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.
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.
Adam Z. Weber et al 2014 J. Electrochem. Soc. 161 F1254
Polymer-electrolyte fuel cells are a promising energy-conversion technology. Over the last several decades significant progress has been made in increasing their performance and durability, of which continuum-level modeling of the transport processes has played an integral part. In this review, we examine the state-of-the-art modeling approaches, with a goal of elucidating the knowledge gaps and needs going forward in the field. In particular, the focus is on multiphase flow, especially in terms of understanding interactions at interfaces, and catalyst layers with a focus on the impacts of ionomer thin-films and multiscale phenomena. Overall, we highlight where there is consensus in terms of modeling approaches as well as opportunities for further improvement and clarification, including identification of several critical areas for future research.
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.
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M.-D. Gerngross et al 2024 J. Electrochem. Soc. 171 059001
Juqiang Feng et al 2024 J. Electrochem. Soc. 171 050514
Accurately assessing battery state of health (SOH) is crucial for ensuring the safety of lithium-ion batteries. However, current SOH evaluation methods suffer from inconsistent criteria and limited accuracy in prediction models. This paper introduces a novel SOH prediction and assessment strategy that relies on multiple indicators to address these challenges. First, multifaceted health factors are extracted based on charge cycle data, including battery charging time, incremental capacity, and dV/dt curve. Subsequently, a support vector regression model optimized by the sparrow search algorithm is proposed to predict SOH. The results show that MAE, RMSE, and MAPE are less than 0.037%, 0.047%, and 0.04%, respectively. Meanwhile, the Kalman filtering method is used to identify the second-order RC model online, and the relative SOH curves are obtained by defining the SOH through the internal resistance. Finally, by analyzing the effects of capacity and internal resistance changes on SOH, a new strategy for SOH assessment is proposed, which considers various factors and selects an appropriate judgment mechanism according to the characteristics exhibited by the battery at different life stages. The strategy is more conservative and reliable, providing a solid guarantee for the safe operation of mining equipment.
Highlights
Carry out cycle aging experiments of MLIBs under different temperature conditions.
The SSA-optimised SVR method is proposed to predict SOH.
Propose a new strategy for SOH assessment that combines capabilities and model parameters.
Lianlian Liu et al 2024 J. Electrochem. Soc. 171 051502
We demonstrate that the corrosion of AISI 1045 medium carbon steel and pure aluminum can be quantified by the turn-off fluorescent sensor Phen Green-SK (PGSK) in ethanol-based solutions. We first evaluate the dependence of the chelation enhanced quenching of PGSK on iron and aluminum ion concentrations. Subsequently, we apply PGSK to examine the anodic dissolution of metal corrosion. The observed time-dependent PGSK-quenching quantifies the corrosion rates of two metals over 24 h of immersion in ethanol-based solutions. The PGSK-based quantification of corrosion is compared to scanning electron microscopy and electrochemical techniques, including open circuit potential and Tafel extrapolation. The corrosion rates calculated from PGSK-quenching and Tafel extrapolation are in agreement, and both indicate a decrease in corrosion rates over 24 h. Our work shows PGSK can efficiently sense and quantify anodic corrosion reactions at metal interfaces, especially in organic solvents or other non-aqueous environments where the application of electrochemical techniques can be limited by the poor conductivity of the surrounding medium.
Highlights
Fluorescent quenching of Phen Green-SK responds to corrosion in organic solvents.
Corrosion rate is calculated from PGSK-quenching via fluorescence spectroscopy.
Corrosion measured by PGSK agrees with electrochemical Tafel and SEM results.
The corrosion rates of aluminum and carbon steel in ethanol decrease with time.
Interactions between metal, dye, and solution species are affected by solvent.
Shilpa Gupta et al 2024 J. Electrochem. Soc. 171 057503
The growing need for faster and more effective data handling and data transfer capabilities of a network require energy-efficient and more powerful smart sensor devices. These devices have become increasingly necessary in wireless sensor networks (WSN). The architecture or topology of WSN can greatly impact the organizational efficacy and connectivity among the sensor nodes employed within the given area. It is foremost important to implement a robust network topology which must be capable of ensuring continuous and reliable communication within the whole network. This research paper presents an effective approach based on Ant colony scheme to optimize mesh network topology ant colony optimization (ACO) is used to place the sensor nodes optimally in the given area of the whole network. The proposed research carries out comprehensive performance evaluation of the network under various QoS parameters such as bandwidth, throughput, delay, residual energy and routing load. These parameters shows the effectiveness or adaptability of the network with different and dynamically changing communication requirements suggested by this topology scheme. The network based on the proposed method has been simulated several times and the achieved simulation patterns have been analyzed under the mentioned QoS constraints.
