Ions-Silica Percolated Ionic Dielectric Elastomer Actuator for Soft Robots.

Soft robotics systems are currently under development using ionic electroactive polymers (i-EAP) as soft actuators for the human-machine interface. However, this endeavor has been impeded by the dilemma of reconciling the competing demands of force and strain in i-EAP actuators. Here, the authors present a novel design called "ions-silica percolated ionic dielectric elastomer (i-SPIDER)", which exhibits ionic liquid-confined silica microstructures that effectively resolve the chronic issue of conventional i-EAP actuators. The i-SPIDER actuator demonstrates remarkable electromechanical conversion capacity at low voltage, thanks to improved ion accumulation facilitated by interpreting electrode polarization at the electrolyte-electrode interface. This approach concurrently enhances both strain (by approximately 1.52%) and force (by roughly 1.06 mN) even at low Young's modulus (merely 5.9 MPa). Additionally, by demonstrating arachnid-inspired soft robots endowed with user-desired tasks through control of various form factors, the development of soft robots using the i-SPIDER that can concomitantly enhance strain and force holds promise as a compelling avenue for ushering in the next generation of miniaturized, low-powered soft robotics.

Unveiling the Electrocatalytic Activity of the GdBa0.5Sr0.5Co2-xCuxO5+δ (x ≥ 1) Oxygen Electrodes for Solid Oxide Cells.

The A-site cation-ordered GdBa0.5Sr0.5Co2-xCuxO5+δ (GBSCC) double perovskites are evaluated regarding the development of high-performance oxygen electrodes for reversible solid oxide cells (rSOCs). The aims are to maximally decrease the content of toxic and expensive cobalt by substitution with copper while at the same time improving or maintaining the required thermomechanical and electrocatalytic properties. Studies reveal that compositions with 1 ≤ x ≤ 1.15 are particularly interesting. Their thermal and chemical expansions are decreased, and sufficient transport properties are observed. Complementary density functional theory calculations give deeper insight into oxygen defect formation in the considered materials. Chemical compatibility with La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) and Ce0.9Gd0.1O2-δ (GDC) solid electrolytes is evaluated. It is documented that the GdBa0.5Sr0.5Co0.9Cu1.1O5+δ oxygen electrode enables obtaining very low electrode polarization resistance (Rp) values of 0.017 Ω cm2 at 850 °C as well as 0.111 Ω cm2 at 700 °C, which is lower in comparison to that of GdBa0.5Sr0.5CoCuO5+δ (respectively, 0.026 and 0.204 Ω cm2). Systematic distribution of relaxation times analyses allows studies of the electrocatalytic activity and distinguishing elementary steps of the electrochemical reaction at different temperatures. The rate-limiting process is found to be oxygen atom reduction, while the charge transfer at the electrode/electrolyte interface is significantly better with LSGM. The studies also allow elaborating on the catalytic role of the Ag current collector as compared with Pt. The electrodes manufactured using materials with x = 1 and 1.1 permit reaching high power outputs, exceeding 1240 mW cm-2 at 850 °C and 1060 mW cm-2 at 800 °C, for the LSGM-supported cells, which can also work in the electrolysis mode.

Applying a nanocomposite hydrogel electrode to mitigate electrochemical polarization and focusing effect in electrokinetic remediation of a Cu- and Pb-contaminated loess.

Inappropriate handling of copper (Cu) and lead (Pb)-containing wastewater resulting from metallurgical and smelting industries in Northwest China encourages their migration to surrounding environments. Their accumulation causes damage to liver and kidney function. The electrokinetic (EK) technology is considered to be an alternative to traditional remediation technologies because of its great maneuverability. The EK remediation is accompanied by the electrode polarization and the focusing effect toward affecting removal efficiency. In this study, a nanocomposite hydrogel (NCH) electrode was proposed and applied to the EK remediation of Cu- and Pb-contaminated loess. The mechanical, adsorption capacity, adsorption kinetics, and electrochemical properties of the NCH electrode were investigated in detail, followed by microscopic analyses of Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and Raman spectrometer. Results showed that the enhancement of the mechanical properties of the NCH electrode was attributed to the crosslinks of graphene nanoparticles, calcium alginate, and hydrogen bonds, while the Cu or Pb adsorption by the NCH electrode was in a chemisorption manner. The second layer formation might address the increase in adsorption capacity with increasing temperature. These results highlight the relative merits of the NCH electrode and verify the potential of applying the NCH electrode to the EK remediation of Cu- and Pb-contamianted loess.

