Common Reference Electrode Research Articles

Comparing Electrode Overpotential Contributions in Vrfbs Amongst Multiple Techniques

Redox flow batteries (RFBs) offer a potential remedy for the escalating need for energy storage amid the ongoing transition from carbon-intensive fossil energy to renewable energy sources. Yet, many RFB chemistries are shown to have low energy efficiencies which can be attributed, in part, to ineffective electrode materials. Identifying overpotential contributions from electrodes under operating conditions is a key step in understanding how to design better RFB electrodes Previously, three-electrode setups using rotating disk electrodes (RDE) were the effective technique at isolating overpotentials; however, this can only be accomplished by looking at one side of the RFB at a time. RDEs do not easily replicate the operational conditions of a power cell or the porous nature of carbon electrodes used in RFBs. Alongside the normal operation of an RFB, symmetry cells are another approach that can be utilized in quantifying the performance of electrodes. The advantage of a symmetrical cell setup allows us to monitor the overpotential contributions of two different electrodes in the same electrolyte concurrently. Membrane-based reference electrodes (MBRE), and other reference electrode integration concepts, allow us to use three-electrode techniques in operational RFB power cells. As a case study, we examined the effect of oxidative electrode treatments on the positive and negative side of the VRFB using multiple methods. While other studies have shown that an untreated negative electrode may be the key inhibitor in VRFB performance, we have quantified the overpotential at 50% state of charge to be 194 mV when 50 mA cm-2 is applied. After an oxidative treatment is applied to the negative electrode, the overpotential is reduced to 111 mV. Applying this to other techniques, we can compare the effectiveness of a non-symmetry cell setup vs. a symmetry cell setup, which displayed that oxidative treatment techniques appear to have an opposite effect on the positive electrode. A treated-positive electrode shows an overpotential of around 100 mV whereas an untreated-positive electrode only contributes 15 mV less of overpotential. These findings are further compared using common reference electrodes placed in the electrolyte tank, providing insights into the effectiveness of power cell techniques in improving RFB electrode performance.

Multiplexing System for Automated Characterization of a Capacitive Field‐Effect Sensor Array

In comparison to single‐analyte devices, multiplexed systems for a multianalyte detection offer a reduced assay time and sample volume, low cost, and high throughput. Herein, a multiplexing platform for an automated quasi‐simultaneous characterization of multiple (up to 16) capacitive field‐effect sensors by the capacitive–voltage (C–V) and the constant‐capacitance (ConCap) mode is presented. The sensors are mounted in a newly designed multicell arrangement with one common reference electrode and are electrically connected to the impedance analyzer via the base station. A Python script for the automated characterization of the sensors executes the user‐defined measurement protocol. The developed multiplexing system is tested for pH measurements and the label‐free detection of ligand‐stabilized, charged gold nanoparticles.

High-Throughput Activity Screening of Oxygen Reduction and Oxygen Evolution Catalysts

High-throughput techniques are being actively studied to expedite the evaluation of the electrocatalytic activity of newly developed materials. These techniques include the use of optical sensing or electrochemical array cells in stagnant or hydrodynamic aqueous electrolytes [1-2]. A new high-throughput electrochemical cell has been developed utilizing multiple glassy carbon working electrodes with dimensions comparable to those of a conventional ring-disk electrode (RDE) that are inserted into a channel flow cell (Figure 1) comprised of two PEEK blocks separated by a gasket that defines the electrolyte channel depth. This cell enables evaluation of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) activity as a function of the potential of multiple catalyst samples simultaneously that are deposited on the glassy carbon electrodes using standard methods used for RDE electrodes (e.g., using a hand-held micropipette). As shown in Figure 1, a common reference electrode is located in the lower cell block across an electrolyte channel from the working electrodes and a common counter electrode is located in the electrolyte outlet. Electrolyte flow has been simulated to ensure that the electrolyte is evenly distributed throughout the shallow flow channel with uniform laminar electrolyte flow and identical flow rate for all working electrodes. The new cell is coupled with a Bio-logic multichannel Potentiostat (VSP) that allows the use of multiple working electrodes simultaneously with a common counter electrode and common reference electrode. The catalyst activity and stability results obtained with the new cell have been verified by comparison with RDE measurements for the same catalysts. Acknowledgments This work was supported by the U.S. Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office under the auspices of the Electrocatalysis Consortium (ElectroCat). Argonne National Laboratory is managed for the U.S Department of Energy by the University of Chicago Argonne, LLC, also under contract DE-AC-02-06CH11357.