Xiaoxiong Feng et al 2024 J. Electrochem. Soc. 171 054506
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.
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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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Liu et al
The microstructural integrity of Ni-based fuel electrodes is important for long-term solid oxide fuel cell (SOFC) operation. Degradation due to microstructural changes such as Ni-agglomeration, coarsening, and densification must be prevented by an appropriate microstructure. Here, the performance of four types of nickel-ceria-based fuel electrodes, which differ concerning layer sequence and manufacturing processes, was evaluated by electrochemical impedance spectroscopy at the nominal operating temperature of 600°C. Electrodes produced through screen-printed GDC exhibited an acceptable polarization resistance (0.260 Ωcm²), whereas electrodes with an additional printed Ni/GDC layer demonstrated inferior performance (0.550 Ωcm²). Electrodes formed through infiltration of GDC into the printed GDC-layer displayed unreproducible performance values ranging from 0.16 to 1.20 Ωcm² despite similar processing. Conversely, electrodes with an extra layer of GDC infiltrated into the Ni-backbone exhibited good performance (0.195 Ωcm²) and stability. Accelerated degradation tests under OCV at increased operating temperatures of 700 and 900°C were performed on the sample based on a GDC infiltrated Ni-backbone that performed best among reproducible samples. The polarization resistance at 600°C recorded at the beginning and the end of life increased by up to 100%. Microstructural analysis of the electrodes at different aging states revealed strong microstructural changes of fine-infiltrated GDC structures and Ni agglomeration at higher operating temperature
Hales et al
Lithium-ion batteries generate heat, degrading faster and becoming unsafe at high temperature. Yet many battery models do not consider the contribution of reversible, entropic heating when evaluating the rate of heat generation from a cell or battery pack. This leads to temperature prediction errors in battery management systems, increased safety risk, and reduced lifetime of the battery pack. Here, a standardised potentiometric method is proposed, allowing anyone with access to a typical battery lab to reliably and accurately extract the entropy coefficient for any electrochemical cell, the key parameter for the inclusion of reversible heating in a battery model. The proposed method takes 7.4 days to complete, representing a reduction of 90% compared to some methods proposed in the literature. Results highlight the importance of moving away from the multiple temperature steps, and the temperature step increases that dominate the existing literature. These arguments are justified through the observation and introduction of voltage relaxation following both kinetic and thermal excitation. These phenomena are termed post-kinetic-potentialisation and post-thermalisation-potentialisation. Post-thermalisation-potentialisation is not discussed in any published literature yet represents an important behavioural trait for any lithium-ion cell with a non-negligible length scale and thermal diffusivity.
Wu et al
Silicon-dominant anode is of great interest because of its potential to boost the cell-level energy of state-of-the-art Li-ion batteries. While silicon materials are extensively studied, the electrode level understanding, especially the coating process of Si particles, are not much investigated which plays an equally important role in unlocking the full potential of silicon anodes. Herein, the electrode processing of Si-dominated anode (52.8 wt.%, 3.5-4.5 mAh/cm2) is being investigated to understand the relationship of processing-morphology-properties of Si anode at electrode level. It has been found that almost-undetectable Si agglomerates easily form during electrode processing, which grow into big protrusions after lithiation and trigger potential internal shorting and self-discharge problems. A facile slurry filtration step is proposed to homogenize the particle distribution within Si-dominant electrode which improves the electrochemical performances and storage stability of Si-based Li ion batteries.
