Battery research depends upon up-to-date information on the cell characteristics found in current electric vehicles, which is exacerbated by the deployment of novel formats and architectures. This necessitates open access to cell characterization data. Therefore, this study examines the architecture and performance of first-generation Tesla 4680 cells in detail, both by electrical characterization and thermal investigations at cell-level and by disassembling one cell down to the material level including a three-electrode analysis. The cell teardown reveals the complex cell architecture with electrode disks of hexagonal symmetry as well as an electrode winding consisting of a double-sided and homogeneously coated cathode and anode, two separators and no mandrel. A solvent-free anode fabrication and coating process can be derived. Energy-dispersive X-ray spectroscopy as well as differential voltage, incremental capacity and three-electrode analysis confirm a NMC811 cathode and a pure graphite anode without silicon. On cell-level, energy densities of 622.4 Wh/L and 232.5 Wh/kg were determined while characteristic state-of-charge dependencies regarding resistance and impedance behavior are revealed using hybrid pulse power characterization and electrochemical impedance spectroscopy. A comparatively high surface temperature of ∼70 °C is observed when charging at 2C without active cooling. All measurement data of this characterization study are provided as open source.
The Electrochemical Society (ECS) was founded in 1902 to advance the theory and practice at the forefront of electrochemical and solid state science and technology, and allied subjects.
ISSN: 1945-7111
JES is the flagship journal of The Electrochemical Society. Published continuously from 1902 to the present, JES remains one of the most highly-cited journals in electrochemistry and solid-state science and technology.
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Manuel Ank et al 2023 J. Electrochem. Soc. 170 120536
Yuliya Preger et al 2020 J. Electrochem. Soc. 167 120532
Energy storage systems with Li-ion batteries are increasingly deployed to maintain a robust and resilient grid and facilitate the integration of renewable energy resources. However, appropriate selection of cells for different applications is difficult due to limited public data comparing the most commonly used off-the-shelf Li-ion chemistries under the same operating conditions. This article details a multi-year cycling study of commercial LiFePO4 (LFP), LiNixCoyAl1−x−yO2 (NCA), and LiNixMnyCo1−x−yO2 (NMC) cells, varying the discharge rate, depth of discharge (DOD), and environment temperature. The capacity and discharge energy retention, as well as the round-trip efficiency, were compared. Even when operated within manufacturer specifications, the range of cycling conditions had a profound effect on cell degradation, with time to reach 80% capacity varying by thousands of hours and cycle counts among cells of each chemistry. The degradation of cells in this study was compared to that of similar cells in previous studies to identify universal trends and to provide a standard deviation for performance. All cycling files have been made publicly available at batteryarchive.org, a recently developed repository for visualization and comparison of battery data, to facilitate future experimental and modeling efforts.
George E. Blomgren 2017 J. Electrochem. Soc. 164 A5019
This year, the battery industry celebrates the 25th anniversary of the introduction of the lithium ion rechargeable battery by Sony Corporation. The discovery of the system dates back to earlier work by Asahi Kasei in Japan, which used a combination of lower temperature carbons for the negative electrode to prevent solvent degradation and lithium cobalt dioxide modified somewhat from Goodenough's earlier work. The development by Sony was carried out within a few years by bringing together technology in film coating from their magnetic tape division and electrochemical technology from their battery division. The past 25 years has shown rapid growth in the sales and in the benefits of lithium ion in comparison to all the earlier rechargeable battery systems. Recent work on new materials shows that there is a good likelihood that the lithium ion battery will continue to improve in cost, energy, safety and power capability and will be a formidable competitor for some years to come.
Peter Keil et al 2016 J. Electrochem. Soc. 163 A1872
In this study, the calendar aging of lithium-ion batteries is investigated at different temperatures for 16 states of charge (SoCs) from 0 to 100%. Three types of 18650 lithium-ion cells, containing different cathode materials, have been examined. Our study demonstrates that calendar aging does not increase steadily with the SoC. Instead, plateau regions, covering SoC intervals of more than 20%–30% of the cell capacity, are observed wherein the capacity fade is similar. Differential voltage analyses confirm that the capacity fade is mainly caused by a shift in the electrode balancing. Furthermore, our study reveals the high impact of the graphite electrode on calendar aging. Lower anode potentials, which aggravate electrolyte reduction and thus promote solid electrolyte interphase growth, have been identified as the main driver of capacity fade during storage. In the high SoC regime where the graphite anode is lithiated more than 50%, the low anode potential accelerates the loss of cyclable lithium, which in turn distorts the electrode balancing. Aging mechanisms induced by high cell potential, such as electrolyte oxidation or transition-metal dissolution, seem to play only a minor role. To maximize battery life, high storage SoCs corresponding to low anode potential should be avoided.
Jorn M. Reniers et al 2019 J. Electrochem. Soc. 166 A3189
The maximum energy that lithium-ion batteries can store decreases as they are used because of various irreversible degradation mechanisms. Many models of degradation have been proposed in the literature, sometimes with a small experimental data set for validation. However, a comprehensive comparison between different model predictions is lacking, making it difficult to select modelling approaches which can explain the degradation trends actually observed from data. Here, various degradation models from literature are implemented within a single particle model framework and their behavior is compared. It is shown that many different models can be fitted to a small experimental data set. The interactions between different models are simulated, showing how some of the models accelerate degradation in other models, altering the overall degradation trend. The effects of operating conditions on the various degradation models is simulated. This identifies which models are enhanced by which operating conditions and might therefore explain specific degradation trends observed in data. Finally, it is shown how a combination of different models is needed to capture different degradation trends observed in a large experimental data set. Vice versa, only a large data set enables to properly select the models which best explain the observed degradation.
