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
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.
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.
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.
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.
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.
E. Peled and S. Menkin 2017 J. Electrochem. Soc. 164 A1703
The Solid-Electrolyte-Interphase (SEI) model for non-aqueous alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the solution is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047 (1979).] new equations for: electrode kinetics (io and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technology of lithium batteries. This paper reviews the past, present and the future of SEI batteries.
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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Benedikt Stumper et al 2024 J. Electrochem. Soc. 171 059002
S. Yanev et al 2024 J. Electrochem. Soc. 171 050530
Increasing the specific capacity and rate performance of thiophosphate composite cathodes is a major challenge in solid-state battery development. Understanding the charge transport kinetics and rate-limiting mechanisms within the cathode is key towards efficient optimization. Herein, we use quantitative analysis of chronoamperometric rate performance data to differentiate between resistive and diffusive rate limitations of NCM811—Li6PS5Cl cathodes with different morphology and composition. We substantiate our findings with separate measurements of the effective ionic conductivity and Li+ diffusion coefficients using impedance spectroscopy and GITT techniques, respectively. Increasing the active material to solid electrolyte ratio is found to increase diffusive limitations, which originate from the small contact area between the active material and solid electrolyte. The diffusive limitation is especially pronounced for single crystal NCM811 cathodes at over 84% AM. Employing fine particle catholyte significantly increases the contact area, alleviates the diffusive limitation, and increases rate performance. These results provide guidelines towards bringing the solid-state battery performance levels closer to practical targets.
Highlights
Chronoamperometry rate tests enable characterization of resistive and diffusive rate performance limitations and bottlenecks.
Solid-state diffusion in the active material limits the rate performance of sulfide cathodes.
Diffusive limitations are caused by low contact surface area between the sulfide electrolyte and active material.
Fine particle sulfide increases the contact surface area between the sulfide electrolyte and active material.
Mitchell Barclay et al 2024 J. Electrochem. Soc. 171 050529
Rechargeable Zn-ion batteries have the potential to address the need for cheap and widely accessible energy storage. Metal-doped manganese oxide cathodes are a common and effective choice for Zn-ion batteries. Zn-ion battery development can be advanced by overcoming the poor cycle life that many metal-doped Mn-oxide cathodes suffer from. Plasma-treated water (PAW) is created using low input power of 0.145 kWh per liter of PAW and is used to accelerate the reduction and precipitation of MnO4− and nickel acetate (Ni(Ac)) to form a multiphase NiMnO3 electrode with Ni2+ and Ni3+ doped into the MnO6 octahedra, which exhibits capacitance dominated charge storage mechanisms. The electrode shows initial specific capacitance of 60.1 F g−1 and a capacitance retention of 100.8% after 10,000 cycles and 92.2% after 12,000 cycles. The beneficial layer of nanoflake morphology is formed during cycling, which causes a rapid increase in specific capacitance due to the larger electrochemically active surface area and the associated surface adsorption-based (pseudo-capacitive) type charge storage. We also demonstrate the capability of our multiphase NiMnO3 electrode to be coupled with a Zn metal anode in a battery cell which exhibits 330 mAh g−1 peak specific capacity and capacity retention of 63.8% after 380 cycles.
Jinxing Li et al 2024 J. Electrochem. Soc. 171 050528
Nickel-rich layered oxides (NCM) are a promising contender material for the cathode electrode of high-energy lithium-ion batteries (LIBs) due to their large reversible capacity and high operating voltage. However, the poor surface/interfacial stability and the dissolution of transition metal ions hinder the commercial application of NCM. To create an artificial cathode electrolyte interphase (CEI) with LiF-rich inorganic phase on the NCM surface, a practical and efficient way of quenching the NCM powder from high temperature in 1,1,2,2-Tetrafluoroethyl 2,2,2-trifluoroethyl ether (HFE) was devised. With this artificial CEI film, the side reactions between NCM and electrolytes are inhibited, and the dissolution of TM ions is retarded. The quenched-NCM achieved fantastic cycling performance and suppressed voltage decay. Our research offers an efficient and worthy approach for improving the surface/interfacial stabilization of nickel-rich cathode materials for high-energy-density LIBs.