Wooden Tongue Depressor Multiplex Saliva Biosensor Fabricated via Diode Laser Engraving

Since wood is a renewable, biodegradable naturally occurring material, the development of conductive patterns on wood substrates is a new and innovative chapter in sustainable electronics and sensors. Herein, we describe the first wooden (bio)sensing device fabricated via diode laser-induced graphitization. For this purpose, a wooden tongue depressor (WTD) is laser-treated and converted to an electrochemical multiplex biosensing device for oral fluid analysis. A low-cost laser engraver, equipped with a low-power (0.5 W) diode laser, programmably irradiates the surface of the WTD, forming two mini electrochemical cells (e-cells). The two e-cells consist of four graphite electrodes: two working electrodes, a common counter, and a common reference electrode. The two e-cells are spatially separated via programmable pen-plotting, using a commercial hydrophobic marker pen. Proof-of-principle for biosensing is demonstrated for the simultaneous determination of glucose and nitrite in artificial saliva. This wooden electrochemical biodevice is an easy-to-fabricate disposable point-of-care chip with a wide scope of applicability to other bioassays, while it paves the way for the low-cost and straightforward production of wooden electrochemical platforms.

In Vivo Transdermal Multi-Ion Monitoring with a Potentiometric Microneedle-Based Sensor Patch.

Microneedle sensor technology offers exciting opportunities for decentralized clinical analyses. A novel issue puts forward herein is to demonstrate the uniqueness of membrane-based microneedles to accomplish real-time, on-body monitoring of multiple ions simultaneously. The use of multi-ion detection is clinically relevant since it is expected to provide a more complete and reliable assessment of the clinical status of a subject concerning electrolyte disorders and others. We present a microneedle system for transdermal multiplexed tracing of pH, Na+, K+, Ca2+, Li+, and Cl-. The device consists of an array of seven solid microneedles externally modified to provide six indicator electrodes, each selective for a different ion, and a common reference electrode, all integrated into a wearable patch read in a potentiometric mode. We show in vitro measurements at the expected clinical levels, resulting in a fast response time, excellent reversibility and repeatability, and adequate selectivity. Close-to-Nernstian sensitivity, sufficient stability and resiliency to skin penetration guarantee the sensor's success in transdermal measurements, which we demonstrate through ex vivo (with pieces of rat skin) and in vivo (on-body measurements in rats) tests. Accuracy is evaluated by comparison with gold standard techniques to characterize collected dermal fluid, blood, and serum. In the past, interstitial fluid (ISF) analysis has been challenging due to difficult sample collection and analysis. For ions, this has resulted in extrapolations from blood concentrations (invasive tests) rather than pure measurements in ISF. The developed microneedle patch is a relevant analytical tool to address this information gap.

Neurostimulators for high-resolution artificial retina: ASIC design challenges and solutions

Objective. Neurostimulator is one of the most important part in artificial retina design. In this paper, we discuss the main challenges in the design of application-specific integrated circuit for high-resolution artificial retina and suggest corresponding solutions. Approach. Problems in the design of the neurostimulator for the existing artificial retina have not been solved yet are analyzed and solutions are presented. For verification of the solutions, mathematical proof, MATLAB and Ansys simulations are used. Main results. The drawbacks of resorting to a high-voltage complementary metal oxide semiconductor (CMOS) process to deal with the large voltage compliance demanded by the stimulator output stage are pointed out, and an alternative approach based on a circuit that switches the voltage of the common reference electrode is proposed to overcome. The necessity of an active discharge circuit to remove the residual charge of electrodes caused by an unbalanced stimulus is investigated. We present a circuit analysis showing that the use of a passive discharge circuit is sufficient to suppress problematic direct current in most situations. Finally, possible restrictions on input and output (I/O) count are investigated by estimating the resistive-capacitive delay caused by the interconnection between the I/O pad and the microelectrode array. Significance. The results of this paper clarified the problems currently faced by neurostimulator design for the artificial retina. Through the solutions presented in this study, circuits with more competitiveness in power and area consumption can be designed.

