstrate reversible lithium cycling at low temperature (298 °C). The nanocomposite electrodes are composed of an electrochemically active species (Li‐Sn, Li‐Al‐Sn and Li‐Al‐Si) imbedded within an inert Li₂O matrix. These electrodes are prepared in the charged state and therefore do not suffer from the first cycle capacity loss that is characteristic of the intermetallic anodes. This novel synthesis technique may also be applied to the preparation of new hydrogen storage compounds.     

On-line gas-free electrodialytic eluent generator for capillary ion chromatography

Both low- and high-pressure, gas-free, capillary-scale electrodialytic generators for eluents in ion chromatography are described. While the low-pressure devices rely on planar or tubular membranes, the high-pressure devices rely on ion-exchange beads used both as one-way ionic gates and as ball-on-seat valves to provide sealing. The high-pressure device is easily implemented in the form of a commercial cross fitting and can withstand at least 1400 psi. By design these devices do not produce gas in the eluent channel; hence, it is not necessary to remove gas afterward. With appropriate electrolytes and electrode polarities, such devices can produce either acid or base or salt. In regard to ionic transport, the behavior of these devices fully corresponds to that of a semiconductor diode. To our knowledge, this is the first time such complete equivalence of ion transport through ion-exchange media and with the more familiar example of electron transport through a semiconductor diode under both forward- and reverse-biased conditions have been demonstrated. Reverse bias can be applied to minimize/prevent Donnan-forbidden leakage or ion exchange. Even with 4 M KOH in the electrode compartments and 4 microL/min water flowing through the eluent channel, with a reverse bias of -12 V, the leakage KOH concentration is <30 microM, whereas the KOH concentration with zero voltage applied, herein after termed open circuit penetration (OCP), is 1600 microM. It is suggested that this OCP occurs not as much through Donnan-forbidden leakage but via ion exchange. Chromatograms and reproducibility data are presented for both isocratic and gradient chromatography, using ion-exchange, latex-modified, open tubular and packed monolithic columns.     

Aerosol‐Assisted Heteroassembly of Oxide Nanocrystals and Carbon Nanotubes into 3D Mesoporous Composites for High‐Rate Electrochemical Energy Storage

Nanostructured composites built from ordinary building units have attracted much attention because of their collective properties for critical applications. Herein, we have demonstrated the heteroassembly of carbon nanotubes and oxide nanocrystals using an aerosol spray method to prepare nanostructured mesoporous composites for electrochemical energy storage. The designed composite architectures show high conductivity and hierarchically structured mesopores, which achieve rapid electron and ion transport in electrodes. Therefore, as‐synthesized carbon nanotube/TiO₂ electrodes exhibit high rate performance through rapid Li⁺ intercalation, making them suitable for ultrafast energy storage devices. Moreover, the synthesis process provides a broadly applicable method to achieve the heteroassembly of vast low‐dimensional building blocks for many important applications.