Weilong Ai et al 2020 J. Electrochem. Soc. 167 013512
Whilst extensive research has been conducted on the effects of temperature in lithium-ion batteries, mechanical effects have not received as much attention despite their importance. In this work, the stress response in electrode particles is investigated through a pseudo-2D model with mechanically coupled diffusion physics. This model can predict the voltage, temperature and thickness change for a lithium cobalt oxide-graphite pouch cell agreeing well with experimental results. Simulations show that the stress level is overestimated by up to 50% using the standard pseudo-2D model (without stress enhanced diffusion), and stresses can accelerate the diffusion in solid phases and increase the discharge cell capacity by 5.4%. The evolution of stresses inside electrode particles and the stress inhomogeneity through the battery electrode have been illustrated. The stress level is determined by the gradients of lithium concentration, and large stresses are generated at the electrode-separator interface when high C-rates are applied, e.g. fast charging. The results can explain the experimental results of particle fragmentation close to the separator and provide novel insights to understand the local aging behaviors of battery cells and to inform improved battery control algorithms for longer lifetimes.
Mark E. Orazem and Burak Ulgut 2024 J. Electrochem. Soc. 171 040526
Recent battery papers commonly employ interpretation models for which diffusion impedances are in series with interfacial impedance. The models are fundamentally flawed because the diffusion impedance is inherently part of the interfacial impedance. A derivation for faradaic impedance is presented which shows how the charge-transfer resistance and diffusion resistance are functions of the concentration of reacting species at the electrode surface, and the resulting impedance model incorporates diffusion impedances as part of the interfacial impedance. Conditions are identified under which the two model formulations yield the same results. These conditions do not apply for batteries.
Chang-Hui Chen et al 2020 J. Electrochem. Soc. 167 080534
Presented here, is an extensive 35 parameter experimental data set of a cylindrical 21700 commercial cell (LGM50), for an electrochemical pseudo-two-dimensional (P2D) model. The experimental methodologies for tear-down and subsequent chemical, physical, electrochemical kinetics and thermodynamic analysis, and their accuracy and validity are discussed. Chemical analysis of the LGM50 cell shows that it is comprised of a NMC 811 positive electrode and bi-component Graphite-SiOx negative electrode. The thermodynamic open circuit voltages (OCV) and lithium stoichiometry in the electrode are obtained using galvanostatic intermittent titration technique (GITT) in half cell and three-electrode full cell configurations. The activation energy and exchange current coefficient through electrochemical impedance spectroscopy (EIS) measurements. Apparent diffusion coefficients are estimated using the Sand equation on the voltage transient during the current pulse; an expansion factor was applied to the bi-component negative electrode data to reflect the average change in effective surface area during lithiation. The 35 parameters are applied within a P2D model to show the fit to experimental validation LGM50 cell discharge and relaxation voltage profiles at room temperature. The accuracy and validity of the processes and the techniques in the determination of these parameters are discussed, including opportunities for further modelling and data analysis improvements.
Yuriy V. Tolmachev 2023 J. Electrochem. Soc. 170 030505
We present a quantitative bibliometric study of flow battery technology from the first zinc-bromine cells in the 1870's to megawatt vanadium RFB installations in the 2020's. We emphasize, that the cost advantage of RFBs in multi-hour charge-discharge cycles is compromised by an inferior energy efficiency of these systems, and that there are limits on the efficiency improvement due to internal cross-over and the cost of power (at low current densities) and due to an acceptable pressure drop (at high current densities). Differences between lithium-ion and vanadium redox flow batteries (VRFBs) are discussed from the end-user perspective. We conclude, that the area-specific resistance, cross-over current and durability of contemporaneous VRFBs are appropriate for commercialization in multi-hour stationary energy storage markets, and the most import direction in the VRFB development today is the reduction of stack materials and manufacturing costs. Chromium-iron RFBs should be given a renewed attention, since it seems to be the most promising durable low-energy-cost chemistry.
Peter M. Attia et al 2022 J. Electrochem. Soc. 169 060517
Lithium-ion batteries can last many years but sometimes exhibit rapid, nonlinear degradation that severely limits battery lifetime. In this work, we review prior work on "knees" in lithium-ion battery aging trajectories. We first review definitions for knees and three classes of "internal state trajectories" (termed snowball, hidden, and threshold trajectories) that can cause a knee. We then discuss six knee "pathways", including lithium plating, electrode saturation, resistance growth, electrolyte and additive depletion, percolation-limited connectivity, and mechanical deformation—some of which have internal state trajectories with signals that are electrochemically undetectable. We also identify key design and usage sensitivities for knees. Finally, we discuss challenges and opportunities for knee modeling and prediction. Our findings illustrate the complexity and subtlety of lithium-ion battery degradation and can aid both academic and industrial efforts to improve battery lifetime.
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Ipek Kucuk et al 2024 J. Electrochem. Soc. 171 057501
Molnupiravir (MLP) is an important antiviral drug recommended for the treatment of COVID-19. In order to design new pharmaceuticals, exploring drug and DNA interaction is crucial. This study aimed to determine the interaction of MLP with calf thymus double-stranded DNA (ct-dsDNA) by electrochemical methods. Investigation of these interactions was carried out using the differential pulse voltammetry technique (DPV) on the biosensor surface and in-solution studies. Changes in ct-dsDNA between deoxyguanosine (dGuo) and deoxyadenosine (dAdo) oxidation signals were examined before and after the interaction. It was found that MLP interacts significantly with bases of ct-dsDNA dAdo. Limits of detection and quantification for MLP-ct-dsDNA interaction were calculated as 2.93 and 9.67 μM in the linear range of 10–200 μM, respectively, based on dAdo's decreasing peak current. To calculate the binding constant of MLP and ct-dsDNA, cyclic voltammetry was used, and it was found to be 8.6 × 104 M. As for molecular docking techniques, the binding energy of MLP with DNA is −8.1 kcal mol−1, and this binding occurred by a combination of strong conventional hydrogen bonding to both adenine and guanine base pair edges, which indicates the interaction of MLP with DNA.