A disposable impedance-based sensor for in-line cell growth monitoring in CAR-T cell manufacturing.

This paper presents the development of low-cost, disposable impedance-based sensors for real-time, in-line monitoring of suspension cell culture. The sensors consist of electrical discharge machining (EDM) cut aluminum electrodes and polydimethylsiloxane (PDMS) spacers, both of which are low-cost materials that can be safely disposed of. Our research demonstrates the capability of these low-cost sensors for in-line, non-invasive monitoring of suspension cell growth in cell manufacturing. We use a hybrid equivalent circuit model to extract key features/parameters from intertwined impedance signals, which are then fed to a novel physics-inspired (gray-box) model designed for α-relaxation. This model determines viable cell count (VCC), a critical quality attribute (CQA) in cell manufacturing. Predicted VCC trends are then compared with image-based cell count data to verify their accuracy.

Polyanionic electrically conductive superabsorbent hydrogel based on sodium alginate-g-poly (AM-co-ECA-co-AMPS): Broadband dielectric spectroscopy investigations.

In this study, the dielectric behavior of polyanionic electrically conductive superabsorbent hydrogel based on sodium alginate-g-poly(AM-co-ECA-co-AMPS) was investigated by broadband dielectric spectroscopy (BDS). The dielectric spectra obtained from -70 to 70 °C showed a superposition of three distinctive processes, electrode polarization, charge carrier's transport, and a molecular relaxation process. These dynamic processes were further analyzed along with the effect of both temperature and reduced graphene oxide (rGO) content. The development of a clear electrochemical double layer (ECDL) at the electrode/hydrogel interface strongly supports its possible application in supercapacitors' forms of energy storage. TGA, DSC, rheology, and electrochemical properties were studied. Furthermore, when the composite hydrogel with rGO content of 2.5 % was assembled into a symmetric supercapacitor, it displayed a specific capacitance of 756 F.g-1 at 1 A.g-1 and 704 F.g-1 after 5000 cycles with high capacitance retention of 93.2 %. The superior conductivity and porous structure of the rGO composite hydrogel are credited with the hydrogel's excellent electrochemical capabilities.

A Microfluidic Dielectric Spectroscopy System for Characterization of Biological Cells in Physiological Media.

Dielectric spectroscopy (DS) is a promising cell screening method that can be used for diagnostic and drug discovery purposes. The primary challenge of using DS in physiological buffers is the electrode polarization (EP) that overwhelms the impedance signal within a large frequency range. These effects further amplify with the miniaturization of the measurement electrodes. In this study, we present a microfluidic system and the associated equivalent circuit models for real-time measurements of cell membrane capacitance and cytoplasm resistance in physiological buffers with 10 s increments. The current device captures several hundreds of biological cells in individual microwells through gravitational settling and measures the system's impedance using microelectrodes covered with dendritic gold nanostructures. Using PC-3 cells (a highly metastatic prostate cancer cell line) suspended in cell growth media (CGM), we demonstrate stable measurements of cell membrane capacitance and cytoplasm resistance in the device for over 15 min. We also describe a consistent application of the equivalent circuit model, starting from the reference measurements used to determine the system parameters. The circuit model is tested using devices with varying dimensions, and the obtained cell parameters between different devices are nearly identical. Further analyses of the impedance data have shown that accurate cell membrane capacitance and cytoplasm resistance can be extracted using a limited number of measurements in the 5 MHz to 10 MHz range. This will potentially reduce the timescale required for real-time DS measurements below 1 s. Overall, the new microfluidic device can be used for the dielectric characterization of biological cells in physiological buffers for various cell screening applications.

Activation of Porous Pt Electrodes Deposited on YSZ Electrolyte by Nitric Acid Treatment.