Detection of breast cancer-related point-mutations using screen-printed and gold-plated electrochemical sensor arrays suitable for point-of-care applications

For anticancer therapy and disease prognosis in breast cancer, three PIK3CA point-mutations (H1047R, E545K, and E542K) play a significant role. To allow for specific and sensitive detection of these point-mutations with a hybridization-based detection concept, the assay conditions were optimized on a microarray technology platform. The resulting fluorescence-based microarray assay enables simultaneous and specific detection of three PIK3CA point-mutations. The optimized protocol was then adapted for use on a screen-printed and gold-plated silver sensor array with twelve working electrodes, one common counter electrode, and one common reference electrode. Chronoamperometric measurements employing an enzyme-amplified electrochemical assay allow for detecting PIK3CA point-mutations with a detection limit of 10 pM for short 24-mer target DNA. The mutant and the wild-type target DNA sequences gave significantly different signals in a broad concentration range of 1 nM – 100 nM, with the best separation found at 10 nM – 20 nM. Comparing the hybridization of short 24-mer and long 80-mer target DNA sequences reveals that the hybridization efficiency is reduced for long target DNA sequences. However, both the 24-mer and the 80-mer target DNA lead to successful detection of point-mutations. Finally, the electrochemical sensor allows for multiplexed detection of the three PIK3CA point-mutations.

Selecting a pre-processing pipeline for the analysis of EEG event-related rhythms modulation.

When deciding how to pre-process EEG data, researchers need to make a choice at each single step of the procedure among different possibilities, equally valid. Therefore, in this work, we illustrate how these decisions may affect the quality of the final cleaned data in an Action Observation/Motor Imagery protocol, using quantitative indices. In particular, we showed the effect of segmenting or not the data in epochs around the stimulus presentation time on the independent component analysis (ICA) used for artifact removal. For ICA analysis, we tested two algorithms (SOBI and Extended Infomax). Finally, three re-reference approaches (Common averaged reference-CAR, robust-CAR and reference electrode standardization technique - REST) were also applied and their effects compared. Results showed that the segmenting method has a prominent effect on the cleaning procedure and consequently on final EEG data quality. Extended Infomax is confirmed as the method of choice for the identification of the artifactual components and, finally, CAR and the REST re-referencing techniques led to similar good results.

Wired Microfabricated Electrochemical Systems.

Metal wires have been used as an alternative to liquid junctions for the connection of solutions in microfabricated electrochemical devices. They exhibit similar performance to liquid junctions, provided that the interfacial potentials at both ends of the wires were appropriately canceled. Cyclic voltammograms of devices with liquid junctions and metal wires were very similar when no current or a low current flowed through the metal wire between the working and reference electrodes. Iridium wires with iridium oxide at both ends facilitated canceling of the interfacial potentials at either end of the junction particularly well, and were used effectively for voltammetry, amperometry, and potentiometry by adjusting the pH of the solutions in the working and reference electrode compartments to be equal. This approach was used to effectively integrate a reliable common reference electrode between multiple working electrodes and to conduct automated electrochemical control of solution transport in microfluidic systems.

Electrochemistry from first-principles in the grand canonical ensemble.

Progress in electrochemical technologies, such as automotive batteries, supercapacitors, and fuel cells, depends greatly on developing improved charged interfaces between electrodes and electrolytes. The rational development of such interfaces can benefit from the atomistic understanding of the materials involved by first-principles quantum mechanical simulations with Density Functional Theory (DFT). However, such simulations are typically performed on the electrode surface in the absence of its electrolyte environment and at constant charge. We have developed a new hybrid computational method combining DFT and the Poisson-Boltzmann equation (P-BE) capable of simulating experimental electrochemistry under potential control in the presence of a solvent and an electrolyte. The charged electrode is represented quantum-mechanically via linear-scaling DFT, which can model nanoscale systems with thousands of atoms and is neutralized by a counter electrolyte charge via the solution of a modified P-BE. Our approach works with the total free energy of the combined multiscale system in a grand canonical ensemble of electrons subject to a constant electrochemical potential. It is calibrated with respect to the reduction potential of common reference electrodes, such as the standard hydrogen electrode and the Li metal electrode, which is used as a reference electrode in Li-ion batteries. Our new method can be used to predict electrochemical properties under constant potential, and we demonstrate this in exemplar simulations of the differential capacitance of few-layer graphene electrodes and the charging of a graphene electrode coupled to a Li metal electrode at different voltages.

