Electrochemical study of the silver-sodium substitution in a borosilicate glass

The study of the silver for sodium ions substitution kinetics is carried out using an electrochemical set-up. A silver metal anode, a reference and counter electrode are deposited as thin films on a 0.6 SiO₂-0.2 B₂O₃-0.2 Na₂O glassy electrolyte. The anode dissolution is studied by a chronoamperometric method. The generally proposed interdiffusion models assuming constant diffusion coefficients for both Ag⁺ and Na⁺ cations are not able to justify the experimental voltage time dependence. The deviation from theoretical predictions can be minimised by assuming a mixed cation effect in the glass, taking into account a concentration dependence of the Ag⁺ and Na⁺ diffusion coefficients.     

An investigation of the salt dissociation effects on solid electrolyte interface (SEI) formation using linear carbonate-based electrolytes in lithium ion batteries

Lithium salts possess dissociating properties that are useful for passivation layer formation. In this study, these properties are investigated in the context of three kinds of linear carbonate electrolytes using several techniques, such as physical properties, AC impedance, electrochemical quartz crystal microbalance (EQCM), and nuclear magnetic resonance (NMR). The lithium salts are completely dissociated to the lithium ions by the unsymmetrical linear carbonate structure; therefore, the transference number and diffusion coefficient of the cations show that the lithium ions are important and dominate the ionic transfer and the passivation layer properties that are important and relate to battery performance. These data suggest that battery performance is influenced by ionic transfer properties, lithium salt and electrolyte structure.     

Synthesis and characterisation of polypyrrole–indium phosphide composite film

Polypyrrole (PPy)–indium phosphide (InP) composite material was electrochemically prepared by the incorporation of InP into a PPy matrix during electrochemical synthesis (cycling) under magnetic stirring from the acetonitrile/LiClO4 electrolyte containing the Py and InP particles. The PPy–InP composite material was designed to explore new approaches to improve light-collection efficiency in polymer photovoltaic. The samples were characterised by cyclic voltammetry, impedance spectroscopy measurement, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV–visible and photoelectrochemical measurements. It was observed that the photocurrent of the composites was higher than that of the single PPy films and increased with InP concentration. The study showed that the presence of InP particles in the polymeric film improves the optical and the photovoltaic properties of PPy and give information on the use possibility of these films for photovoltaic cells' application.     

Electrochemical Studies on Substituted Iron-Hexacyanoiron(III) Bi-Layered Thin Films at Glassy Carbon Electrode/Electrolyte Interface

Thin films (30–50 nm) of bilayered HCM (hexacyanometalates) were prepared using direct electrodeposition or electrochemically driven insertion-substitution of PB (Prussian Blue) or InHCF (Indium Hexacyanoferrate) or K..In _x [Fe{CN}₆] _y , as starting material. The redox behavior of the immobilized counter/central ions at GCE/electrolyte interface have been investigated in aqueous KCl (pH 1) electrolytes using dynamic voltammetric techniques. Studies show that when the counter Fe or In ion is replaced by expandable partially filled d orbits elements such as Ru³⁺ a redox wave of the inserted counter ion is observed. Furthermore, the substitution of Fe as a counter ion with other poly-valent cations was found to be reversible if PB was the starting material. Studies were extended to include the EC (electrochemical) behavior of related HCM compounds such as K...Al _x [Fe{CN}₆] _y K, Ni _x [Fe{CN}₆] _y Cu _x [Fe{CN}₆] _y , K..Zn _x [Fe{CN}₆] _y and, K..Ru[Fe{CN}₆]₃. Unlike studied 3d cations, GCE modified with thin films of copper-hexacyanoiron (III) KCu _x [Fe{CN}₆] _y or CHF showed two redox waves with E^o _f 0.6, 0.9 V vs Ag/AgCl. Studies showed that even immobilized Cu ions were capable of catalyzing the oxidation of hydrazine and sulfite. The mechanism for electro-oxidation is also included.     