The effect of nitric acid treatment on the electrochemical performance of porous Pt electrodes deposited on YSZ (abbreviation from yttria stabilized zirconia) electrolyte was investigated. Two identical symmetrical Pt/YSZ/Pt cells with porous Pt electrodes were fabricated, after which the electrodes of the first cell were kept as sintered, while those of the second cell were impregnated with HNO3 solution. The electrochemical behavior of the prepared electrodes was studied using impedance spectroscopy and cyclic voltammetry. Significant reduction of the polarization resistance of the HNO3-treated electrodes was revealed. The observed enhancement of the electrochemical performance of porous Pt electrodes was assumed to be caused by adsorption of NOx-species on YSZ and Pt surfaces, which promotes oxygen molecules dissociation and transport to the triple phase boundary by the "relay-race" mechanism. The obtained results allow for considering the nitric acid treatment of a porous Pt electrode as an effective way of electrode activation.

Ambiguity in the interpretation of the low-frequency dielectric properties of biological tissues.

The frequency-dependent behaviour of the dielectric properties of biological tissues in the frequency range below 1 kHz has been under debate since the past century. Here, we reanalyse the raw data of the main resource of the dielectric properties of biological tissues in impedance representation. Employing a Kramers-Kronig validity test and parameter estimation techniques, we can describe the data by two physical parametric models that correspond to opposing biophysical interpretations: on the one hand the data can be explained only by intrinsic tissue properties, but on the other hand evidence for electrode-specific effects can be found for all tissues under investigation. The first interpretation would justify the continued use of a parametric model comprising four Cole-Cole dispersions, which describe the dielectric properties from extremely low to very high frequencies. As an alternative that is in accordance with the second interpretation, we suggest to omit the slowest of the four dispersions in the model and increase the static conductivity to account for a frequency-independent conductivity below 1 kHz.

Development of Ni-Sr(V,Ti)O3-δ Fuel Electrodes for Solid Oxide Fuel Cells.

A series of strontium titanates-vanadates (STVN) with nominal cation composition Sr1-xTi1-y-zVyNizO3-δ (x = 0-0.04, y = 0.20-0.40 and z = 0.02-0.12) were prepared by a solid-state reaction route in 10% H2-N2 atmosphere and characterized under reducing conditions as potential fuel electrode materials for solid oxide fuel cells. Detailed phase evolution studies using XRD and SEM/EDS demonstrated that firing at temperatures as high as 1200 °C is required to eliminate undesirable secondary phases. Under such conditions, nickel tends to segregate as a metallic phase and is unlikely to incorporate into the perovskite lattice. Ceramic samples sintered at 1500 °C exhibited temperature-activated electrical conductivity that showed a weak p(O2) dependence and increased with vanadium content, reaching a maximum of ~17 S/cm at 1000 °C. STVN ceramics showed moderate thermal expansion coefficients (12.5-14.3 ppm/K at 25-1100 °C) compatible with that of yttria-stabilized zirconia (8YSZ). Porous STVN electrodes on 8YSZ solid electrolytes were fabricated at 1100 °C and studied using electrochemical impedance spectroscopy at 700-900 °C in an atmosphere of diluted humidified H2 under zero DC conditions. As-prepared STVN electrodes demonstrated comparatively poor electrochemical performance, which was attributed to insufficient intrinsic electrocatalytic activity and agglomeration of metallic nickel during the high-temperature synthetic procedure. Incorporation of an oxygen-ion-conducting Ce0.9Gd0.1O2-δ phase (20-30 wt.%) and nano-sized Ni as electrocatalyst (≥1 wt.%) into the porous electrode structure via infiltration resulted in a substantial improvement in electrochemical activity and reduction of electrode polarization resistance by 6-8 times at 900 °C and ≥ one order of magnitude at 800 °C.

Guidelines to Study and Develop Soft Electrode Systems for Neural Stimulation.