Highlights
This electrochemical study examined Molnupiravir's (MLP) interaction with calf thymus double-stranded DNA (ct-dsDNA) for the first time.
In a solution with both, the biosensor surface investigated the interaction of ct-dsDNA immobilized on the GCE surface and the bare GCE examined the interaction of MLP-ct-dsDNA.
Differential pulse voltammetry shows that MLP-dAdo binding mode decreases oxidation signals after incubation with various doses.
The binding constant of MLP and ct-dsDNA was calculated using cyclic voltammetry.
A molecular docking simulation contributed electrochemical interaction study.
Jiaxu Wang et al 2024 J. Electrochem. Soc. 171 055501
A green protocol for construction of C−Se bonds from ketene dithioacetals and diselenides through direct electrochemical oxidative cross-coupling has been developed. This reaction was carried out in an undivided cell system with NaBF4 as the electrolyte and CH3CN as the solvent through galvanostatic electrolysis. A series of substituted ketene dithioacetals and diselenides were tolerant and the desired tetrasubstituted alkenyl selenides were obtained in moderate to excellent yields. In addition, construction of C−S bond from ketene dithioacetals and disulfides through electrochemical method in the presence of KI was also successfully realized. It exhibited high efficiency and broad functional group tolerance.
M. Sepe et al 2024 J. Electrochem. Soc. 171 054501
Optimization of proton exchange membrane water electrolyzers (PEMWE) has become a focus of researchers looking for a reliable way to generate power. A vital component to PEMWE operation is the porous transport layer (PTL) on the anode side, which is where oxygen is produced. The PTL must allow water access to the catalyst layer and remove oxygen simultaneously. In this work, a previously developed imaging technique is used to generate bilayer PTL structures. A multiscale modeling approach was used to study the effect of a bilayer PTL on oxygen evolution and PEMWE performance. First, a micro scale model was used to predict oxygen transport pathways through different PTL structures. Results showed that the bilayer PTL results in higher oxygen saturation and faster oxygen transport through the PTL. Second, a macro scale model was used to predict performance using bilayer PTLs. Predictions showed potential values between 10 and 20 mV below single layer potential values. This points to the bilayer improving PEMWE operation. Findings from this work show how the addition of a mesoporous layer to a PTL substrate will improve oxygen transport and removal from the catalyst surface, which will improve PEMWE performance.
Jieyu Zhao et al 2024 J. Electrochem. Soc. 171 046507
As a result of issues related to pH control and the competition between H2O2 production and activation at the same sites, the applications of electro-Fenton (EF) pollutant remediation systems are limited. This work designed a synergistic dual-cathode EF system that exhibits self-adjustment of pH and stable electrode coatings. This system is based on using biomass as the active cathode material for H2O2 generation and the interaction between a stainless-steel mesh and FeOCl to reduce Fe3+ ions. The synergistic factor for this dual-cathode system was calculated to be 85.2%. Significantly, the production and activation of H2O2 in this composite system are unaffected by pH and the pH value can be adjusted between 9.67 and 3.7 without adding any acidic reagents. This process allows for the degradation of recalcitrant organic pollutants over the pH range of 3 to 9 without pre-acidification or challenges related to iron sludge and effluent chromaticity. Various organic pollutants, including antibiotics and organic dyes, can be effectively decomposed using this technology, which also exhibits good stability throughout 22 continuous trials over 1400 min. This work demonstrates a novel yet viable approach to highly efficient, inexpensive pollutant treatment with good reusability, a wide pH range and no iron leaching.
D. A. Vetrova et al 2024 J. Electrochem. Soc. 171 046506
The standard rate constants of charge transfer (ks) for the Nb(V)/Nb(IV) redox couple in the NaCl-KCl(equimol.)-NaF(10 wt%)-K2NbF7 melt with addition of alkaline Earth metal cations (Mg2+, Ca2+, Sr2+, Ba2+) were determined. It was found that addition of alkaline Earth metal cations resulted in increasing of ks to the certain ratio of Me2+/Nb(V) for the all alkaline Earth metal cations due to substitution of Na+ and K+ cations by Me2+ in the second coordination sphere of niobium complexes that leads to decreasing of niobium fluoride complexes stability. Further addition brought to some decrease of the standard rate constants because the viscosity of melts increasing, which brings to decrease of the diffusion coefficients. The standard rate constants increase with increasing of the ionic potential and reach maximum values for the complexes with outer-sphere magnesium cations. Comparative analysis of the electrochemical behavior of Nb(V)/Nb(IV) and Ti(IV/Ti(III)) redox couples in the NaCl-KCl(equimol.)-NaF(10 wt%) melt without and with addition of alkaline Earth metal cations has been done. It was determined that mechanism of electron transfer from the cathode to niobium and titanium complexes in melts containing alkaline Earth metal cations is the same and has a bridge nature.
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Jiashuai Wang et al 2024 J. Electrochem. Soc. 171 040527
The growing demand for energy storage application has facilitated the development of Li-ion rechargeable batteries (LIBs). As such, there is an urgent need to design electrodes with a high specific energy and long cycle life. The evolution of conventional LIBs cathode materials in past 30 years has arrived at a bottleneck. Fortunately, the finding of the lithium-rich cation disordered rocksalt (DRXs) has largely broadened the element ranges of the promising cathode in the past several years. Compared with the classical cation-ordered oxides, the DRXs display a large charge storage capacity based on both transition metal and oxygen redox capacity. In addition, their wide compositional space and cobalt-free characteristic would greatly reduce production costs in promoting the commercialization process. Herein, we make an overview of the recent progress for DRXs materials, in terms of their compositions and structure, Li diffusion, charge storage mechanisms, and different redox centra-based system. The key challenges to practical application are also discussed. Last but not least, in order to design high-performance DRXs, we outlined perspectives in developing DRXs for the next generation of LIB cathodes.