Use of non-aqueous electrochemical cells to investigate air- and water-sensitive hydrogen storage materials

Electrochemical methods have been used to study hydrogen in vanadium, titanium and three binary magnesium alloy systems. These materials are all sensitive to air and/or water, which prohibits the use of aqueous electrolytes. The measurements have involved the use of alkali halide and lower temperature organic-anion molten salts saturated with an alkali hydride so that they conduct charge by the transport of hydride ions, rather than protons. Alkali metals, or their alloys, can be used as indirect reference electrodes for hydrogen in these electrolytes.     

Diffusivity and conductivity of a primitive model electrolyte in a nanopore

Equilibrium and non-equilibrium molecular dynamics simulations are applied to obtain the diffusion coefficient and electric conductivity of ions in dilute electrolytes confined in neutral cylindrical pores. The electrolyte is described with the restricted primitive model and the wall of the pore is modelled as a soft wall. The equilibrium molecular dynamics simulations show that the axial diffusion coefficient of ions decreases with increasing confinement. For a fixed pore radius the diffusion coefficient decreases with increasing number density of the ions. The current response of the system to an applied electric field is maintained at constant temperature by Gaussian isokinetic equations of motion, and at constant concentration by periodic boundary conditions with recycling of ions in the axial direction. The electric conductivity is calculated from the current density and the electric field applied for different pore sizes. In contrast to the trend in diffusivity, conductivity increases slightly in smaller pores. For a very small pore, however, conductivity is lower than the bulk, because oppositely charged ions moving in opposite directions under the electric field cannot avoid collisions with each other in a narrow channel.     

Structural and electrical studies of sodium iodide doped poly(vinyl alcohol) polymer electrolyte films for their application in electrochemical cells

Solid polymer electrolyte films based on poly(vinyl alcohol) (PVA) complexed with sodium iodide (NaI) were prepared using solution cast technique. The structural properties of pure and complexed PVA polymer electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD results revealed that the amorphous domains of PVA polymer matrix was increased with the increase in NaI salt concentration. The variation of film morphology was examined by scanning electron microscopy (SEM) studies. Fourier transform infrared spectral studies for pure and complexed PVA films revealed the vibrational changes that occurred due to the effect of dopant salt in the polymer. Direct current conductivity was measured in the temperature range of 303–373 K, and the conductivity was found to increase with the increase in dopant concentration as well as temperature. Measurement of transference number was carried out to investigate the nature of charge transport in these polymer electrolyte films using Wagner’s polarization technique. Transport number data showed that the charge transport in these polymer electrolyte systems was predominantly due to ions. Using these polymer electrolytes, solid-state electrochemical cells were fabricated. Various cell parameters like open-circuit voltage, short circuit current, power density, and energy density were determined.     

氮/硫共掺杂多孔碳纳米片的制备及其电化学性能

二维多孔碳材料能够提供较短的电解质扩散通道和较快的电子传输过程,因此在能量转换和储存装置中表现出优异的电化学性能.近年来的理论和实验研究表明,两元素共掺杂可使二维多孔碳材料的电化学性能得到明显提高.因此,共掺杂二维多孔碳材料的制备成为目前的研究热点之一.本文以甲基橙-FeCl₃复合物为模板引发剂制备了甲基橙掺杂的聚吡咯纳米管,通过对聚吡咯纳米管与KOH混合物（重量比为1：2）在700 ℃进行热处理,制备了二维石墨烯状氮/硫共掺杂多孔碳纳米片.所制备的氮/硫共掺杂多孔碳纳米片相互连结,形成了多级孔结构.氮气吸附分析表明多级孔结构包含微孔、介孔和大孔,这使所制备的氮/硫共掺杂多孔碳纳米片具有较高的比表面积（1744.58 m²/g）和孔体积（1.01 cm³/g）.共掺杂多孔碳纳米片中的掺杂氮以吡啶氮、吡咯氮和季胺氮形式存在,掺杂硫以噻吩硫和氧化态硫形式存在,二者之间的协同效应能够明显改善碳纳米片表面的浸润性,增加表面电化学活性点.这些特征使所制备的氮/硫共掺杂多孔碳纳米片表现出优异的电化学性能.用氮/硫共掺杂多孔碳纳米片制备的量子点敏化太阳能电池对电极,对多硫电解质再生反应的电催化活性与传统PbS对电极相近,所组装电池的光电转换效率可达到4.30%（100 mW/cm²）.氮/硫共掺杂多孔碳纳米片作为超级电容器电极材料,以6 M（1 M=1 mol/L）KOH为电解质,电流密度为0.4 A/g,比电容达到312.8 F/g.即使电流密度增加到20 A/g,比电容仍达到200.6 F/g,表明其具有较好的倍率性能.     

