Interpreting electrochemical noise resistance as a statistical linear polarisation resistance

A theoretical analysis on the electrochemical noise resistance is carried out based on basic electrochemical corrosion theory. It is proven that the noise resistance is equivalent to the polarisation resistance and is in fact a special form of linear polarisation resistance, namely statistical linear polarisation resistance.

Applications of scanning electrochemical microscopy (SECM) for local characterization of AZ31 surface during corrosion in a buffered media

Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH. © 2014 Elsevier Ltd.

An electrochemical method for measuring localized corrosion under cathodic protection

 A new method has been developed to measure metal corrosion rates and their distribution under cathodic protection (CP). This method uses an electrochemically integrated multi-electrode array to take local measurements of cathodic current density while simulating a continuous metallic surface. The distribution of cathodic current densities obtained under CP was analyzed to estimate the anodic current component at each electrode of the array. Corrosion patterns determined by this new method have shown good correlation with visual inspection and surface profilometry of the multi-electrode array surface.

Excellent electrochemical performance of LiFe0.4Mn0.6PO4 microspheres produced using a double carbon coating process

Composite LiFe0.4Mn0.6PO4/C microspheres are considered advanced cathode materials for electric vehicles and other high-energy density applications due to their advantages of high energy density and excellent cycling stability. LiFe0.4Mn0.6PO4/C microspheres have been produced using a double carbon coating process employing traditional industrial techniques (ball milling, spray-drying and annealing). The obtained LiFe0.4Mn0.6PO4 microspheres exhibit a high discharge capacity of around 166 mA h g-1 at 0.1 C and excellent rate capabilities of 132, 103, and 72 mA h g-1 at 5, 10, and 20 C, respectively. A reversible capacity of about 152 mA h g-1 after 500 cycles at a current density of 1 C indicates an outstanding cycling stability. The excellent electrochemical performance is attributed to the micrometer-sized spheres of double carbon-coated LiFe0.4Mn0.6PO4 nanoparticles with improved electric conductivity and higher Li ion diffusion coefficients, ensuring full redox reactions of all nanoparticles. The results show that the advanced high-energy density cathode materials can be produced using existing industry techniques.

New opportunities for quantitative and time efficient 3D MRI of liquid and solid electrochemical cell components: Sectoral Fast Spin Echo and SPRITE.

The ability to image electrochemical processes in situ using nuclear magnetic resonance imaging (MRI) offers exciting possibilities for understanding and optimizing materials in batteries, fuel cells and supercapacitors. In these applications, however, the quality of the MRI measurement is inherently limited by the presence of conductive elements in the cell or device. To overcome related difficulties, optimal methodologies have to be employed. We show that time-efficient three dimensional (3D) imaging of liquid and solid lithium battery components can be performed by Sectoral Fast Spin Echo and Single Point Imaging with T1 Enhancement (SPRITE), respectively. The former method is based on the generalized phase encoding concept employed in clinical MRI, which we have adapted and optimized for materials science and electrochemistry applications. Hard radio frequency pulses, short echo spacing and centrically ordered sectoral phase encoding ensure accurate and time-efficient full volume imaging. Mapping of density, diffusivity and relaxation time constants in metal-containing liquid electrolytes is demonstrated. 1, 2 and 3D SPRITE approaches show strong potential for rapid high resolution (7)Li MRI of lithium electrode components.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

General approach for electrochemical functionalization of glassy carbon surface by in situ generation of diazonium ion under acidic and non-acidic condition with a cascade protocol

Immobilization of catechol derivatives on GC electrode surfaces can be performed by in situ generation and reduction of nitrocatechol. We present the oxidative nitration of catechol in the presence of nitrous acid followed by electrochemically reduction of the generated nitro aromatic group to the corresponding amine group and its conversion to diazonium cation at the electrode surface to yield a surface covalently modified with catechol. In this manner, some derivatives of catechol can be immobilized on the electrode surface. Whole of the process is carried out in Triethylammonium acetate ionic liquid as an inert and neutral medium (pH∼7.0). Surface coverage can be easily controlled by the applied potential, time and concentration of catechol. After modification, the electrochemical features of modified surface have been studied. Also modified GC electrode exhibited remarkable catalytic activity in the oxidation of NADH. The catalytic currents were proportional to the concentration of NADH over the range 0.01-0.80 mM. This condition can be used for modification of GC surfaces by various aromatic molecules for different application such as design of sensors and biosensors. © 2014 Elsevier Ltd. All rights reserved.