Development of oxygen sensor for pyrochemical reactors of spent nuclear fuel reprocessing

The problem of closing the nuclear fuel cycle is not only related to the development of new types of nuclear fuel and the operation of fast neutron reactors, but also to the complex schemes for the pyrochemical reprocessing of spent nuclear fuel (SNF), which, in turn, require adherence to strict process parameters. In particular, this concerns the operation of the reduction of oxidized SNF mainly by metallic lithium. The paper presents the basic scientific principles and the results of experimental verification of the operation of an electrochemical sensor for measuring oxygen in molten salts in pyrochemical reactors for the reprocessing of spent nuclear fuel. The sensor design consists of two combined electrochemical cells based on the solid electrolyte ZrO2-Y2O3 with a common reference electrode. The sensor allows continuous measurement of the oxygen activity in the oxide-chloride melt and the partial pressure of oxygen in the gas atmosphere above the melt directly during the process of pyrochemical processing. Experimental verification of the sensor performance was performed in a reactor with LiCl-Li2O melts at a temperature of 650 ° C. The resource of continuous sensor operation exceeded 500 hours, and the number of thermal cycles without destruction was at least 20. The sensor readings were found to depend on the specified Li2O content in the LiCl melt.

Design of multichannel potentiostat for remote and longtime monitoring of glucose concentration during yeast fermentation.

This paper presents the design of a wireless portable and multichannel potentiostat for remote monitoring in enclosed environments for long-time applications. In this paper, the proposed potentiostat is tested for monitoring the glucose concentration during the fermentation of yeast in real time for more than 24 h. The potentiostat is powered by a USB-connected battery and operated through a Bluetooth using a LabVIEW designed data monitoring and control panel. The potentiostat is capable of performing cyclic voltammetry or chronoamperometry on six biosensors simultaneously and gives the real-time response using Bluetooth connection. The potentiostat has a common counter electrode and reference electrode connection to all biosensors and independent working electrodes for all biosensors. The potentiostat was tested and validated by comparing the results obtained by a commercial potentiostat. The tests performed for monitoring the glucose concentration during the fermentation process showed a current detection limit of 180 nA and reported a standard deviation of ±2% for anodic and cathodic current peaks for cyclic voltammetry measurements when compared with the commercially available device. This study enables the novel method of monitoring the fermentation process wirelessly for days.

Designing and Using 3D-Printed Components That Allow Students To Fabricate Low-Cost, Adaptable, Disposable, and Reliable Ag/AgCl Reference Electrodes

A reference electrode is an essential component of all three-electrode electrochemical measurements. Common commercial reference electrodes, including the saturated calomel electrode and Ag/AgCl reference electrode, are expensive with the former containing toxic mercury. Cheaper alternatives have been proposed including Ag/AgCl references made from pipets and test tubes. However, electrodes prepared in this way are difficult to work with and are limited by the size and shape of glass casings that are available. This paper proposes an in-house manufactured Ag/AgCl reference electrode that uses some 3D-printed components in the fabrication process. This electrode is cheap to manufacture ($5 vs $60–100 CAD for the commercial reference electrode), and the design can be quickly altered due to the 3D printer’s capabilities in rapidly printing new electrode shapes to suit different analysts’ needs. The lab-made reference electrodes demonstrated stability and consistency in peak potential measurements in the cyclic voltammetry (CV) experiments. In ferricyanide CV tests, the recorded differences in anodic and cathodic peak potential (ΔEp) values for the commercial reference electrode and both lab-made electrodes were 68 ± 9%, 70 ± 12%, and 69 ± 13%, respectively. For all tests, the results were statistically comparable with those of the commercial Ag/AgCl reference electrode.