Pooja Saxena and Prashant Shukla 2024 J. Electrochem. Soc. 171 047504
Wearable sensors offer a non-invasive, continuous, and personalized approach to monitor various physiological and environmental parameters. Among the various materials used in the fabrication of wearable sensors, polymers have gained significant attention due to their versatile properties, low cost, and ease of integration. We present a comprehensive review of recent advances and challenges in the development of polymer-based wearable sensors. We begin by highlighting the key characteristics of wearable sensors, emphasizing their potential applications and advantages. Subsequently, we delve into the various types of polymers employed for sensor fabrication, such as conductive polymers, elastomers, and hydrogels. The unique properties of each polymer and its suitability for specific sensing applications are discussed in detail. We also address the challenges faced in the development of polymer-based wearable sensors and describes the mechanism of action in these kinds of wearable sensor-capable smart polymer systems. Contact lens-based, textile-based, patch-based, and tattoo-like designs are taken into consideration. Additionally, we paper discuss the performance of polymer-based sensors in real-world scenarios, highlighting their accuracy, sensitivity, and reliability when applied to healthcare monitoring, motion tracking, and environmental sensing. In conclusion, we provide valuable insights into the current state of polymer-based wearable sensors, their fabrication techniques, challenges, and potential applications.
Bianca-Maria Tuchiu et al 2024 J. Electrochem. Soc. 171 047502
Topical treatments rely on drugs that play a crucial role in addressing skin and mucous membrane disorders. Therefore, it is highly needed to utilize accurate analytical techniques that can determine the concentration of these chemicals in various sample matrices, including pharmaceuticals, food, and water. Currently, electrochemical sensors are predominantly used in specific fields such as biomedical, industrial, and environmental monitoring, while they have not yet been incorporated into the pharmaceutical manufacturing industry. However, electrochemical methods employing an expanding range of sensors provide a reliable, cost-effective, and efficient substitute for classical analytical methods. Their potential is highly favorable, offering possibilities for simultaneous determination, miniaturization, and real-time on-site monitoring. This work covers numerous sensors designed between 2020 and 2023 for the determination of topical drugs, highlighting their respective benefits and drawbacks while illuminating emerging trends. Moreover, it discusses the correlation between the used materials and the ease of manufacturing, to the achieved results, including dynamic range, detection limit, sensitivity, and selectivity. This work aims to serve as a valuable resource for researchers, engineers, and policymakers in the evolving field of electrochemical sensing by providing guidance and facilitating decision-making, which could lead to significant innovations in sensor technology.
Richard Bertram Church and A. John Hart 2024 J. Electrochem. Soc. 171 040512
Three-dimensional (3D) battery architectures have been envisioned to enable high energy density electrodes without the associated power drop experienced by planar cells. However, the development of 3D cells is hampered by difficulties producing conformal solid-state electrolytes (SSE), solid polymer electrolytes (SPE) and gel polymer electrolytes (GPE) that are pinhole-free and have adequate ionic conductivities. Fortunately, electrolytes in 3D cells are often utilized at lower thickness, which may compensate the decreased ionic conductivity. Here, we comprehensively review potential 3D SSE, SPE and GPE electrolyte materials by compiling their thickness and room temperature ionic conductivity. We use area specific resistance (ASR) as a metric to compare 3D electrolytes with one another and conventional electrolytes. We find that certain process-material combinations, such as atomic layer deposition of SSEs, electrodeposition of SPEs and GPEs, and initiated chemical vapor deposition of SPEs demonstrate ASRs beneath the interfacial impedances of Li-based systems and approach state-of-the-art electrolytes. We also comment on additional factors, such as electrochemical stability, that should be evaluated when determining 3D electrolyte suitability. Future research should focus on adapting known materials chemistries for conformal deposition techniques to further improve the ionic conductivity, as these techniques are capable of producing the necessary thicknesses and conformality.
Raphaël Gass et al 2024 J. Electrochem. Soc. 171 034511
Technologies based on the use of hydrogen are promising for future energy requirements in a more sustainable world. Consequently, modelling fuel cells is crucial, for instance, to optimize their control to achieve excellent performance, to test new materials and configurations on a limited budget, or to consider their degradation for improved lifespan. To develop such models, a comprehensive study is required, encompassing both well-established and the latest governing laws on matter transport and voltage polarization for Proton Exchange Membrane Fuel Cells (PEMFCs). Recent articles often rely on outdated or inappropriate equations, lacking clear explanations regarding their background. Indeed, inconsistent understanding of theoretical and experimental choices or model requirements hinders comprehension and contributes to the misuse of these equations. Additionally, specific researches are needed to construct more accurate models. This study aims to offer a comprehensive understanding of the current state-of-the-art in PEMFC modeling. It clarifies the corresponding governing equations, their usage conditions, and assumptions, thus serving as a foundation for future developments. The presented laws and equations are applicable in most multi-dimensional, dynamic, and two-phase PEMFC models.
