Ion Transfer Properties Research Articles

Bottom Deposition Enables Stable All-Solid-State Batteries with Ultrathin Lithium Metal Anode.

Modern strides in energy storage underscore the significance of all-solid-state batteries (ASSBs) predicated on solid electrolytes and lithium (Li) metal anodes in response to the demand for safer batteries. Nonetheless, ASSBs are often beleaguered by non-uniform Li deposition during cycling, leading to compromised cell performance from internal short circuits and hindered charge transfer. In this study, the concept of "bottom deposition" is introduced to stabilize metal deposition based on the lithiophilic current collector and a protective layer composed of a polymeric binder and carbon black. The bottom deposition, wherein Li plating ensues between the protective layer and the current collector, circumvents internal short circuits and facilitates uniform volumetric changes of Li. The prepared functional binder for the protective layer presents outstanding mechanical robustness and adhesive properties, which can withstand the volume expansion caused by metal growth. Furthermore, its excellent ion transfer properties promote uniform Li bottom deposition even under a current density of 6 mA·cm-2. Also, scanning electron microscopy analysis reveals a consistent plating/stripping morphology of Li after cycling. Consequently, the proposed system exhibits enhanced electrochemical performance when assessed within the ASSB framework, operating under a configuration marked by a high Li utilization rate reliant on an ultrathin Li.

A-Site Nonstoichiometric BaxCo0.4Fe0.4Zr0.1Y0.1O3-δ Cathode for Protonic Ceramics Fuel Cells.

Highly active triple (proton, oxygen-ion, and electron) conducting materials BaxCo0.4Fe0.4Zr0.1Y0.1O3-δ (BxCFZY, x = 0.9-1.1) were prepared and characterized as potential cathodes for protonic ceramic fuel cells (PCFCs) in this work. The crystal structure, oxygen vacancy concentration, electrical conductivity, oxygen ion transfer properties, and electrochemical performance of BxCFZY oxides were systematically evaluated. The electrical conductivity of BxCFZY decreases but oxygen vacancies increase with increasing Ba content, indicating that the charge compensation was mainly achieved by the production of oxygen vacancy rather than the increase in the valence of transition metal cations. The power density of 1170 mW cm-2 and the polarization resistance of 0.05 Ω cm2 were achieved at 700 °C for the anode-supported single cells with B1.1CFZY cathode, suggesting that the excess A site on the BxCFZY had a positive effect on the catalytic activity for the oxygen reduction reaction. Furthermore, the distribution of relaxation time (DRT) analysis method was adopted to determine the electrochemical processes of the cells with BxCFZY cathodes. The calculated results confirmed that the cell with B1.1CFZY cathode exhibited the optimum performance due to the best oxygen ion transfer properties in BxCFZY cathodes.

Improved electrochemical properties of In2S3/g-C3N4 nanocomposite for application as anodes in lithium and sodium ion batteries

In this work, the electrochemical properties of In2S3 anode material have been successfully enhanced by its composite formation using graphitic carbon nitride (g-C3N4). The 0.8In2S3:0.2 g-C3N4 composite delivers a reversible capacity of ∼ 358 mAh g−1 /1000 cycles vs. Li metal and ∼ 302 mAh g−1 /500 cycles vs. Na metal at current rate of 0.5 A g−1. The g-C3N4 matrix improves the ion transfer properties, alleviates the volume alteration happening in the anode during the discharge/charge process and also helps in preventing the leaching of polysulfides generated during the electrochemical process.

Conductive Geopolymers as Low-Cost Electrode Materials for Microbial Fuel Cells.