How Electroencephalogram Reference Influences the Movement Readiness Potential?

Readiness potential (RP) based on electroencephalograms (EEG) has been studied extensively in recent years, but no studies have investigated the influence of the reference electrode on RP. In order to investigate the reference effect, 10 subjects were recruited and the original vertex reference (Cz) was used to record the raw EEG signal when the subjects performed a motor preparation task. The EEG was then transformed to the common average reference (CAR) and reference electrode standardization technique (REST) reference, and we analyzed the RP waveform and voltage topographies and calculated the classification accuracy of idle and RP EEG segments. Our results showed that the RP waveform and voltage topographies were greatly influenced by the reference, but the classification accuracy was less affected if proper channels were selected as features. Since the Cz channel is near the primary motor cortex, where the source of RP is located, using the REST and CAR references is recommended to get accurate RP waveforms and voltage topographies.

Multi-parametric rigid and flexible, low-cost, disposable sensing platforms for biomedical applications

The measurement of Na+, K+ and H+ is essential in medicine and plays an important role in the assessment of tissue ischemia. Microfabrication, inkjet- and screen-printing can be used for solid contact ion selective electrodes (ISE) realization; these, however, can be non-standardized, costly and time consuming processes. We present the realization of ISEs on post-processed electrodes fabricated via standardized printed circuit board (PCB) manufacturing techniques. In vitro results are presented from two rigid platforms (32 ISEs) for liquid sample dip-stick measurements and two flexible platforms (6 and 32 ISEs) for post-surgical intestinal tissue monitoring, each with a common reference electrode (RE). These are combined with optimized tetrapolar bioimpedance sensors for tissue ischemia detection. Both electroless and hard gold PCB finishes are examined. Apart from the electroless rigid platform, the rest demonstrated comparable and superior performance, with the pH sensors demonstrating the greatest deviation; the flexible hard gold platform achieved a sensitivity 4.6mV/pH and 49.2mV/pH greater than the electroless flexible and rigid platforms, respectively. The best overall performance was achieved with the hard gold flexible platform with sensitivities as large as 73.4mV/pH, 56.3mV/log [Na+], and 57.4mV/log [K+] vs. custom REs on the same substrate. Simultaneous measurement of target analytes is demonstrated with test solutions and saliva samples. The results demonstrate superior performance to other PCB-based pH sensors and Na+ and K+ PCB-based sensors with comparable performance to potentiometric sensors fabricated with other techniques, paving the way towards mass-produced, low-cost, disposable, multi-parametric chemical sensing diagnostic platforms.

On the Keyhole Hypothesis: High Mutual Information between Ear and Scalp EEG

We propose and test the keyhole hypothesis—that measurements from low dimensional EEG, such as ear-EEG reflect a broadly distributed set of neural processes. We formulate the keyhole hypothesis in information theoretical terms. The experimental investigation is based on legacy data consisting of 10 subjects exposed to a battery of stimuli, including alpha-attenuation, auditory onset, and mismatch-negativity responses and a new medium-long EEG experiment involving data acquisition during 13 h. Linear models were estimated to lower bound the scalp-to-ear capacity, i.e., predicting ear-EEG data from simultaneously recorded scalp EEG. A cross-validation procedure was employed to ensure unbiased estimates. We present several pieces of evidence in support of the keyhole hypothesis: There is a high mutual information between data acquired at scalp electrodes and through the ear-EEG “keyhole,” furthermore we show that the view—represented as a linear mapping—is stable across both time and mental states. Specifically, we find that ear-EEG data can be predicted reliably from scalp EEG. We also address the reverse view, and demonstrate that large portions of the scalp EEG can be predicted from ear-EEG, with the highest predictability achieved in the temporal regions and when using ear-EEG electrodes with a common reference electrode.