Polaron and ion diffusion in a poly(3-hexylthiophene) thin-film transistor gated with polymer electrolyte dielectric

Electrolytes are finding applications as dielectric materials in low-voltage organic thin-film transistors (OTFT). The presence of mobile ions in these materials (polymer electrolytes or ion gels) gives rise to very high capacitance (>10 μF/cm²) and thus low transistor turn-on voltage. In order to establish fundamental limits in switching speeds of electrolyte gated OFETs, we carry out in situ optical spectroscopy measurement of a poly(3-hexylthiophene) (P3HT) OTFT gated with a LiClO₄:poly(ethyleneoxide) (PEO) dielectric. Based on spectroscopic signatures of molecular vibrations and polaron transitions, we quantitatively determine charge carrier concentration and diffusion constants. We find two distinctively different regions: at V _G≥−1.5 V, drift-diffusion (parallel to the semiconductor/dielectric interface) of hole-polarons in P3HT controls charging of the device; at V _G<−1.5 V, electrochemical doping of the entire P3HT film occurs and charging is controlled by drift/diffusion (perpendicular to the interface) of ClO₄ ⁻ counter ions into the polymer semiconductor.     

Metal-ammonia solutions

In dilute solutions of alkali metals in ammonia electrons are localized in cavities in the solvent, and thermodynamic and transport properties are very similar to those found for dilute solutions of strong electrolytes. At higher concentrations the properties deviate markedly from those of electrolyte solutions and approach those of a liquid metal. In this paper we propose an explanation for cavity formation, and discuss the metal-non-metal transition in the light of recent information about the transition in vanadium oxides and doped semiconductors.     

Nanocomposite of p-type conductive polymer/Cu (II)-based metal-organic frameworks as a novel and hybrid electrode material for highly capacitive pseudocapacitors

In this paper firstly, Cu (II)-based metal-organic framework (MOF; Cu-bipy-BTC, bipy = 2,2′-bipyridine, BTC = 1,3,5-tricarboxylate) was synthesized using chemical approach and then fabricated hybrid poly ortho aminophenol (POAP)/Cu-bipy-BTC films by electropolymerization of POAP in the presence of Cu-bipy-BTC nanoparticles to serve as the active electrode for electrochemical storage device. Surface analysis and electrochemical analysis have been used for characterization of POAP/Cu-bipy-BTC composite film. Different electrochemical methods including galvanostatic charge–discharge experiments, cyclic voltammetry, and electrochemical impedance spectroscopy are carried out in order to investigate the performance of the system. This work introduces new nanocomposite materials for electrochemical redox capacitors with advantages including ease synthesis, high active surface area, and stability in an aqueous electrolyte.     

一种高电导率PVA聚合物电解质的制备与表征

通过溶液浇注法制备了一种polymer in salt型PVA KOH H2O聚合物电解质.对该电解质进行了X射线衍射、热性质及电化学性质测试与分析.X射线衍射显示PVA和KOH在聚合物电解质中均以非晶态存在.随着KOH含量的增加,聚合物的玻璃转化点温度逐渐上升,而电解质电导率也随之增加.该电解质的电化学窗口可达1.4V,阻抗测试显示当电解质组成PVA/KOH为1/3(质量比)时,室温电导率可达0.15S/cm,电导率与温度关系符合Arrhenius方程.该电解质热力学稳定性好,机械强度高、电化学性质优越.     