Electrochemical performance of LiFe1-xMnxPO4/C materials prepared by ball milling

LiFe1-xMnxPO4/C composite materials as cathode materials in Li-ion batteries have been synthesised and their electrochemical properties have been investigated. The samples were synthesised by using high energy ball milling of commercially available precursors (Li2C2O4, FeC2O4.2H2O, MnC2O4.2H2O, NH4H2PO4) and then heated at 600°C. The morphology and structure of the heated samples were analysed by means of SEM and X-ray diffraction. The olivine structure of the LiFe1-xMnxPO4/C composite was obtained. A slight shift of the peaks to smaller 2θ angles with the increasing Mn/Fe ratios is observed due to the increase in lattice parameters. The influence of different Mn/Fe ratios on electrical and electrochemical performances were studied by charge-discharge and cyclic voltammetry (CV) testing. The CV curves of the pure LiFePO4 and LiMnPO4 show the expected Fe2+/Fe3+ peak around 3·5 V and Mn2+/Mn3+ peak around 4·1 V, respectively. The addition of manganese increases the discharge voltage from 3·5 to 4·1 V.

Evolution of the electrochemical capacitance of transition metal oxynitrides with time: the effect of ageing and passivation

A number of transition metal nitrides and oxynitrides, which are actively investigated today as electrode materials in a wide range of energy conversion and storage devices, possess an oxide layer on the surface. Upon exposure to ambient air, properties of this layer progressively change in the process known as "ageing". Since a number of electrochemical processes involve the surface or sub-surface layers of the active electrode compounds only, ageing could have a significant effect on the overall performance of energy conversion and storage devices. In this work, the influence of the ageing of tungsten and molybdenum oxynitrides on their electrochemical properties in supercapacitors is explored for the first time. Samples are synthesised by the temperature-programmed reduction in NH3 and are treated with different gases prior to exposure to air in order to evaluate the role of passivation in the ageing process. After the synthesis, products are subjected to controlled ageing and are characterised by low temperature nitrogen adsorption, X-ray photoelectron spectroscopy and transmission electron microscopy. Capacitive properties of the compounds are evaluated by performing cyclic voltammetry and galvanostatic charge and discharge measurements in the 1 M H2SO4 electrolyte. © 2014 the Partner Organisations.

Effect of sintering temperature on electrochemical performance of LiFe0·4Mn0·6PO4/C cathode materials

Carbon coated LiFe0·4Mn0·6PO4 (LiFe0·4Mn0·6PO4/C) was synthesised using high energy ball milling and annealing processes. The starting materials of Li2C2O4, FeC2O4.2H2O, MnC2O4.2H2O, NH4H2PO4 were firstly milled for 40 h, and followed by further milling for 5 h after adding glucose solution. The milled sample was heated at different temperatures (550, 600, 650 and 700°C) for 10 h to produce LiFe0·4Mn0·6PO4/C composites. The structure and morphology of the samples were investigated using X-ray diffraction, field emission scanning electron microscopy, and high resolution electron microscopy. The phase of samples annealed at 550 and 600°C mainly consists of olivine type LiFePO4, but a small amount of Fe2P impurity phase is formed in the samples annealed at 650 and 700°C. Electrochemical analysis results show that LiFe0·4Mn0·6PO4/C synthesised at 600°C exhibits the best performance with the initial discharge capacity of 128 mAh g-1 at 0·1 C, and 109 mAh g-1 at 1 C after 500 cycles. The LiFe0·4Mn0·6PO4/C exhibits excellent electrochemical properties for high energy density lithium ion batteries.