Electrical stimulation of nervous structures is a widely used experimental and clinical method to probe neural circuits, perform diagnostics, or treat neurological disorders. The recent introduction of soft materials to design electrodes that conform to and mimic neural tissue led to neural interfaces with improved functionality and biointegration. The shift from stiff to soft electrode materials requires adaptation of the models and characterization methods to understand and predict electrode performance. This guideline aims at providing (1) an overview of the most common techniques to test soft electrodes in vitro and in vivo; (2) a step-by-step design of a complete study protocol, from the lab bench to in vivo experiments; (3) a case study illustrating the characterization of soft spinal electrodes in rodents; and (4) examples of how interpreting characterization data can inform experimental decisions. Comprehensive characterization is paramount to advancing soft neurotechnology that meets the requisites for long-term functionality in vivo.

Influence of surface chemistry of activated carbon electrodes on electro-assisted adsorption of arsenate.

In this work, the influence of oxygen-containing surface groups of activated carbon electrodes on the charge efficiency of electro-assisted adsorption of As(V) was investigated. It was distinguished between activated carbons modified through acidic (oxidation) and thermal (reduction) treatments, starting with a granular pristine commercial activated carbon of bituminous origin. The textural characterization of the three materials showed that the treatments did not produce significant changes in the surface area and in the distribution of pores. The three carbon samples were used to fabricate packed electrodes with stainless-steel mesh as electric current collector. This work report that the application of anodic potentials (1.01 and 1.41 V vs. NHE) increased the adsorption capacity and rate of arsenate uptake in solutions containing only this contaminant (2.5 mg L-1) at pH 7. The oxidized carbon electrode presented the lowest capacitance and adsorption capacity during electroadsorption (0.33 mg g-1), compared to pristine material (1.77 mg g-1). On the other hand, the reduced electrode displayed the highest adsorption capacity of arsenate (3.14 mg g-1) when applying a potential of 1.01 V. The results were correlated with the potential of zero charge values. In addition, for this material, the rate of kinetics increased 26.7 % compared to experiments without applied potential.

Microbial electrochemical technologies: Electronic circuitry and characterization tools.

Microbial electrochemistry merges microbiology, electrochemistry and electronics to provide a set of technologies for environmental engineering applications. Understanding the electronic concepts is crucial for effectively adopting these systems, but the importance of electronic circuitry is often overlooked by microbial electrochemistry researchers. This review provides the background on the electronics and electrochemical concepts involved in the study of microorganisms interacting with electricity, and their applications in microbial electrochemical technology (MET). The potentiostat circuitry is described along with its working principles. Electrochemical analyses are presented together with the rational and parameters employed to study MET devices and electroactive microorganisms. Finally, future directions are delineated towards the adoption of MET, and the related electronics, in environmental engineering applications.

Impedance and conductivity of bovine myocardium during freezing and thawing at slow rates - implications for cardiac cryo-ablation.

Increasing impedance during freezing might be a valuable marker for guiding cardiac cryo-ablation. We provide model based insights on how decreasing temperature below the freezing point of tissue relates to the percentage of frozen water. Furthermore, we provide experimental data for comparing this percentage with the increase in impedance. Measurements were performed on a bovine tissue sample at frequencies between 5 and 80 kHz. Slow cooling and heating rates were applied to minimize temperature gradients in the myocardial sample and to allow accurate assessment of the freezing point. Computer simulation was applied to link impedance with temperature dependent conductivities. The osmotic virial equation was used to estimate the percentage of frozen water. Measurements identified the freezing point at -0.6 ∘C. At -5 ∘C, impedance rose by more than a factor of ten compared to that at the freezing point and the percentage of frozen water was estimated as being 89%. At -49 ∘C impedance had increased by up to three orders of magnitude and ice formation was most pronounced in the extracellular space. Progressive ice formation in tissue is reflected by a large increase in impedance, and impedance increases monotonically with the percentage of frozen water. Its analysis allows for experimental assessment of factors relevant to cell death. Solid ice contributes to the rupture of the micro-vasculature, while phase shifts reflect concentration differences between extra- and intracellular space driving osmotic water transfer across cell membranes.

Electrode polarization effects on interfacial kinetics of ionic liquid at graphite surface: An extended lagrangian-based constant potential molecular dynamics simulation study.

