Solid Reference Electrode of Metallurgical Oxygen Sensor

The thermal equilibrium state of the reference electrode was investigated. The results show that the temperature difference between the inside and the outside of zirconia tube was very small and the Seebeck effect can be ignored after the sensor was dipped into liquid steel for more than 2 s. A special sensor was designed to test the relation between the EMF （electromotive force） of sensor and the thermal equilibrium state of the reference elec- trode. Based on these results, it is suggested that the peak in EMF curve was caused by the change of oxygen potential in reference electrode before the thermal equilibrium was reached. If NiO was added by 2 M- 5 M to the Cr/Cr2O3 reference electrode, the peak in EMF curve could be eliminated.

Preparation and Properties of Embeddable Ag/Ag Cl Gelling Reference Electrode for Rebars Corrosion Monitoring in Concrete

Reference electrodes are a key part for corrosion monitoring and measurement of rebars in concrete. A reference electrode that can be buried in concrete is fabricated by using Ag/Ag Cl electrode and methyl cellulose gelling electrolyte. The stability, repeatability and anti-polarization of the reference electrode are investigated; the influences of the inner electrolyte loss, exterior OH- contamination, and temperature on the potential of the reference electrode are also investigated in this paper. The results show that the reference electrode has good stability, repeatability, and antipolarization. The influences of inner electrolyte loss, exterior OH- contamination, and temperature on the potential of the reference electrode are minimal. Therefore, it can be used for corrosion monitoring and measurement of rebars in concrete.

Electrochemical study of different membrane materials for the fabrication of stable,reproducible and reusable reference electrode

Fabrication of stable,reproducible and reusable reference electrodes for low energy and high-temperature steam splitting is of great interest for hydrogen fuel production without anthropogenic carbon dioxide(CO2)emission.This study has been conducted for the detection of suitable material for the fabrication of novel reference electrode.In the present scenario,this research is designed to fabricate a novel nickel reference electrode by using operating conditions of eutectic molten hydroxide(NaOH-KOH,49-51 mol%)at temperature 300℃in an ion-conducting membrane of alumina and mullite tube.Afterwards,the designed nickel reference electrode has been examined for its reusability and stability by using electrochemical technique and cyclic voltammetry.Five scans of cyclic voltammetry are performed for both membrane fabricated reference electrode.A slight positive shift in oxidation peaks is observed for mullite membrane electrode(64 mV from scan 1 to 5).The stability measurements are noted by changing the scan rate between 50 and 150 mV s−1.Furthermore,the results show that the Ni/Ni(OH)2 reference electrode covered with a mullite membrane is stable and reusable at 300℃temperature without any deterioration.The stability and reusability of prepared nickel reference electrode covered by mullite tube in the eutectic molten hydroxide were up to 9 days to carry out an electrochemical investigation,while for alumina tube reference electrode the stability and reliability were up to 3 days.The internal electrolytic material and ionic conductance can play an important role for future studies with this reference electrode along with optimisation of temperature and scan rate parameters.

Study on the High Conductive Polymer as the Miniaturized Reference Electrode

The polypyrrole is the high conductive polymer which was coated onto indium tin oxide (ITO) glass substrate by electroplated technique to fabricate a miniaturized reference electrode.Besides,the morphology of the ITO glass reference electrode electroplated with pyrrole has been studied through the instrumental analysis utilizing cyclic voltammetry (CV). Furthermore,the sensing characteristics of the reference electrode have been measured by using commercial instrumental amplifier as the readout circuit.Using the high conductive polymer as miniaturized reference electrode has many advantages such as easy fabrication of coating polymer,without any expensive fabricating equipment,easy carry by the miniaturized technique.Hence,it is suitable for the reference electrode production.

Preparation of Ti/MnO_2 Reference Electrode and Its Application in Concrete Structures

A novel Ti/MnO2 reference electrode (TMRE) used for concrete environment was fabricated by the electro-deposition method and encapsulated carefully.The properties of the electrode were characterized by open-circuit potential,potentiodynamic polarization behavior in synthetic concrete pore solutions and electrochemical performance in cement mortar.The experimental results indicate that the TMRE shows good stability with and without the addition of Cl-ions and desirable polarization behavior in synthetic pore solution.Results of tests in cement mortar indicate that the potential of TMRE will be stable after about 7 days.The stability and desirable polarization behavior make it a promising reference electrode for concrete environment.

Parameter-independent error correction for potential measurements by reference electrode in lithium-ion batteries

The safety monitoring of lithium-ion batteries(LIBs) is of great significance for realizing all-climate and full-lifespan battery management. In-situ measurement of anode potential with implanted reference electrodes(REs) has proven to be effective to monitor and avoid the occurrence of severe side reactions like Li plating to ensure the safe and fast charging. However, the intrinsic measurement errors caused by local blocking effects, which also can be referred to as potential artefacts, are seldom taken into consideration in existing studies, yet they highly dominate the correctness of conclusions inferred from REs. In this study, aiming at exploring the physical origin of the measurement errors and ensure reliable potential monitoring, electrochemical and post-mortem tests are conducted using commercial pouch cells with implanted REs. Corresponding electrochemical model which describes the blocking effects, is established to validate the abnormal absence of lithium plating that predicted by measured anode potentials under various charging rates. Theoretical derivation is further presented to explain the error sources, which can be attributed to increased local liquid potential of the RE position. Most importantly, with the guidance of error analysis, a novel parameter-independent error correction method for RE measurements is proposed for the first time, which is proven to be adequate to estimate the real anode potentials and deduce the critical C-rate of Li plating with extra safety margin. After error correction, the resulting critical C-rates are all within the range of 0.55 ± 0.03 C, which is close to the C-rate of 0.6–0.7 C obtained from experiments. In addition, this error correction method can be performed conveniently with only some simple RE measurements of polarization voltages, totally independent of battery electrochemical and geometric parameters. This study provides highly practical error correction method for RE measurements in real LIBs, substantially facilitating the fast diagnosis and safety evaluation of Li plating during charging of LIBs.