Geopolymer (GP) inorganic binders have a superior acid resistance compared to conventional cement (e.g., Portland cement, PC) binders, have better microbial compatibility, and are suitable for introducing electrically conductive additives to improve electron and ion transfer properties. In this study, GP–graphite (GPG) composites and PC–graphite (PCG) composites with a graphite content of 1–10 vol % were prepared and characterized. The electrical conductivity percolation threshold of the GPG and PCG composites was around 7 and 8 vol %, respectively. GPG and PCG composites with a graphite content of 8 to 10 vol % were selected as anode electrodes for the electrochemical analysis in two-chamber polarized microbial fuel cells (MFCs). Graphite electrodes were used as the positive control reference material. Geobacter sulfurreducens was used as a biofilm-forming and electroactive model organism for MFC experiments. Compared to the conventional graphite anodes, the anode-respiring biofilms resulted in equal current production on GPG composite anodes, whereas the PCG composites showed a very poor performance. The largest mean value of the measured current densities of a GPG composite used as anodes in MFCs was 380.4 μA cm–2 with a standard deviation of 129.5 μA cm–2. Overall, the best results were obtained with electrodes having a relatively low Ohmic resistance, that is, GPG composites and graphite. The very first approach employing sustainable GPs as a low-cost electrode binder material in an MFC showed promising results with the potential to greatly reduce the production costs of MFCs, which would also increase the feasibility of MFC large-scale applications.

Investigating the Proton and Ion Transfer Properties of Supported Ionic Liquid Membranes Prepared for Bioelectrochemical Applications Using Hydrophobic Imidazolium-Type Ionic Liquids.

Hydrophobic ionic liquids (IL) may offer a special electrolyte in the form of supported ionic liquid membranes (SILM) for microbial fuel cells (MFC) due to their advantageous mass transfer characteristics. In this work, the proton and ion transfer properties of SILMs made with IL containing imidazolium cation and [PF6]− and [NTf2]− anions were studied and compared to Nafion. It resulted that both ILs show better proton mass transfer and diffusion coefficient than Nafion. The data implied the presence of water microclusters permeating through [hmim][PF6]-SILM to assist the proton transfer. This mechanism could not be assumed in the case of [NTf2]− containing IL. Ion transport numbers of K+, Na+, and H+ showed that the IL with [PF6]− anion could be beneficial in terms of reducing ion transfer losses in MFCs. Moreover, the conductivity of [bmim][PF6]-SILM at low electrolyte concentration (such as in MFCs) was comparable to Nafion.

Electrical conductivity and ion transfer behavior of NiCo2O4 with different micro structures

The commercial graphite anode material in lithium-ion batteries has been limited by the low capacity and safety issue own to its low Li-intercalation potential. Spinel transition metal oxides have attracted tremendous attention because their high specific capacity and relatively high Li-intercalation potential. Herein, we investigated the influence of micro-structure on the ion transport properties of NiCo2O4 and their electronic conductivity. The optimized material with nano-cluster constructed macro-sphere demonstrates weak crystal structure and improved electrical conductivity when surrounded with amorphous carbon. Electrochemical impedance spectroscopy (EIS) combined with CV results give more clear explanation of the improved charge transfer resistance and ion transfer properties, which suggests the readjustment of microstructure is an important route for improving electrical conductivity and ion transfer behavior of NiCo2O4 anode.

Interphases in Sodium‐Ion Batteries

AbstractSodium‐ion batteries (SIBs) as economical, high energy alternatives to lithium‐ion batteries (LIBs) have received significant attention for large‐scale energy storage in the last few years. While the efforts of developing SIBs have benefited from the knowledge learned in LIBs, thanks to the apparent proximity between Na‐ions and Li‐ions, the unique physical and chemical properties of Na‐ions also distinctly differ themselves from Li‐ions. It is expected that SIBs have drastically different electrode material structure, solvation–desolvation behavior, electrode–electrolyte interphase stabilities, ion transfer properties, and hence electrochemical performance of batteries. In this review, the authors comprehensively summarize the current understanding of the anode solid electrolyte interphase and cathode electrolyte interphase in SIBs, with an emphasis on how the tuning of the stability and ion transfer properties of interphases fundamentally determines the reversibility and efficiency of electrochemical reactions. Through these carefully screened references, the authors intend to reveal the intrinsic correlation between the properties/functionalities of the interphases and the electrochemical performance of batteries.