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Hong Zhang et al 2024 J. Electrochem. Soc. 171 047510
Ordered Pt/SnO2 composite porous thin films were prepared for fabrication of planar mixed-potential hydrogen sensors. Characterization of the Pt/SnO2 films revealed that Pt elements were primarily loaded in Pt° form on the SnO2 film surface and did not significantly change the morphology of the film electrodes. The potentiometric response of Pt/SnO2 thin films to hydrogen varied with the Pt loading contents. Compared to the pristine SnO2 film, the 1 at% and 2 at% Pt-loaded SnO2 composite films exhibited 1.6 and 2.0 times higher potentiometric response to 300 ppm hydrogen at 500 °C, with a similar response time of 6–10.5 s. By assembling an array of sensors composed of SnO2 films loaded with 1 at% and 2 at% Pt, and using principal component analysis, discrimination of hydrogen and four interfering gases (ammonia, carbon monoxide, nitrogen dioxide, and propane) in the concentration range of 100–300 ppm was achieved. The sensing behaviors of the Pt/SnO2 composite thin films were discussed in relation to the competitive promotion effects for the heterogeneous and electrochemical catalytic activities by Pt loading.
Highlights
Potentiometric hydrogen sensors based on Pt/SnO2 thin films were fabricated.
Hydrogen sensing response was enhanced by loading 1 at% and 2 at% Pt.
The sensing behavior was discussed by the Pt competitive promotion effects.
Discrimination of hydrogen and four interfering gases was achieved.
S. Yanev et al 2024 J. Electrochem. Soc. 171 020512
Li-In electrodes are widely applied as counter electrodes in fundamental research on Li-metal all-solid-state batteries. It is commonly assumed that the Li-In anode is not rate limiting, i.e. the measurement results are expected to be representative of the investigated electrode of interest. However, this assumption is rarely verified, and some counterexamples were recently demonstrated in literature. Herein, we fabricate Li-In anodes in three different ways and systematically evaluate the electrochemical properties in two- and three-electrode half-cells. The most common method of pressing Li and In metal sheets together during cell assembly resulted in poor homogeneity and low rate performance, which may result in data misinterpretation when applied for investigations on cathodic phenomena. The formation of a Li-poor region on the separator side of the anode is identified as a major kinetic bottleneck. An alternative fabrication of a Li-In powder anode resulted in no kinetic benefits. In contrast, preparing a composite from Li-In powder and sulfide electrolyte powder alleviated the kinetic limitation, resulted in superior rate performance, and minimized the impedance. The results emphasize the need to fabricate optimized Li-In anodes to ensure suitability as a counter electrode in solid-state cells.
Highlights
The fabrication of Li-In anodes needs to be optimized to ensure suitability as a counter electrode in sulfide all-solid-state batteries.
The Li-In counter electrode may often be the limiting factor of sulfide all-solid-state halfcells.
Pressing Li and In foil together results in a kinetically limited anode.
Composites from Li-In and sulfide electrolyte result in stable reference potential, superior rate performance and low impedance of the counter electrode.
Ramver Singh et al 2024 J. Electrochem. Soc. 171 013501
Electrical discharge micromachining (EDM) poses challenges to the fatigue-life performance of machined surfaces due to thermal damage, including recast layers, heat-affected zones, residual stress, micro-cracks, and pores. Existing literature proposes various ex situ post-processing techniques to mitigate these effects, albeit requiring separate facilities, leading to increased time and costs. This research involves an in situ sequential electrochemical post-processing (ECPP) technique to enhance the quality of EDMed micro-holes on titanium. The study develops an understanding of the evolution of overcutting during ECPP, conducting unique experiments that involve adjusting the initial radial interelectrode gap (utilizing in situ wire-electrical discharge grinding) and applied voltage. Additionally, an experimentally validated transient finite element method (FEM) model is developed, incorporating the passive film formation phenomenon for improved accuracy. Compared to EDM alone, the sequential EDM-ECPP approach produced micro-holes with superior surface integrity and form accuracy, completely eliminating thermal damage. Notably, surface roughness (Sa) was reduced by 80% after the ECPP. Increasing the voltage from 8 to 16 V or decreasing the gap from 60 to 20 μm rendered a larger overcut. This research's novelty lies in using a two-phase dielectric (water-air), effectively addressing dielectric and electrolyte cross-contamination issues, rendering it suitable for commercial applications.
Highlights
Better micro-hole quality through in situ sequential eco-friendly near-dry EDM & ECM
Successfully resolved dielectric-electrolyte cross-contamination in sequential processes
Unique experiments that adjust the initial radial IEG using in situ wire-EDG
Developed and validated a transient FEM model, incorporating passivation aspect
Achieved recast layer-free holes with Sa values approximately 80% lower than EDM holes
Yuefan Ji and Daniel T. Schwartz 2023 J. Electrochem. Soc. 170 123511
Analytical theory for second harmonic nonlinear electrochemical impedance spectroscopy (2nd-NLEIS) of planar and porous electrodes is developed for interfaces governed by Butler-Volmer kinetics, a Helmholtz (mainly) or Gouy-Chapman (introduced) double layer, and transport by ion migration and diffusion. A continuum of analytical EIS and 2nd-NLEIS models is presented, from nonlinear Randles circuits with or without diffusion impedances to nonlinear macrohomogeneous porous electrode theory that is shown to be analogous to a nonlinear transmission-line model. EIS and 2nd-NLEIS for planar electrodes share classic charge transfer RC and diffusion time-scales, whereas porous electrode EIS and 2nd-NLEIS share three characteristic time constants. In both cases, the magnitude of 2nd-NLEIS is proportional to nonlinear charge transfer asymmetry and thermodynamic curvature parameters. The phase behavior of 2nd-NLEIS is more complex and model-sensitive than in EIS, with half-cell NLEIS spectra potentially traversing all four quadrants of a Nyquist plot. We explore the power of simultaneously analyzing the linear EIS and 2nd-NLEIS spectra for two-electrode configurations, where the full-cell linear EIS signal arises from the sum of the half-cell spectra, while the 2nd-NLEIS signal arises from their difference.