High-temperature Reference Electrodes Used in Molten Fluorides

The thermodynamic and dynamic behaviour of Ni^(2+)|Ni couple in FLINAK melt is investigated by us- ing EMF measurement and micropolarization method.The couple shows the Nernstian reversibility and a large exchange current density(6 mA·cm^(-2)).A single crystal LaF_3 which is a fluoride ion conductor used as a membrane of the Ni^(2+)|Ni couple reference electrode is reliable in FLINAK melts at 973 K.The poten- tial of LaF_3 membrane reference electrode is constant within±2 mV.The boron nitride used as a salt bridge was not good in FLINAK melts.The platinum electrode is studied by using micropolarization.The equilibrium potential of Pt electrode is dependent on the absorption and the electrochemical reaction.The potential is stable for a constant composition at constant temperature.

A Reliable Reference Electrode in Molten Carbonate and Its Applications

A Ag|AgCl reference electrode which can be used in molten carbonate media has been described in this paper.It consists of a silver wire immersed in a solution of AgCl(1mol%) in (Li 0.62 ,K 0.38 ) 2CO 3,with a zirconia junction.The main properties of reference electrode,such as reproducibility ,stability and reversibility, were checked.The results have demonstrated that the reference electrode is reliable.With such reference electrode catalysis of various electrode materials to oxygen reduction in molten alkali carbonate media was investigated.It is found that as catalysts for oxygen reduction oxidized nickel niobium alloy is superior to nickel oxide.

Electrochemical Performance of High Purity Zinc and Zn-Al-Cd Alloy as Reference Electrodes

The effects of Cl-concentration,temperature,pH,flow velocity,soluble oxygen content of seawater and anodic current on the potential of high purity zinc and Zn-Al-Cd reference electrodes were investigated. The results show that the investigated metal materials are liable to establish stable potential and act as reference electrodes in seawater,diluted seawater and urban tap water. Cl-concentration,temperature,seawater flow velocity and anodic current have an obvious effect on zinc potentials. However,seawater pH has no obvious effect on zinc potentials.

Enhanced high temperature cycling performance of LiMn_2O_4/graphite cells with methylene methanedisulfonate(MMDS) as electrolyte additive and its acting mechanism

The effects of methylene methanedisulfonate（MMDS） on the high-temperature（0℃） cycle performance of LiMnO/graphite cells are investigated.By addition of 2 wt%MMDS into a routine electrolyte,the high-temperature cycling performance of LiMn204/graphite cells can be significantly improved.The analysis of differential capacity curves and energy-dispersive X-ray spectrometry（EDX） indicates that MMDS decomposed on both cathode and anode.The three-electrode system of pouch cell is used to reveal the capacity loss mechanism in the cells.It is shown that the capacity fading of cells without MMDS in the electrolytes is due to irreversible lithium consumption during cycling and irreversible damage of LiMnOmaterial,while the capacity fading of cell with 2 wt%MMDS in electrolytes mainly originated from irreversible lithium consumption during cycling.

Thermodynamic Foundation for High Temperature Electrochemistry

Thermodynamic concepts required for the thermodynamic calculation of the potentials of electrodes for high temperature applications are briefly reviewed. A thermodynamic approach to the calculation of half cell potentials and the standard chemical potential of an electron at high temperatures which are related to the Standard Hydrogen Electrode(SHE) is discussed. As examples, an external Ag/AgCl reference electrode and a YSZ(Ag|O_2) pH sensor for high temperature applications are analyzed by using the thermodynamic approach to derive a high temperature pH measurement equation. The two electrodes are employed to measure high temperature pH and the measured pH was compared with the calculated pH by using a solution chemistry method. Concepts and principles for electrode kinetics are also briefly introduced and a modification to the Tafel equations is suggested.

Multiscale observation of Li plating for lithium-ion batteries

As the most hazardous side reaction,Li plating poses high risks of undermining electrochemical performance of Li-ion batteries by accelerating degradation.Under some extreme abuse conditions,Li plating can even jeopardize safety performance and induce catastrophic results like thermal runaway.Therefore,multiscale observation of Li plating is of great significance for understanding the internal mechanisms and early detection of Li plating.In this mini-review,the recent progress of formation mechanisms of plated metallic lithium was introduced.Then,the in situ and ex situ observation methods of macroscopic,microscopic and atomic level were summarized.Reference electrode provides a promising tool for real-time monitoring of anode potential,which is the critical factor of Li plating,showing great potentials in cloudbased battery management systems.Finally,some perspectives for future researches on Li plating observation and corresponding utilizations in developing Li plating free control strategies were proposed.

Localized Corrosion of Binary Mg-Ca Alloy in 0.9 wt%Sodium Chloride Solution

To further understand the localized corrosion of magnesium alloy, various in situ electrochemical techmques and ex situ electron microprobe analysis and SEM were used to monitor the corrosion process of Mg-l.0Ca alloy in 0.9 wt% sodium chloride solution. The results indicated that the localized corrosion was accompanied by the formation and thickening of a corrosion product film on the Mg-l.0Ca alloy. A localized corrosion of the alloy initiated selectively on the eutectic micro-constituent zones, then enhanced with the exposure, developed in depth with ring-shaped corrosion products accumulated around and finally formed a volcanic-like pitting. Based on the measurements, an electrochemical corrosion model was proposed accordingly to describe the formation mechanism of the volcanic-like pitting on the alloy in 0.9 wt% sodium chloride solution.