Wakamatsu et al
Power generation with renewable energy using solid oxide cells (SOCs) has been widely researched. To solve the existing problems of SOCs, such as degradation and efficiency improvement, it is essential to understand reaction mechanisms on the surface/interface such as triple phase boundary (TPB) composed of catalysts, electrolytes, and gas phases. However, a reliable TPB model has not been uniquely defined to discuss the property. This study focused on the TPB model comprising Ni catalysts, yttria-stabilized zirconia (YSZ) electrolytes, and gas phases, and aimed to theoretically identify a reliable TPB model by using density functional theory calculations. The stable structure of YSZ surface models was first identified considering various oxygen vacancy positions, yttrium atom arrangements, yttria concentration, and YSZ surfaces. Thereafter, a reliable Ni/YSZ interface model was discussed by evaluating various Ni structure types, Ni interfaces in contact with the YSZ surface, and interface positions. As a result, we have proposed a more reliable YSZ surface structure than previous reports and reasonable Ni/YSZ interface models considering the computational cost to discuss the properties of TPB. These findings will contribute to the improved design of SOCs as high-performance energy conversion systems for sustainable energy storage.
Sharma et al
Implications of rate coefficients, concentration ratio, and electron-transfer number of the redox species present in the anolyte and catholyte on the performance characteristics of a redox flow battery (RFB) were investigated. Toward this, a polyoxometalate (POM)-V4+/V5+ RFB (with order 104 of magnitude difference in their rate coefficients) was assembled by replacing the anolyte (V2+/V3+) of a well-established vanadium RFB (VRFB); the redox potential of POM is comparable to that of V2+/V3+. The performance of the POM-V4+/V5+ RFB improves by ~100 mV at reasonable operating current densities (~ 200 mA cm-2) as compared to that of a VRFB, in a 5 cm2 cell, even though the solubility of tungstosilicic acid (TSA) is 300 mM as compared to 1.8 M VOSO4. Only four electrons can be reversibly extracted from the POM, although extraction of 14 electrons (theoretical) is possible from TSA, limiting the charging voltage to 1.4 V. Overcharging leads to capacity loss and concentration ratio (Catholyte: Anolyte) impacts the overall performance of RFB. Significant vanadium crossover loss is also observed at the anode side.
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Lianlian Liu et al 2024 J. Electrochem. Soc. 171 051502
We demonstrate that the corrosion of AISI 1045 medium carbon steel and pure aluminum can be quantified by the turn-off fluorescent sensor Phen Green-SK (PGSK) in ethanol-based solutions. We first evaluate the dependence of the chelation enhanced quenching of PGSK on iron and aluminum ion concentrations. Subsequently, we apply PGSK to examine the anodic dissolution of metal corrosion. The observed time-dependent PGSK-quenching quantifies the corrosion rates of two metals over 24 h of immersion in ethanol-based solutions. The PGSK-based quantification of corrosion is compared to scanning electron microscopy and electrochemical techniques, including open circuit potential and Tafel extrapolation. The corrosion rates calculated from PGSK-quenching and Tafel extrapolation are in agreement, and both indicate a decrease in corrosion rates over 24 h. Our work shows PGSK can efficiently sense and quantify anodic corrosion reactions at metal interfaces, especially in organic solvents or other non-aqueous environments where the application of electrochemical techniques can be limited by the poor conductivity of the surrounding medium.
Highlights
Fluorescent quenching of Phen Green-SK responds to corrosion in organic solvents.
Corrosion rate is calculated from PGSK-quenching via fluorescence spectroscopy.
Corrosion measured by PGSK agrees with electrochemical Tafel and SEM results.
The corrosion rates of aluminum and carbon steel in ethanol decrease with time.
Interactions between metal, dye, and solution species are affected by solvent.
Yanting Liu et al 2024 J. Electrochem. Soc.
The microstructural integrity of Ni-based fuel electrodes is important for long-term solid oxide fuel cell (SOFC) operation. Degradation due to microstructural changes such as Ni-agglomeration, coarsening, and densification must be prevented by an appropriate microstructure. Here, the performance of four types of nickel-ceria-based fuel electrodes, which differ concerning layer sequence and manufacturing processes, was evaluated by electrochemical impedance spectroscopy at the nominal operating temperature of 600°C. Electrodes produced through screen-printed GDC exhibited an acceptable polarization resistance (0.260 Ωcm²), whereas electrodes with an additional printed Ni/GDC layer demonstrated inferior performance (0.550 Ωcm²). Electrodes formed through infiltration of GDC into the printed GDC-layer displayed unreproducible performance values ranging from 0.16 to 1.20 Ωcm² despite similar processing. Conversely, electrodes with an extra layer of GDC infiltrated into the Ni-backbone exhibited good performance (0.195 Ωcm²) and stability. Accelerated degradation tests under OCV at increased operating temperatures of 700 and 900°C were performed on the sample based on a GDC infiltrated Ni-backbone that performed best among reproducible samples. The polarization resistance at 600°C recorded at the beginning and the end of life increased by up to 100%. Microstructural analysis of the electrodes at different aging states revealed strong microstructural changes of fine-infiltrated GDC structures and Ni agglomeration at higher operating temperature
Alastair Hales and James Bulman 2024 J. Electrochem. Soc.