Leonardo I. Astudillo and Hubert A. Gasteiger 2023 J. Electrochem. Soc. 170 124512
A major degradation mechanism of polymer electrolyte membrane fuel cells (PEMFCs) in transportation applications is the loss of the electrochemically active surface area (ECSA) of platinum cathode catalysts upon dynamic load cycling (resulting in cathode potential cycles). This is commonly investigated by accelerated stress tests (ASTs), cycling the cell voltage under H2/N2 (anode/cathode). Here we examine the degradation of membrane electrode assemblies with Vulcan carbon supported Pt catalysts over extended square-wave voltage cycles between 0.6-1.0 VRHE at 80 °C and 30%-100% RH under either H2/N2 or H2/Air; for the latter case, differential reactant flows were used, and the lower potential limit is controlled to correspond to the high-frequency resistance corrected cell voltage, assuring comparable aging conditions. Over the course of the ASTs, changes of the ECSA, the hydrogen crossover current, the proton conduction resistance and the oxygen transport resistance of the cathode electrode, as well as the differential-flow H2/O2 and H2/Air performance at 80 °C/100% RH were monitored. While the ECSA loss decreases with decreasing RH, it is independent of the gas feeds. Furthermore, the H2/Air performance loss only depends on the ECSA loss. ASTs under H2/N2 versus H2/Air only differ with regards to the chemical/mechanical degradation of the membrane.
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Kendre et al
Precise revealing and early detection of 3-Nitro-L-Tyrosine (3-NLT), a biomarker of oxidative stress in biological media is critical for the early treatment of cancer tumorigenic cells and immunologic disorders. In this study, zinc tungstate (ZnWO4) was incorporated with functionalized carbon nanofibers (f-CNF) to form a ZnWO4/f-CNF composite. The composite improves detection of 3-NLT by increasing the electrical conductivity, electrocatalytic activity, and rapid electron transfer kinetics. Various physical characterization techniques were employed to confirm the ZnWO4/f-CNF composite. Electrochemical impedance spectroscopy, cyclic voltammetry, and differential pulse voltammetry were utilized to detect 3-NLT after modifying ZnWO4/f-CNF on glassy carbon electrode (GCE). The ZnWO4/f-CNF/GCE achieved an elevated electrochemically active surface area (0.08 cm2), a linear range of 1.0-117.0 µM, and a low detection limit of 0.07 µM. Finally, the ZnWO4/f-CNF/GCE was tested with bovine serum albumin and tap water in the real sample investigation.
Stiegeler et al
Polymer electrolyte fuel cells for heavy-duty applications require lifetimes beyond 30,000 hours, which poses a durability challenge. In this study, we investigated the influence of various factors on loss of electrochemically active surface area (ECSA) in the cathode, which is a major limiting factor. We derive a parameter range from simulated drive cycles showing that the voltage ranges between 0.70 and 0.85 V and that the cells are in idle state at upper potential limit (UPL) most of the time. We evaluate the influence and interaction of UPL, lower potential limit (LPL), temperature, relative humidity, and cycle time on ECSA and performance at four different operating conditions after 10,000 potential cycles based on 25 experiments. The results indicate that UPL and the hold time at UPL have the strongest impact on degradation, while LPL has a small impact, which does not increase below the potential of full platinum reduction (0.55 V) or hold times longer than 2 seconds. Furthermore, the interaction of humidity with other factors becomes significant for long experiment times. In summary, the findings of this work can serve as guidelines for minimizing ECSA loss, e.g. by keeping the fuel cell in a benign operation regime via systems control
Feng et al
Developing low Pt or non-precious metal catalysts for oxygen reduction reaction (ORR) has becoming necessary in recent years. Herein, PtM alloy anchored on nitrogen-doped carbon (PtM/NC, M=Fe, Co) catalyst with ultralow Pt loading (~1 wt%) is prepared from the simple two-process pyrolysis, namely from C to M-NC then to PtM/NC. The as-prepared PtM/NC (M=Fe, Co) shows an excellent ORR catalytic performance with the peak potential and half-wave potential of 0.901 and 0.870 V for PtFe/NC, 0.868 and 0.845 V for Pt3Co/NC. The ORR on PtM/NC (M=Fe, Co) is a mainly direct 4-electron reaction pathway (3.75-3.90) in alkaline solution. Moreover, they possess good methanol tolerance and stability. Synergistic effect of Pt and M together with N species result in the excellent ORR catalytic activity of PtM/NC (M=Fe, Co). The negative shift of Pt binding energy caused by both lattice contraction and electron orbital coupling from M is beneficial for reducing the d-band center of Pt, weakening the oxygen binding energy and enhancing the ORR intrinsic activity of Pt. The strong interactions between NC and PtM alloy are beneficial for anchoring PtM nanoparticles, promoting the stability of catalyst. This work provides a new strategy for preparing ultralow Pt loading catalysts.
Walton et al
Aluminum alloy, AlSi10Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8 % sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi10Mg surface produced a porous oxide layer with a thickness of 5 μm. The oxide coating weight was 698 ± 29 mg/ft2. The oxide coating forms in the aluminum cells that are isolated from one another by the silicon phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (Rp) values increased by 279× after anodization. The corrosion current density values (jcorr) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.
Nguyen Le et al
We have introduced potential modifiers synthesized from attached Ag nanoparticles (NPs) on MnO2 nanostructural surfaces, and fabricated an electrochemical sensor toward 4-nitrophenol (4-NP) detection. MnO2 with various morphologies (nanowires, nanorods, and nanosheets) has been prepared by hydrothermal and microwave-assisted hydrothermal methods, while AgNPs have been prepared by the simple electrochemical method. The structural characteristics and surface morphologies have been investigated via X-ray diffraction and scanning electron microscopy measurements. The effect of the change in morphology on the electrochemical behaviors and sensing performance has been investigated and discussed in detail. A parameter series involving the redox reaction of [Fe(CN)6]3-/4- and 4-NP reduction process has been calculated for each as-prepared modified electrode. Electrochemical results evidenced that benefiting from possessing outstanding electrochemical behaviors such as better conductivity, faster electron transfer ability, larger electroactive surface area, and higher charge transfer kinetics, MnO2 sheets-Ag/SPE has offered wider linear concentration range of 0.5-50 μM, LOD value as low as 0.073 µM, and high selectivity/repeatability. Furthermore, the optimization in the morphological aspect of MnO2 nanosheets and synergic effects arising from the effective combination with AgNPs make it become a model material for modifying electrode surfaces, indicating great potential for advanced electrochemical sensing applications.