Ex situ electrochemical sodiation/desodiation observation of Co₃O₄ anchored carbon nanotubes: a high performance sodium-ion battery anode produced by pulsed plasma in a liquid

Liquid plasma, produced by nanosecond pulses, provides an efficient and simple way to fabricate a nanocomposite architecture of Co3O4/CNTs from carbon nanotubes (CNTs) and clusters of Co3O4 nanoparticles in deionized water. The crucial feature of the composite's structure is that Co3O4 nanoparticle clusters are uniformly dispersed and anchored to CNT networks in which Co3O4 guarantees high electrochemical reactivity towards sodium, and CNTs provide conductivity and stabilize the anode structure. We demonstrated that the Co3O4/CNT nanocomposite is capable of delivering a stable and high capacity of 403 mA h g(-1) at 50 mA g(-1) after 100 cycles where the sodium uptake/extract is confirmed in the way of reversible conversion reaction by adopting ex situ techniques. The rate capability of the composite is significantly improved and its reversible capacity is measured to be 212 mA h g(-1) at 1.6 A g(-1) and 190 mA h g(-1) at 3.2 A g(-1), respectively. Due to the simple synthesis technique with high electrochemical performance, Co3O4/CNT nanocomposites have great potential as anode materials for sodium-ion batteries.

Graphene nanodots-encaged porous gold electrode fabricated via ion beam sputtering deposition for electrochemical analysis of heavy metal ions

All rights reserved. A graphene nanodots-encaged porous gold electrode via ion beam sputtering deposition (IBSD) for electrochemical sensing is presented. The electrodes were fabricated using Au target, and a composite target of Al and graphene, which were simultaneously sputtered onto glass substrates by Ar ion beam, followed with hydrochloric acid corrosion. The as-prepared graphene nanodots-encaged porous gold electrodes were then used for the analysis of heavy metal ions, e.g. Cu2+ and Pb2+ by Osteryoung square wave voltammetry (OSWV). These porous electrodes exhibited enhanced detection range for the heavy metal ions due to the entrapped graphene nanodots in 3-D porous structure. In addition, it was also found that when the thickness of porous electrode reached 40 nm the detection sensitivity came into saturation. The linear detection range is 0.009-4 μM for Cu2+ and 0.006-2.5 μM for Pb2+. Good reusability and repeatability were also observed. The formation mechanism and 3-D structure of the porous electrode were also investigated using scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectra (XPS). This graphene entrapped 3-D porous structure may envision promising applications in sensing devices.

Real-time electrochemical monitoring of covalent bond formation in solution via nanoparticle-electrode collisions

We describe an alternative electrochemical technique to monitor covalent bond formation in real-time using nanoparticle-electrode collisions. The method is based on recognising the redox current when MP-11 functionalised chemical reduced graphene oxide (rGO) nanosheets collide with Lomant's reagent modified gold microelectrode. This facile and highly sensitive monitoring method can be useful for investigating the fundamental of single-molecule reactions.

Electrochemical impedance spectroscopy as a tool to measure cathodic disbondment on coated steel surfaces: capabilities and limitations

The disbondment of protective organic coatings under excessive cathodic protection potentials is a widely reported coating failure mechanism. Traditional methods of evaluating cathodic disbondment are based on ex situ visual inspection of coated metal surfaces after being exposed to standard cathodic disbondment testing conditions for a long period of time. Although electrochemical impedance spectroscopy (EIS) has been employed as an effective means of evaluating various anti-corrosion properties of organic coatings; its application for assessing the cathodic disbondment resistance of coatings has not been sufficiently exploited. This paper reports an experimental study aimed at developing EIS into a tool for in situ measurement and monitoring of cathodic disbondment of coatings. A clear correlation between EIS parameters and the disbonded coating areas has been confirmed upon short term exposure of epoxy-coated steel electrodes to cathodic disbondment conditions; however the degree of this correlation was found to decrease with the extension of exposure duration. This observation suggests that EIS loses its sensitivity with the propagation of coating disbondment, and that in order to achieve quantitative determination of the coating cathodic disbondment localized EIS measurements are required to measure the parameters related to local disbonded areas.