电解质对浓悬浮液中胶体颗粒扩散特性的影响

本文利用相位调制光纤低相干动态光散射装置, 研究了不同物质量浓度下电解质 (NaCl及 BaCl₂) 对浓悬浮液中聚苯乙烯胶体颗粒扩散特性的影响. 实验结果表明, 当电解质浓度低于0.01 mol/L 时, 恒温条件下浓悬浮液中聚苯乙烯胶体颗粒扩散系数随电解质离子浓度以及离子化合价的增大而增大, 实验测量得到的扩散系数与Stern模型所得到的扩散系数符合较好. 关键词： 测量 电解质 浓悬浮液 低相干动态光散射     

Performance evaluation of PVdF gel polymer electrolytes

A series of gel polymer electrolytes containing PVdF as homo polymer, a mixture of 1:1 Ethylene Carbonate (EC) : Propylene Carbonate (PC) as plasticizer and lithium-bistrifluoromethane sulphone imide [imide — LiN (CF₃SO₂)₂] has been developed. Amounts of polymer (PVdF), plasticizer and the imide lithium salt have been varied as a function of their weight ratio composition in this regard. Dimensionally stable films possessing appreciable room temperature conductivity values have been obtained with respect to certain weight ratio compositions. However, conductivity data have been recorded at different possible temperatures, i.e., from 20 °C to 65 °C. XRD and DSC studies were carried out to characterize the polymer films for better amorphicity and reduced glass transition temperature, respectively. The electrochemical interface stability of the PVdF based gel polymer electrolytes over a range of storage period (24 h – 10 days) have been investigated using A.C. impedance studies. Test cells containing Li/gel polymer electrolyte (GPE)/Li have been subjected to undergo 50 charge-discharge cycles in order to understand the electrochemical performance behaviour of the dimensionally stable films of superior conductivity. The observed capacity fade of less than 20% even after 50 cycles is in favour of the electrochemical stability of the gel polymer electrolyte containing 27.5% PVdF −67.5 % EC+PC −5% imide salt. Cyclic voltammetry studies establish the possibility of a reversible intercalation — deintercalation process involving Li⁺ ions through the gel polymer electrolyte.     

Investigations on electrical properties of (PVA:NaF) polymer electrolytes for electrochemical cell applications

Solid polymer electrolytes based on poly (vinyl alcohol) (PVA) complexed with sodium fluoride (NaF) at different weight percent ratios were prepared using solution cast technique. The structural properties of these electrolyte films were examined by XRD studies. The XRD data revealed that the amorphous domains of PVA polymer matrix increased with increase of NaF salt concentration. The complexation of the salt with the polymer was confirmed by FT-IR studies. Electrical conductivity was measured in the temperature range of 303–373 K and the conductivity was found to increase with the increase of dopant concentration as well as temperature. The dielectric constant (ε′) increased with the increase in temperature and decreased with the increase in frequency. A loss peak was identified at 365 K in the dielectric loss spectra and is attributed to the orientation of polar groups. Measurement of transference number was carried out to investigate the nature of charge transport in these polymer electrolyte films using Wagner’s polarization technique and Watanabe technique. Transport number data showed that the charge transport in these polymer electrolyte systems was predominantly due to ions and in particular due to anions. Using these polymer electrolytes, solid state electrochemical cells were fabricated. Various cell parameters like open circuit voltage (OCV), short circuit current (SCC), power density and energy density were determined.     

Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) gel electrolytes: a detailed investigation of their conductivity and characterization

Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PEG/PAMPS) with a transparent appearance were prepared in the presence of ammonium persulfate (APS) as an initiator at 70 °C for 24 h. PEG/PAMPS-based polymer gel electrolytes in a motionless and uniform state were obtained by adding the required amount of liquid electrolytes to a dry PEG/PAMPS polymer. Liquid electrolytes include organic solvents with high boiling points (-1-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL)) and a redox couple (alkali metal iodide salt/iodine). The optimized conditions for PEG/PAMPS-based gel electrolytes based on the salt type, the concentration of alkali metal iodide salt/iodine, and solvent volume ratio were determined to be NaI, 0.4 M NaI/0.04 M I₂, and NMP:GBL (7:3, v/v), respectively. The highest ionic conductivity and the liquid electrolyte absorbency were 2.58 mS cm^?1 and 3.6 g g^?1 at 25 °C, respectively. The ion transport mechanism in both the polymer gel electrolytes and liquid electrolytes is investigated extensively, and their best fits with respect to the temperature dependence of the ionic conductivity are determined with the Arrhenius equation.     