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M. Sepe et al 2024 J. Electrochem. Soc. 171 054501
Optimization of proton exchange membrane water electrolyzers (PEMWE) has become a focus of researchers looking for a reliable way to generate power. A vital component to PEMWE operation is the porous transport layer (PTL) on the anode side, which is where oxygen is produced. The PTL must allow water access to the catalyst layer and remove oxygen simultaneously. In this work, a previously developed imaging technique is used to generate bilayer PTL structures. A multiscale modeling approach was used to study the effect of a bilayer PTL on oxygen evolution and PEMWE performance. First, a micro scale model was used to predict oxygen transport pathways through different PTL structures. Results showed that the bilayer PTL results in higher oxygen saturation and faster oxygen transport through the PTL. Second, a macro scale model was used to predict performance using bilayer PTLs. Predictions showed potential values between 10 and 20 mV below single layer potential values. This points to the bilayer improving PEMWE operation. Findings from this work show how the addition of a mesoporous layer to a PTL substrate will improve oxygen transport and removal from the catalyst surface, which will improve PEMWE performance.
Julian Stiegeler et al 2024 J. Electrochem. Soc.
Polymer electrolyte fuel cells for heavy-duty applications require lifetimes beyond 30,000 hours, which poses a durability challenge. In this study, we investigated the influence of various factors on loss of electrochemically active surface area (ECSA) in the cathode, which is a major limiting factor. We derive a parameter range from simulated drive cycles showing that the voltage ranges between 0.70 and 0.85 V and that the cells are in idle state at upper potential limit (UPL) most of the time. We evaluate the influence and interaction of UPL, lower potential limit (LPL), temperature, relative humidity, and cycle time on ECSA and performance at four different operating conditions after 10,000 potential cycles based on 25 experiments. The results indicate that UPL and the hold time at UPL have the strongest impact on degradation, while LPL has a small impact, which does not increase below the potential of full platinum reduction (0.55 V) or hold times longer than 2 seconds. Furthermore, the interaction of humidity with other factors becomes significant for long experiment times. In summary, the findings of this work can serve as guidelines for minimizing ECSA loss, e.g. by keeping the fuel cell in a benign operation regime via systems control
Jack Walton et al 2024 J. Electrochem. Soc.
Aluminum alloy, AlSi10Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8 % sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi10Mg surface produced a porous oxide layer with a thickness of 5 μm. The oxide coating weight was 698 ± 29 mg/ft2. The oxide coating forms in the aluminum cells that are isolated from one another by the silicon phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (Rp) values increased by 279× after anodization. The corrosion current density values (jcorr) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.
Jieyu Zhao et al 2024 J. Electrochem. Soc. 171 046507
As a result of issues related to pH control and the competition between H2O2 production and activation at the same sites, the applications of electro-Fenton (EF) pollutant remediation systems are limited. This work designed a synergistic dual-cathode EF system that exhibits self-adjustment of pH and stable electrode coatings. This system is based on using biomass as the active cathode material for H2O2 generation and the interaction between a stainless-steel mesh and FeOCl to reduce Fe3+ ions. The synergistic factor for this dual-cathode system was calculated to be 85.2%. Significantly, the production and activation of H2O2 in this composite system are unaffected by pH and the pH value can be adjusted between 9.67 and 3.7 without adding any acidic reagents. This process allows for the degradation of recalcitrant organic pollutants over the pH range of 3 to 9 without pre-acidification or challenges related to iron sludge and effluent chromaticity. Various organic pollutants, including antibiotics and organic dyes, can be effectively decomposed using this technology, which also exhibits good stability throughout 22 continuous trials over 1400 min. This work demonstrates a novel yet viable approach to highly efficient, inexpensive pollutant treatment with good reusability, a wide pH range and no iron leaching.
Cedric Grosselindemann et al 2024 J. Electrochem. Soc.
Performance of a solid oxide cell (SOC) depends on the operating environment. Regarding single cell tests with ideal contacting (gold, platinum, nickel meshes) and inert flow fields (Al2O3), performance is limited by intrinsic losses in the cell. Contact losses and poisoning effects are minimized. In a SOC-stack with metallic interconnectors, performance is affected by contact resistances, chromium (Cr) evaporation, and limitations in gas supply. Here, 1 cm² single cells were tested with a stack-like contact applying metallic flow fields made from three different steel grades (Crofer 22 APU, AISI 441, UNS S44330) with and without a cerium-cobalt PVD-coating. Cell performance and losses were analyzed by IV-characteristics, impedance spectroscopy, and DRT analysis. For all uncoated interconnectors, significant performance losses due to increased contact losses and air electrode polarization were observed, which is attributed to Cr-oxide scale formation on the metallic interconnectors and Cr-poisoning of the air electrode as revealed by scanning electron microscopy-energy-dispersive X-ray spectroscopy. A CeCo-coating leads to similar oxide scales irrespective of the substrate material. Moreover, with the coating the electrochemical performance drastically improved due to decreased contact losses and an effective blocking of Cr-evaporation leading to a cell performance close to the ideal case for all three steel grades
Hannes Liepold et al 2024 J. Electrochem. Soc.