Computational models including electrode polarization can be essential to study electrode/electrolyte interfacial phenomena more realistically. We present here a constant-potential classical molecular dynamics simulation method based on the extended Lagrangian formulation where the fluctuating electrode atomic charges are treated as independent dynamical variables. The method is applied to a graphite/ionic liquid system for the validation and the interfacial kinetics study. While the correct adiabatic dynamics is achieved with a sufficiently small fictitious mass of charge, static properties have been shown to be almost insensitive to the fictitious mass. As for the kinetics study, electrical double layer (EDL) relaxation and ion desorption from the electrode surface are considered. We found that the polarization slows EDL relaxation greatly whereas it has little impact on the ion desorption kinetics. The findings suggest that the polarization is essential to estimate the kinetics in nonequilibrium processes, not in equilibrium. © 2019 Wiley Periodicals, Inc.

Effect of Fullerene Passivation on the Charging and Discharging Behavior of Perovskite Solar Cells: Reduction of Bound Charges and Ion Accumulation.

Ion accumulation of organometal halide perovskites (OHPs) induced by electrode polarization of perovskite solar cells (PSCs) under illumination has been intensely studied and associated with a widely observed current-voltage hysteresis behavior. This work is dedicated to the investigation of the behavior of charged species at the compact TiO2/OHP interface with respect to electrode polarization in PSC devices. By providing a comprehensive discussion of open-circuit voltage ( VOC) buildup and VOC decay under illumination and in the dark for the PSCs modified with [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) at the TiO2/OHP interface and their corresponding electrochemical impedance spectroscopies (EISs), a justified mechanism is proposed attempting to elucidate the dynamics of interfacial species with respect to the time and frequency domains. Our results demonstrate that the retarded VOC buildup and decay observed in PSC devices are related to the formation of bound charges in TiO2, which is essential to neutralize the oppositely charged ions accumulating at the OHP side. Besides, inserting a thicker PCBM at the TiO2/OHP interface as a passivation layer can alleviate the electrode polarization more efficiently as verified by the low dielectric constant measured from EIS. Moreover, photoluminescence measurements indicate that PCBM at the TiO2/OHP interface is capable of passivating a trap state and improving charge transfer. However, with respect to the time scale investigated in this work, the reduction of the hysteresis behavior on a millisecond scale is more likely due to less bound charge formation at the interface rather than shallow trap-state passivation by PCBM. After all, this work comprehensively demonstrates the interfacial properties of PSCs associated with PCBM passivation and helps to further understand its impact on charging/discharging as well as device performance.

Solution-Processed Lithium-Doped ZnO Electron Transport Layer for Efficient Triple Cation (Rb, MA, FA) Perovskite Solar Cells.

The current work reports the lithium (Li) doping of a low-temperature processed zinc oxide (ZnO) electron transport layer (ETL) for highly efficient, triple-cation-based MA0.57FA0.38Rb0.05PbI3 (MA: methylammonium, FA: formamidinium, Rb: rubidium) perovskite solar cells (PSCs). Lithium intercalation in the host ZnO lattice structure is dominated by interstitial doping phenomena, which passivates the intrinsic defects in ZnO film. In addition, interstitial Li doping also downshifts the Fermi energy position of Li-doped ETL by 30 meV, which contributes to the reduction of the electron injection barrier from the photoactive perovskite layer. Compared to the pristine ZnO, the power conversion efficiency (PCE) of the PSCs incorporating lithium-doped ZnO (Li-doped) is raised from 14.07 to 16.14%. The superior performance is attributed to the reduced current leakage, enhanced charge extraction characteristics, and mitigated trap-assisted recombination phenomena in Li-doped devices, thoroughly investigated by means of electrochemical impedance spectroscopy (EIS) analysis. Li-doped PSCs also exhibit lower photocurrent hysteresis than ZnO devices, which is investigated with regard to the electrode polarization phenomena of the fabricated devices.

Rough Gold Electrodes for Decreasing Impedance at the Electrolyte/Electrode Interface.