Nicholas S. Wilson et al 2024 J. Electrochem. Soc. 171 050527
Matched glassy carbon electrodes in aqueous K2SO4 electrolytes were used to examine the effects of opposing electrode spacing on capacitive performance. Planar non-porous glassy carbon electrodes were used to avoid complications with porosity and roughness. Electrode spacing effects were examined in terms of device and individual electrode performance, using cyclic voltammetry, coupled with its deconvolution into residual, diffusional, and capacitive processes. Decreasing the spacing between electrodes led to a decrease in capacitive contributions, and a relative increase in diffusional and residual contributions, implying that individual electrodes were influencing the behaviour of each other. This is also consistent with the use of more dilute electrolytes. Electrode behaviour was modelled using the Poisson-Boltzmann equation, together with its integrated outputs of electric field and potential difference. For electrodes with the same amount of charge and a similar diffuse layer thickness, the electric field and potential drop was diminished because of their charge interaction. Conversely, it is shown that for a similar potential drop across the electrodes, the variable controlled in a cyclic voltammetry experiment, more charge accumulation is needed at the electrode-electrolyte interface to compensate for the counter charge generate from the opposing electrode.
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Durgalakshmi Dhinasekaran et al 2024 J. Electrochem. Soc. 171 057505
Uric acid (UA) is an important biomarker in blood to diagnosis diseases linked with hyperuricemia. Although several detection methods exist for UA sensing, electrochemical method has emerged as a promising alternative. For effective performance of a biosensor, the choice of electroactive material plays a crucial role. The developed electrodes are enzymatic and non-enzymatic with modified nano-structures of metal oxides, ferrites and carbon-based materials. Several combinations of nanocomposites using metal oxides with carbon-based compounds show promising results for biosensor applications. This is attributed to its functional groups, higher surface area and porous nature that can improve the sensing performance as it requires only quick-time processing with inexpensive and direct detection methods. The electrochemical method uses anodic peak current which is the analytical signal to sense the electrochemical oxidation of UA. This technique paves a new way to make electrodes for point-of-detection devices in near future. It could be the next generation of non-invasive analysis for food hygiene as well as biomedical and clinical applications. This review focuses on materials used in electrochemical sensing of UA and discusses on the application of different electrochemical techniques in UA detection.
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.
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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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R et al
Immunosensors have emerged as vital tools in cancer diagnostics, providing simplified and rapid detection of biomarkers that are necessary for timely diagnosis. The objective of using an electrochemical immunosensor is to detect cancers at early stages, so that obtained biological information can be analyzed using artificial intelligence (AI) for deciding an appropriate treatment, avoiding false diagnosis, and preventing patient fatalities. The focus of this article is on four major reproductive cancers—breast, ovarian, cervical, and prostate cancers. Specifically, it explores the identification and optimization of biomarkers crucial for precise detection in these cancers. Examining a decade of research, the review delves into nanotechnology-assisted electrochemical immunosensors (affinity biosensors), outlining advancements and emphasizing their potential in reproductive cancer diagnostics. Furthermore, the review contemplates avenues for enhancing sensor characteristics to pave the way for their application in field diagnosis, with a forward-looking perspective on AI-assisted diagnostics for the next generation of personalized healthcare. In navigating the landscape of reproductive cancer diagnostics, the integration of advanced technologies promises to transform our approach, offering improved accuracy and outcomes for patients.
Torrie et al
A simply constructed, stable, Ni/Ni2+ saturated reference electrode (SRE) has potential to measure thermodynamic behavior of molten chloride salts more reliably. Like the Ag/Ag+ reference electrode (RE), the Ni/Ni2+ SRE is made of commercially available materials. Initial experiments in molten CaCl2 and LiCl show the Ag/Ag+ RE potential drifting two times faster than the SRE. Furthermore, experiments show the replicability of SREs by comparing two Ni/Ni2+ SREs with different compositions of NiCl2 which is supportive of saturated phase behavior.
Zhang et al
Hydrogen is a prime candidate for replacing fossil fuels. Electrolyzing water to produce hydrogen stands out as a particularly clean method, garnering significant attention from researchers in recent years. Among the various techniques for electrolyzing water to produce hydrogen, alkaline electrolysis holds the most promise for large-scale industrialization. The key to advancing this technology lies in the development of durable and cost-effective electrocatalysts for the hydrogen evolution reaction (HER). Self-supporting electrode is an electrode structure in which a catalyst layer is formed directly on a substrate (such as carbon cloth, nickel foam, stainless steel, etc.) without using a binder and with good structural stability. In contrast to traditional nanocatalysts, self-supporting electrocatalysts offer significant advantages, including reduced resistance, enhanced stability, and prolonged usability under high currents. This paper reviews recent advancements in HER electrochemical catalysts for alkaline water electrolysis, focusing on the utilization of hydrogen-evolving catalysts such as metal sulfides, phosphides, selenides, oxides, and hydroxides. With self-supported electrocatalysts as the focal point, the paper delves into progress made in their preparation techniques, structural design, understanding of reaction mechanisms, and strategies for performance enhancement. Ultimately, the future development direction of promoting hydrogen evolution by self-supported electrocatalysts in alkaline water electrolysis is summarized.