Nanopore-enabled electrode arrays and ensembles

This review (with 116 refs.) addresses recent developments in nanoelectrode arrays and ensembles with particular attention to nanopore-enabled arrays and ensembles. Nanoelectrode-based arrays exhibit unique mass transport and ion transfer properties, which can be exploited for electroanalytical measurements with enhanced figures-of-merit with respect to microscale and larger components. Following an introduction into the topic, we cover (a) methods for fabrication of solid-state nanopore electrodes, (b) chemical and biochemical sensors, (c) nanochannel arrays with embedded nanoelectrodes; (d) recessed nanodisk electrode arrays; (e) redox cycling in nanopore electrode arrays, (f) finally discuss novel nanoarrays for electrochemistry, and then give a future outlook. A wide variety of nanoelectrode array-based chemical and biochemical sensors properties are discussed in addition to faradaic, ion transfer and spectroelectrochemical applications.

Crumpled Nitrogen-Doped Graphene for Supercapacitors with High Gravimetric and Volumetric Performances.

Graphene is considered a promising electrochemical capacitors electrode material due to its high surface area and high electrical conductivity. However, restacking interactions between graphene nanosheets significantly decrease the ion-accessible surface area and impede electronic and ionic transfer. This would, in turn, severely hinder the realization of high energy density. Herein, we report a strategy for preparation of few-layer graphene material with abundant crumples and high-level nitrogen doping. The two-dimensional graphene nanosheets (CNG) feature high ion-available surface area, excellent electronic and ion transfer properties, and high packing density, permitting the CNG electrode to exhibit excellent electrochemical performance. In ionic liquid electrolyte, the CNG electrode exhibits gravimetric and volumetric capacitances of 128 F g(-1) and 98 F cm(-3), respectively, achieving gravimetric and volumetric energy densities of 56 Wh kg(-1) and 43 Wh L(-1). The preparation strategy described here provides a new approach for developing a graphene-based supercapacitor with high gravimetric and volumetric energy densities.

Nanostructured TiO2 for energy conversion and storage

Nanostructured TiO2 possesses unique optical and physical properties as well as exhibiting quantum confinement effects and has attracted much attention in energy conversion and storage research. The energy related applications of nanostructured TiO2 can be grouped into four main categories: lithium-ion batteries, dye-sensitized solar cells (DSSCs), fuel cells, and super-capacitors. Nanostructured TiO2 with high crystallinity and/or a porous structure exhibits enhanced electron or ion transfer properties, enabling the fast diffusion of electrolytes, and consequently electrochemical processes proceed with high efficiency due to accelerated molecular adsorption. Its unique optical properties lead to improved photovoltaic performance and its bifunctional mechanism produces anti-poisoning effects on catalysts. This review discusses recent scientific and technological advances of nanostructured TiO2 from the perspectives of energy conversion and storage.

Effects of Electrolytes in a Liquid Thin Layer System

The effects of electrolytes on electrochemical behavior from an oil thin layer interposed between a graphite electrode and an aqueous solution phase were examined. A hydrophobic electroactive species, tetrachloro-1,4-benzoquinone (TCQ), in a benzonitrile (EN) layer was employed to study ion transfer properties across the BN-water interface. Experimental results showed that hydrophobic cations as well as anions could be successfully used as ionic charge carriers. The addition of various salts into either the oil layers or the aqueous solutions offers deeper insight for the electrochemistry of the liquid thin layer system. When aqueous perchloric acid is interfaced with the BN films, the perchlorate ion of tetrahexylammonium perchlorate (THAP) substantially suppresses the dissociated proton concentration in the layer by the common ion effect while there is only a little change in the total acid concentration. Further approach by theoretical calculation makes it possible to quantitatively understand the effect of the electrolytes to the electrochemical responses of TCQ, which were previously reported (Anal. Chem. 73, 337 (2001)).