Natural polymer-based electrolytes for electrochemical devices: a review

Polymer electrolytes are an important component of many electrochemical devices. Researchers have carried out a significant work for the development of polymer electrolytes. This paper reviews the recent developments in the area of polymer electrolytes using aqueous and nonaqueous-based natural polymers for developing a cheaper, ecofriendly, biodegradable, and widely used electrolytes as a substitute for existing synthetic polymer electrolytes. This paper also encompasses the merits and demerits of the different natural polymers used by the researcher. There is a scope to develop a nonaqueous-based natural polymer electrolyte as an alternate for synthetic polymer electrolyte for batteries and other electronic devices.     

FT-Raman spectroscopy study of solvent-in-salt electrolytes

Cation–anion interaction with different ratios of salt to solvent is investigated by FT-Raman spectroscopy. The fitting result of the C–N–C bending vibration manifests that the cation–anion coordination structure changes tremendously with the variation of salt concentration. It is well known that lithium-ion transport in ultrahigh salt concentration electrolyte is dramatically different from that in dilute electrolyte, due to high viscosity and strong cation–anion interaction. In ultrahigh salt concentrated "solvent-in-salt" electrolyte(SIS-7#), we found, on one hand, that the cation and anion in the solution mainly formed cation–anion pairs with a high Li~+coordination number(≥ 1), including intimate ion pairs(20.1%) and aggregated ion pairs(79.9%), which not only cause low total ionic conductivity but also cause a high lithium transference number(0.73). A possible lithium transport mechanism is proposed: in solvent-in-salt electrolytes, lithium ions' direct movement presumably depends on Li-ion exchange between aggregated ion pairs and solvent molecules, which repeats a dissolving and re-complexing process between different oxygen groups of solvent molecules.     

Quasi-solid state polymer electrolytes for dye-sensitized solar cells: Effect of the electrolyte components variation on the triiodide ion diffusion properties and charge-transfer resistance at platinum electrode

Quasi-solid state polymer electrolytes have been prepared from poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) as gelator for 1-ethyl-3-methylimidazolium based ionic liquids (with anions like trifluoromethanesulfonate [EMIM][TfO], bis(trifluoromethanesulfonyl)imide [EMIM][Tf₂N]) and polyacrylonitrile (PAN) for gelation of 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA] as well as I⁻/I₃⁻ as the redox couple. All electrolytes exhibit high ionic conductivity in the range of 10^− 3 S/cm. The effect of gelation, redox couple concentration, I⁻/I₃⁻ ratio, choice of cations and additives on the triiodide diffusion and charge-transfer resistance of the platinum/electrolyte interface (R_ct) were studied. The apparent diffusion coefficient of triiodide ion (D(I₃⁻)) at various iodide/triiodide ratios in liquid and gelified electrolytes has been calculated from measurements of the diffusion limited current (I_lim) in electrochemical cell resembling the set-up of a dye-sensitized solar cell. The charge-transfer resistance of the platinum/electrolyte interface as well as the capacitance of the electrical double layer (C_dl) have been calculated from impedance measurements. Electrolytes with reduced content of polymer (2.5 wt.%) were doped with Al₂O₃ particles of different sizes (50 nm, 300 nm, 1 μm). The dispersion of the particles proceeds by speedy stirring of the hot electrolyte and the addition of PAN provides a homogeneous suspension. The addition of Al₂O₃ particles causes a slight increase of the triiodide diffusion constants. Furthermore the suggested enhancement of the charge transfer rate shows a dependence on the size of the particles.