New method for characterizing electron mediators in microbial systems using a thin-layer twin-working electrode cell

Microbial biofilms are significant ecosystems where the existence of redox gradients drive electron transfer often via soluble electron mediators. This study describes the use of two interfacing working electrodes (WEs) to simulate redox gradients within close proximity (250µm) for the detection and quantification of electron mediators. By using a common counter and reference electrode, the potentials of the two WEs were independently controlled to maintain a suitable “voltage window”, which enabled simultaneous oxidation and reduction of electron mediators as evidenced by the concurrent anodic and cathodic currents, respectively. To validate the method, the electrochemical properties of different mediators (hexacyanoferrate, HCF, riboflavin, RF) were characterized by stepwise shifting the “voltage window” (ranging between 25 and 200mV) within a range of potentials after steady equilibrium current of both WEs was established. The resulting differences in electrical currents between the two WEs were recorded across a defined potential spectrum (between −1V and +0.5V vs. Ag/AgCl). Results indicated that the technique enabled identification (by the distinct peak locations at the potential scale) and quantification (by the peak of current) of the mediators for individual species as well as in an aqueous mixture. It enabled a precise determination of mid-potentials of the externally added mediators (HCF, RF) and mediators produced by pyocyanin-producing Pseudomonas aeruginosa (WACC 91) culture. The twin working electrode described is particularly suitable for studying mediator-dependent microbial electron transfer processes or simulating redox gradients as they exist in microbial biofilms.

Hydrogel-based flexible micro-reference electrodes for use in alkaline and neutral pH solutions

Two types of nonbreakable, flexible micro-reference electrodes filled with gel-electrolytes were prepared for use in solutions with alkaline and neutral pH. The electrodes are intended for electrochemical measurements, in which chloride-free conditions are important. Due to the flexible, bendable construction of the electrodes, electrochemical experiments at locations difficult to access with common reference electrodes are enabled. Hg|HgO-type electrodes were prepared from amalgamated Au wires, followed by oxidation of the amalgam, which is mounted in a PTFE tube filled with 0.1M NaOH solution immobilized in a PAA-g-PEO gel. The potential of this type of electrode was found to be 0.162 ± 0.002 V (SHE) at room temperature. Cu|CuSO4 electrodes, consisting of a Cu wire immersed in a saturated CuSO4 solution jellied with gelatin, showed a stable open-circuit potential of 0.312 ± 0.001 V (SHE). Further characterization of the electrodes was performed in terms of electrochemical impedance spectroscopy and micro-polarization measurements. As an alternative to the flexible electrodes, rigid electrodes in glass enclosure were fabricated in analogy to the flexible-type electrodes.

Design and Fabrication of Ag / AgCl Reference Electrode Based on PDMS Conductive Composite Material

A vital part of any electrochemical sensing system is the reference electrode, which is a probe that is capable of measuring the potential on the solution side of an electrochemical interface. Ag/Agcl reference electrode is one kind of the most widely used among them. Common reference electrode is individually packaged and its volume is relatively large, which isn’t appropriate for microfludic systems. In microfluidic chips, electrochemical measurement is always challenging to realize, such as real-time monitoring of pH in micro-reactors. In this paper, we introduce a kind of Ag / AgCl reference electrode in microchips based on PDMS-based conductive composites. This conductive composite of good electrical conductivity was synthesized by PDMS and silver powders via uniformly mixing. Two chloride methods, electrolysis and chemical immersion, were selected to the sample compared with pure silver wire as a reference. Packaging thin film was fabricated by mixing agar with saturated Kcl gel. A three-electrode system was used to measure the potential of Ag/Agcl reference electrode. SEM pictures showed the surface profile of the reference electrode clearly. Here we demonstrate that electrolytic process and chemical immersion method both have great influence on the electrode surface. Fluffy and rough morphology increased the contact area between reference electrode and solution so as to improve the adequacy and accuracy of measurement.

Analysis of soluble intermediates in the lithium–sulfur battery by a simple in situ electrochemical probe

This paper describes a simple setup using a thin, insulated platinum wire as an in situ electrochemical probe for analysis of the soluble polysulfide intermediates formed and consumed during the course of the discharge process of a lithium–sulfur cell. The probe, sharing common reference and counter electrodes with the cell, can be used to follow the changes in concentration of polysulfides in the electrolyte. The results herein both support and complement more advanced techniques studied elsewhere for understanding the dominant processes occurring in the cell.