A quantitative description of the E-4031-sensitive repolarization current in rabbit ventricular myocytes

We have measured the E-4031-sensitive repolarization current (IKr) in single ventricular myocytes isolated from rabbit hearts. The primary goal of this analysis was a description of the IKr kinetic and ion transfer properties. Surprisingly, the maximum time constant of this component was 0.8 s at 33-34 degrees C, which is significantly greater than the value of 0.18 s previously reported under similar conditions in the original measurements of IKr from guinea pig ventricular myocytes. The primary, novel feature of our analysis concerns the relationship of the bell-shaped curve that describes the voltage dependence of the kinetics and the sigmoidal curve that describes the activation of IKr. The midpoint of the latter occurred at approximately +10 mV on the voltage axis, as compared to -30 mV for the point on the voltage axis at which the maximum time constant occurred. Moreover, the voltage dependence of the kinetics was much broader than the steepness of the activation curve would predict. Taken together, these results comprise a gating current paradox that is not resolved by the incorporation of a fast inactivated state in the analysis. The fully activated current-voltage relation for IKr exhibited strong inward-going rectification, so much so that the current was essentially nil at +30 mV, even though the channel opens rapidly in this voltage range. This result is consistent with the lack of effect of E-4031 on the early part of the plateau phase of the action potential. Surprisingly, the reversal potential Of /Kr was ~15 mV positive to the potassium ion equilibrium potential,which indicates that this channel carries inward current during the latter part of the repolarization phase of the action potential.

Conformations, cation binding, and transmembrane ion transfer properties of a cyclooctapeptide built by an alternation of d and l residues

The conformations of a cyclic octapeptide built with an alternation of D and L residues are investigated on the basis of 1H n.m.r. and CD data. The cyclooctapeptide can form structures which are specific to the alternating D-L sequence. This peptide can form two types of complexes with cations (peptide 2-cation and peptide-cation complexes) and the binding with monovalent cation is weak. This peptide is able to induce transmembrane ion transfer through both a carrier mechanism and pore formation.

Recent aspects of single ion transfer properties

Abstract

Sodium current in single cells from bullfrog atrium: voltage dependence and ion transfer properties.

1. Whole-cell and patch-clamp techniques (Hamill, Marty, Neher, Sakmann & Sigworth, 1981) have been used to make quantitative measurements of the transient inward sodium current (INa) in single cells from bullfrog atrium. This preparation is particularly suitable for the study of INa: (i) the current density is relatively low, (ii) the cells lack a transverse tubule system, (iii) isolated myocytes can be maintained at reduced temperatures (approximately 8-12 degrees C); therefore kinetics can be studied quantitatively. 2. INa was pharmacologically and kinetically isolated from other transmembrane currents by blocking ICa with CdCl2 (0.2-0.5 mM) or LaCl3 (5 x 10(-6) M), and by using only relatively short voltage-clamp depolarizations which did not activate IK (the delayed rectifier). 3. The voltage dependence of INa in bullfrog atrium is similar to that in amphibian node of Ranvier or fast skeletal muscle. The threshold for activation is approximately -50 mV. The peak of the INa vs. membrane potential relation is near -5 to -10 mV. The reversal potential in 'normal' (115 mM-Na+) Ringer solution is +59.0 mV (S.D. +/- 3.4, n = 10). Reduction of external Na+ concentration to one-third of normal resulted in an approximately -27 mV shift of the reversal potential, close to that expected for a highly Na+-selective conductance. 4. Steady-state inactivation of INa (h infinity), measured with a conventional two-pulse voltage-clamp protocol, spanned the membrane potential range from -90 to -50 mV. The potential dependence of h infinity was well described by a single Boltzmann function with half-inactivation at -71 mV and maximum slope of 6.0 mV. 5. Steady-state activation of INa (m infinity) was determined from fits of INa records to a Hodgkin-Huxley model. The potential dependence of m infinity was fitted to a Boltzmann function with half-activation at -33 mV and maximum slope of 9.5 mV. Thus at temperatures around 10 degrees C there was very little overlap of the m infinity and h infinity curves, and only very small steady-state 'window' currents are predicted. 6. The activation time constant, tau m, had a 'bell-shaped' dependence on membrane potential. The peak value of tau m was about 4.2 ms, at a membrane potential of -35 mV (9 degrees C). 7. The time course of inactivation of INa was consistently better described by the sum of two exponentials than by one exponential.(ABSTRACT TRUNCATED AT 400 WORDS)