Recent developments in hydrocarbon-based proton exchange membrane fuel cells have significantly narrowed the performance gap compared to state-of-the-art cells using perfluorosulfonic acid ionomers (PFSA). However, balancing protonic resistance and gas transport resistance in the catalyst layer remains a challenge at low humidity. This study investigates gas transport resistance and its components in sulfonated phenylated polyphenylene-based catalyst layers using various limiting current methods. Results show that increasing the dry ionomer to carbon (I/C) ratio from 0.2 to 0.4, a measure to catch up with protonic resistance of PFSA-based catalyst layers, significantly increases gas transport resistance in the cathode catalyst layer by 28 %. The data suggest a strong correlation between local gas transport resistance and IEC. A high IEC is beneficial for the gas transport through the ionomer film. However, at low ionomer volume fractions the local gas transport resistance is dominated by the I/C independent interfacial resistance. Furthermore, a low IEC hydrocarbon ionomer, such as Pemion® PP1-HNN4-00-X (IEC = 2.5 meq g-1), not only exhibits a beneficial interfacial resistance, but also suppresses excessive ionomer swelling, which typically occurs during operating conditions where liquid water is forming.
Lena Viviane Bühre et al 2024 J. Electrochem. Soc.
The commercialization of proton exchange membrane water electrolysis cells (PEMWEs), which are essential for a greener and more sustainable future, is hindered by the high costs of noble metal catalysts, as well as the degradation of the catalysts and membranes. Examining the electrodes' characteristics with reference electrodes (REs) yields insights into their individual performance and can, e.g., help assess new catalyst layer designs, their interplay with the adjacent porous transport layer, or understand the complex and multi-faceted degradation mechanisms. This review provides an overview of previous approaches and the evolution of RE designs in PEMWE. By discussing the strengths and limitations of different RE setups, readers are enabled to make more informed decisions about their experiments' design and choose the best RE setup for their specific research question.
Yuki Tsuda et al 2024 J. Electrochem. Soc.
This study investigates the effect of five amino acids on the electrodeposition of Cu to enhance its electrocatalytic performance in CO2 reduction reactions (CO2RR). The amino acids significantly influenced the deposition potential, crystallite size, and surface morphology of the electrodeposited Cu. Electrodeposited Cu with amino acids exhibit significantly smaller crystallites and higher particle density on carbon paper relative to amino acid-free samples. The integration of amino acids into the electrodeposited Cu was confirmed via high-angle annular dark-field scanning transmission electron microscopy, energy dispersive X-ray spectroscopy and hard X-ray photoelectron spectroscopy. All electrodeposited Cu exhibits a higher faradaic efficiency (FE) in the electrochemical reduction of CO2 to CH4 relative to Cu foil (24.2%), regardless of the presence or absence (55.0%) of amino acids when the electrolysis was conducted at −1.27 V vs. RHE. Electrodeposited Cu with L-histidine, containing an imidazole group, demonstrates a higher FE of CH4 (67.6%) and effectively suppressed the hydrogen evolution reaction, highlighting the crucial role of amino acid functional groups, particularly imidazole, in augmenting the electrochemical conversion of CO2 to CH4. The study demonstrates the critical influence of specific functional groups in amino acids on the catalytic efficiency of electrodeposited Cu in CO2RR electrocatalysis applications.
Nicholas R. Cross et al 2024 J. Electrochem. Soc. 171 040547
Thermally regenerative ammonia batteries (TRABs) are an emerging technology that use low temperature heat (T < 150 °C) to recharge a flow battery that produces electrical power on demand. The all-aqueous copper TRAB can provide high power densities and thermal energy efficiencies relative to other devices that harvest energy from waste heat, but its performance is adversely impacted by the crossover of undesired species through the membrane and lower cell voltages compared to conventional batteries. In this work, we developed a numerical model to simulate discharge curves while accounting for crossover inefficiencies without tracking all electrolyte species through the membrane. The model was able to successfully reproduce discharge curves across a diverse range of battery conditions using a single fitting parameter to account for decay of electrode standard potential due to species crossover with minimal error (< 5%). The model was then used to simulate different design scenarios to estimate changes in energy output from alterations to the aspects of the battery electrolyte chemistry. Results from this study are used to identify pathways for improving future TRAB designs with respect to energy capacity and cost-effectiveness of the technology.
F. Kullmann et al 2024 J. Electrochem. Soc. 171 044511
The trend of operating the solid oxide fuel cell at significantly lower operation temperatures enables the application of electrodes with finer microstructure or even nanostructured electrodes with increased active surface and enhanced performance. To maintain the high performance in hydrocarbon fuels commonly impurified with sulfur compounds, a required sulfur tolerance has to be maintained. In this study we compare performance and H2S-poisoning of four ceria-based electrodes: conventional Ni/Ce0.9Gd0.1O2−δ cermets and sub-μm scaled Ce0.8Gd0.2O2−δ-electrodes with and without infiltrated nickel. Symmetrical cells were operated in a hydrogen/steam/nitrogen gas mixture with and without minor amounts of H2S at 600 °C. The performance is analyzed by electrochemical impedance spectroscopy. The distribution of relaxation times is applied to deconvolute the electrochemical processes followed by a complex nonlinear least square fit to quantify the loss processes and the impact of sulfur. Whereas two different Ni/Ce0.9Gd0.1O2−δ cermet electrodes exhibit polarization resistances at 600 °C without/with 0.1 ppm H2S of 2.89/5.56 Ωcm2 and 2.15/2.75 Ωcm2, the single phase Ce0.8Gd0.2O2−δ electrode reaches 0.98/2.37 Ωcm2. With an infiltration of Ni-nitrate forming nickel nanoparticles on the gadolinia-doped ceria-surfaces, the ASR could be drastically reduced to 0.32/0.37 Ωcm2.