Electrode polarization at the electrolyte/electrode interface is often undesirable for bio-sensing applications, where charge accumulated over an electrode at constant potential causes large potential drop at the interface and low measurement sensitivity. In this study, novel rough electrodes were developed for decreasing electrical impedance at the interface. The electrodes were fabricated using electrochemical deposition of gold and sintering of gold nanoparticles. The performances of the gold electrodes were compared with platinum black electrodes. A constant phase element model was used to describe the interfacial impedance. Hundred folds of decrease in interfacial impedance were observed for fractal gold electrodes and platinum black. Biotoxicity, contact angle, and surface morphology of the electrodes were investigated. Relatively low toxicity and hydrophilic nature of the fractal and granulated gold electrodes make them suitable for bioimpedance and cell electromanipulation studies compared to platinum black electrodes which are both hydrophobic and toxic.

Compensating for Electrode Polarization in Dielectric Spectroscopy Studies of Colloidal Suspensions: Theoretical Assessment of Existing Methods.

Dielectric spectroscopy can be used to determine the dipole moment of colloidal particles from which important interfacial electrokinetic properties, for instance their zeta potential, can be deduced. Unfortunately, dielectric spectroscopy measurements are hampered by electrode polarization (EP). In this article, we review several procedures to compensate for this effect. First EP in electrolyte solutions is described: the complex conductivity is derived as function of frequency, for two cell geometries (planar and cylindrical) with blocking electrodes. The corresponding equivalent circuit for the electrolyte solution is given for each geometry. This equivalent circuit model is extended to suspensions. The complex conductivity of a suspension, in the presence of EP, is then calculated from the impedance. Different methods for compensating for EP are critically assessed, with the help of the theoretical findings. Their limit of validity is given in terms of characteristic frequencies. We can identify with one of these frequencies the frequency range within which data uncorrected for EP may be used to assess the dipole moment of colloidal particles. In order to extract this dipole moment from the measured data, two methods are reviewed: one is based on the use of existing models for the complex conductivity of suspensions, the other is the logarithmic derivative method. An extension to multiple relaxations of the logarithmic derivative method is proposed.

Better Resolved Low Frequency Dispersions by the Apt Use of Kramers-Kronig Relations, Differential Operators, and All-In-1 Modeling.

The dielectric spectra of colloidal systems often contain a typical low frequency dispersion, which usually remains unnoticed, because of the presence of strong conduction losses. The KK relations offer a means for converting ε' into ε″ data. This allows us to calculate conduction free ε″ spectra in which the l.f. dispersion will show up undisturbed. This interconversion can be done on line with a moving frame of logarithmically spaced ε' data. The coefficients of the conversion frames were obtained by kernel matching and by using symbolic differential operators. Logarithmic derivatives and differences of ε' and ε″ provide another option for conduction free data analysis. These difference-based functions actually derived from approximations to the distribution function, have the additional advantage of improving the resolution power of dielectric studies. A high resolution is important because of the rich relaxation structure of colloidal suspensions. The development of all-in-1 modeling facilitates the conduction free and high resolution data analysis. This mathematical tool allows the apart-together fitting of multiple data and multiple model functions. It proved also useful to go around the KK conversion altogether. This was achieved by the combined approximating ε' and ε″ data with a complex rational fractional power function. The all-in-1 minimization turned out to be also highly useful for the dielectric modeling of a suspension with the complex dipolar coefficient. It guarantees a secure correction for the electrode polarization, so that the modeling with the help of the differences ε' and ε″ can zoom in on the genuine colloidal relaxations.

Capacitive Dark Currents, Hysteresis, and Electrode Polarization in Lead Halide Perovskite Solar Cells.

Despite spectacular advances in conversion efficiency of perovskite solar cell many aspects of its operating modes are still poorly understood. Capacitance constitutes a key parameter to explore which mechanisms control particular functioning and undesired effects as current hysteresis. Analyzing capacitive responses allows addressing not only the nature of charge distribution in the device but also the kinetics of the charging processes and how they alter the solar cell current. Two main polarization processes are identified. Dielectric properties of the microscopic dipolar units through the orthorhombic-to-tetragonal phase transition account for the measured intermediate frequency capacitance. Electrode polarization caused by interfacial effects, presumably related to kinetically slow ions piled up in the vicinity of the outer interfaces, consistently explain the reported excess capacitance values at low frequencies. In addition, current-voltage curves and capacitive responses of perovskite-based solar cells are connected. The observed hysteretic effect in the dark current originates from the slow capacitive mechanisms.