Tran et al
The quest for economical and sustainable electrocatalysts to facilitate the hydrogen evolution reaction (HER) is paramount in addressing the pressing challenges associated with carbon dioxide emissions. Molybdenum carbide-based nanomaterials have emerged as highly promising electrocatalysts for HER due to their Pt-like catalytic proficiency, exceptional stability, and the versatility of their crystal phases. Within this comprehensive review, we explore the diverse methodologies for synthesizing molybdenum carbides, including solid-gas, solid-solid, and solid-liquid phase reactions. In addition, a thorough elucidation of the hydrogen generation process through water electrolysis is provided. Furthermore, a spectrum of innovative strategies aimed at augmenting the performance of molybdenum carbides in the HER milieu is introduced, encompassing cutting-edge techniques such as phase-transition engineering, the construction of heterostructures, hetero-atom doping, the integration of hybrid structures with carbon materials, defect engineering, and meticulous surface modification. The review culminates by underscoring the current challenges and the promising prospects in the advancement of electrocatalysts for hydrogen production, with a dedicated focus on molybdenum carbide-based catalysts.
Saberi et al
This study investigates the impact of process-induced defects such as gas pores, lack of fusions, and surface roughness on corrosion behavior of stainless steel 304L (SS304L) fabricated by laser powder bed fusion additive manufacturing. Specimens are printed with optimized process parameters but selected from different locations on the build plate. Parallel and perpendicular surfaces to the build direction are investigated and compared with corrosion properties of wrought SS304L in 5wt.% NaCl. The results reveal significant difference in corrosion behavior among specimens due to variations in their defect features. Pitting potential, pit initiation, and growth rates are found to be influenced by specimen location on the build plate. The specimen located in downstream of the shielding gas flow shows the least corrosion resistance. While no clear trends are observed between some corrosion properties and defect features, other properties show strong correlations. For example, no trend is observed for the corrosion properties in relation to pore average area fraction. However, strong correlations are observed for the corrosion properties as functions of defects maximum area. Corrosion properties linearly deteriorate as the defects maximum area increases. Roughness shows a mixed relationship with pitting potential. Comprehensive discussions on all these effects are presented.
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Benedikt Stumper et al 2024 J. Electrochem. Soc. 171 059002
S. Yanev et al 2024 J. Electrochem. Soc. 171 050530
Increasing the specific capacity and rate performance of thiophosphate composite cathodes is a major challenge in solid-state battery development. Understanding the charge transport kinetics and rate-limiting mechanisms within the cathode is key towards efficient optimization. Herein, we use quantitative analysis of chronoamperometric rate performance data to differentiate between resistive and diffusive rate limitations of NCM811—Li6PS5Cl cathodes with different morphology and composition. We substantiate our findings with separate measurements of the effective ionic conductivity and Li+ diffusion coefficients using impedance spectroscopy and GITT techniques, respectively. Increasing the active material to solid electrolyte ratio is found to increase diffusive limitations, which originate from the small contact area between the active material and solid electrolyte. The diffusive limitation is especially pronounced for single crystal NCM811 cathodes at over 84% AM. Employing fine particle catholyte significantly increases the contact area, alleviates the diffusive limitation, and increases rate performance. These results provide guidelines towards bringing the solid-state battery performance levels closer to practical targets.
Highlights
Chronoamperometry rate tests enable characterization of resistive and diffusive rate performance limitations and bottlenecks.
Solid-state diffusion in the active material limits the rate performance of sulfide cathodes.
Diffusive limitations are caused by low contact surface area between the sulfide electrolyte and active material.
Fine particle sulfide increases the contact surface area between the sulfide electrolyte and active material.
Mitchell Barclay et al 2024 J. Electrochem. Soc. 171 050529
Rechargeable Zn-ion batteries have the potential to address the need for cheap and widely accessible energy storage. Metal-doped manganese oxide cathodes are a common and effective choice for Zn-ion batteries. Zn-ion battery development can be advanced by overcoming the poor cycle life that many metal-doped Mn-oxide cathodes suffer from. Plasma-treated water (PAW) is created using low input power of 0.145 kWh per liter of PAW and is used to accelerate the reduction and precipitation of MnO4− and nickel acetate (Ni(Ac)) to form a multiphase NiMnO3 electrode with Ni2+ and Ni3+ doped into the MnO6 octahedra, which exhibits capacitance dominated charge storage mechanisms. The electrode shows initial specific capacitance of 60.1 F g−1 and a capacitance retention of 100.8% after 10,000 cycles and 92.2% after 12,000 cycles. The beneficial layer of nanoflake morphology is formed during cycling, which causes a rapid increase in specific capacitance due to the larger electrochemically active surface area and the associated surface adsorption-based (pseudo-capacitive) type charge storage. We also demonstrate the capability of our multiphase NiMnO3 electrode to be coupled with a Zn metal anode in a battery cell which exhibits 330 mAh g−1 peak specific capacity and capacity retention of 63.8% after 380 cycles.
Nicholas S. Wilson et al 2024 J. Electrochem. Soc. 171 050527
Matched glassy carbon electrodes in aqueous K2SO4 electrolytes were used to examine the effects of opposing electrode spacing on capacitive performance. Planar non-porous glassy carbon electrodes were used to avoid complications with porosity and roughness. Electrode spacing effects were examined in terms of device and individual electrode performance, using cyclic voltammetry, coupled with its deconvolution into residual, diffusional, and capacitive processes. Decreasing the spacing between electrodes led to a decrease in capacitive contributions, and a relative increase in diffusional and residual contributions, implying that individual electrodes were influencing the behaviour of each other. This is also consistent with the use of more dilute electrolytes. Electrode behaviour was modelled using the Poisson-Boltzmann equation, together with its integrated outputs of electric field and potential difference. For electrodes with the same amount of charge and a similar diffuse layer thickness, the electric field and potential drop was diminished because of their charge interaction. Conversely, it is shown that for a similar potential drop across the electrodes, the variable controlled in a cyclic voltammetry experiment, more charge accumulation is needed at the electrode-electrolyte interface to compensate for the counter charge generate from the opposing electrode.
Yoshiki Yokoyama et al 2024 J. Electrochem. Soc. 171 050525
There is a demand for low-melting-point molten-salt electrolytes with high thermal and electrochemical stability for the development of high-performance sodium-ion batteries. Mixing sodium bis(fluorosulfonyl)amide (NaFSA) and sodium (fluorosulfonyl)(trifluoromethylsulfonyl)amide (NaFTA) results in a large depression in their melting points. In this study, the phase behavior and Na+ transport properties of binary mixtures of NaFSA and NaFTA were investigated. The mixture of NaFSA and NaFTA with a molar ratio of 8:2 has a melting temperature (Tm) of 363 K, successfully achieving an ionic liquid consisting of single cationic (Na+) salts. This mixture easily forms a super-cooled liquid. The ionic conductivity (σ) of Na[(FSA)0.8(FTA)0.2] continuously varied from above Tm to below Tm, obeying the Vogel–Tamman–Fulcher equation, which coincides with its super-cooling nature. The ionic conductivity and apparent Na+ transference number (tNa+) under anion-blocking conditions at Tm approached 10−3 S cm−1 and 0.92, respectively.
Jason Marvin Torrie et al 2024 J. Electrochem. Soc.
A simply constructed, stable, Ni/Ni2+ saturated reference electrode (SRE) has potential to measure thermodynamic behavior of molten chloride salts more reliably. Like the Ag/Ag+ reference electrode (RE), the Ni/Ni2+ SRE is made of commercially available materials. Initial experiments in molten CaCl2 and LiCl show the Ag/Ag+ RE potential drifting two times faster than the SRE. Furthermore, experiments show the replicability of SREs by comparing two Ni/Ni2+ SREs with different compositions of NiCl2 which is supportive of saturated phase behavior.
Endao Zhang and Wei Song 2024 J. Electrochem. Soc.
Hydrogen is a prime candidate for replacing fossil fuels. Electrolyzing water to produce hydrogen stands out as a particularly clean method, garnering significant attention from researchers in recent years. Among the various techniques for electrolyzing water to produce hydrogen, alkaline electrolysis holds the most promise for large-scale industrialization. The key to advancing this technology lies in the development of durable and cost-effective electrocatalysts for the hydrogen evolution reaction (HER). Self-supporting electrode is an electrode structure in which a catalyst layer is formed directly on a substrate (such as carbon cloth, nickel foam, stainless steel, etc.) without using a binder and with good structural stability. In contrast to traditional nanocatalysts, self-supporting electrocatalysts offer significant advantages, including reduced resistance, enhanced stability, and prolonged usability under high currents. This paper reviews recent advancements in HER electrochemical catalysts for alkaline water electrolysis, focusing on the utilization of hydrogen-evolving catalysts such as metal sulfides, phosphides, selenides, oxides, and hydroxides. With self-supported electrocatalysts as the focal point, the paper delves into progress made in their preparation techniques, structural design, understanding of reaction mechanisms, and strategies for performance enhancement. Ultimately, the future development direction of promoting hydrogen evolution by self-supported electrocatalysts in alkaline water electrolysis is summarized.
Leila Saberi et al 2024 J. Electrochem. Soc.
This study investigates the impact of process-induced defects such as gas pores, lack of fusions, and surface roughness on corrosion behavior of stainless steel 304L (SS304L) fabricated by laser powder bed fusion additive manufacturing. Specimens are printed with optimized process parameters but selected from different locations on the build plate. Parallel and perpendicular surfaces to the build direction are investigated and compared with corrosion properties of wrought SS304L in 5wt.% NaCl. The results reveal significant difference in corrosion behavior among specimens due to variations in their defect features. Pitting potential, pit initiation, and growth rates are found to be influenced by specimen location on the build plate. The specimen located in downstream of the shielding gas flow shows the least corrosion resistance. While no clear trends are observed between some corrosion properties and defect features, other properties show strong correlations. For example, no trend is observed for the corrosion properties in relation to pore average area fraction. However, strong correlations are observed for the corrosion properties as functions of defects maximum area. Corrosion properties linearly deteriorate as the defects maximum area increases. Roughness shows a mixed relationship with pitting potential. Comprehensive discussions on all these effects are presented.
Daniel Esau et al 2024 J. Electrochem. Soc.
Modelling of the co-electrolysis process requires understanding of the underlying reaction pathways under H2/H2O/CO/CO2-atmospheres. These include the electrochemical steam reduction/hydrogen oxidation, the electrochemical CO2 reduction/CO oxidation and their coupling via the catalytic (reverse) water gas shift reaction ((R)WGS). The assumption of a very fast RWGS and therefore neglectable electrochemical CO2 conversion is commonly used to model the co-electrolysis process. In contrast, previous studies on Ni/GDC fuel electrodes suggest that the electrochemical conversion of CO / CO2 can be present in H2/H2O/CO/CO2-atmospheres. To deconvolute surface-related and non-surface-related processes in the impedance response we present results from a complex variation of operating parameters for process identification by the use of electrochemical impedance spectroscopy and the subsequent impedance analysis by the distribution of relaxation times. A physically meaningful equivalent circuit model, based on a single channel transmission line, is then derived. The model enables quantification of the surface reaction resistance under varied C/H-ratios. From a kinetic analysis it is shown that the electrochemical H2/H2O conversion is dominant for y_CO+y_(CO_2 )≤ 50% and electrochemical CO/CO2-conversion onsets from y_CO+y_(CO_2 )≥ 60%.
Jonas Stoll et al 2024 J. Electrochem. Soc.
Utilizing a direct film coating method (DFCM), such as doctor blade coating, offers a promising approach for efficient and scalable catalyst layer (CL) production for fuel cells. To further widen the understanding of lab-scale DFCM, the present research investigates how different Pt-based catalyst ink formulations coated via doctor blade coating with varying blade gap thickness (BGT) affect the CL quality and catalyst loading. In total, 120 CL samples were prepared by coating 20 different catalyst ink formulations with varying solids content, ionomer-to-carbon (I/C) ratio, and water-to-isopropanol solvent ratio with BGTs of 75, 125, and 200 μm. Inspection of these samples showed that the solvent ratio affects the coating uniformity, with the most uniform films achieved with a ratio of 1.67 or greater. Furthermore, increasing the I/C ratio for a given solids content ink formulation decreases the Pt loading, whereas an I/C ratio above or below 1.0 reduces cell performance due to mass transport or proton conductivity impacts, respectively. In addition, a relationship factor and equations are presented to estimate the solid weight and catalyst loading of the fabricated CL based on the ink formulation and BGT. Overall, this work provides important guidance for lab-scale DFCM fabrication of industrially relevant CLs