Lithium-ion batteries generate heat, degrading faster and becoming unsafe at high temperature. Yet many battery models do not consider the contribution of reversible, entropic heating when evaluating the rate of heat generation from a cell or battery pack. This leads to temperature prediction errors in battery management systems, increased safety risk, and reduced lifetime of the battery pack. Here, a standardised potentiometric method is proposed, allowing anyone with access to a typical battery lab to reliably and accurately extract the entropy coefficient for any electrochemical cell, the key parameter for the inclusion of reversible heating in a battery model. The proposed method takes 7.4 days to complete, representing a reduction of 90% compared to some methods proposed in the literature. Results highlight the importance of moving away from the multiple temperature steps, and the temperature step increases that dominate the existing literature. These arguments are justified through the observation and introduction of voltage relaxation following both kinetic and thermal excitation. These phenomena are termed post-kinetic-potentialisation and post-thermalisation-potentialisation. Post-thermalisation-potentialisation is not discussed in any published literature yet represents an important behavioural trait for any lithium-ion cell with a non-negligible length scale and thermal diffusivity.
Bingbin Wu et al 2024 J. Electrochem. Soc.
Silicon-dominant anode is of great interest because of its potential to boost the cell-level energy of state-of-the-art Li-ion batteries. While silicon materials are extensively studied, the electrode level understanding, especially the coating process of Si particles, are not much investigated which plays an equally important role in unlocking the full potential of silicon anodes. Herein, the electrode processing of Si-dominated anode (52.8 wt.%, 3.5-4.5 mAh/cm2) is being investigated to understand the relationship of processing-morphology-properties of Si anode at electrode level. It has been found that almost-undetectable Si agglomerates easily form during electrode processing, which grow into big protrusions after lithiation and trigger potential internal shorting and self-discharge problems. A facile slurry filtration step is proposed to homogenize the particle distribution within Si-dominant electrode which improves the electrochemical performances and storage stability of Si-based Li ion batteries.
Timothy C. Hudak et al 2024 J. Electrochem. Soc. 171 053502
Redox-Electrodialysis (r-ED) is an electrochemical desalination cell architecture that has recently received considerable interest, due to its low energy demand relative to electrochemical desalination technologies that rely on electrode-based ion removal. To further improve the energy efficiency of r-ED, we developed a lumped mathematical model with no adjustable parameters to investigate the various sources of overpotential within the cell. Existing models of electrodialysis and r-ED cells either do not accurately incorporate all phenomena contributing to the overpotential or utilize empirical fitting parameters. The model developed here indicates that ohmic overpotentials, especially in the diluate chamber, are the most significant contributors to energy losses. Based on this insight, we hypothesized that adding an ion exchange resin wafer in the diluate compartment would increase the ionic conductivity and decrease the energy demand. Experimental results showed an 18% reduction in specific energy use while achieving the same degree of salt removal (20 mM to 12 mM). Furthermore, the resin wafer enabled complete desalination to potable drinking levels at a current density previously unachievable within practical operating voltage limits (4.93 mA cm−2). We also expanded the model to explore differences in r-ED energy use between configurations using multiple cells and a single cell with increased area.
Meng Yue et al 2024 J. Electrochem. Soc. 171 050515
N-methyl-2-pyrrolidone (NMP) is the most common solvent used in coating positive electrode materials on aluminum foil during the manufacturing of lithium-ion batteries. NMP is a strongly polar aprotic solvent that effectively dissolves the polyvinylidene difluoride binder. While the majority of NMP typically evaporates during the electrode baking process, trace amounts may persist, particularly in positive electrodes containing nano-sized and highly-porous active materials. We noted residual NMP in the positive electrodes of Li-ion pouch cells containing LiMn0.8Fe0.2PO4 due to the extremely high surface area of the material and we wanted to determine the impact of this residual NMP. Therefore, a control electrolyte was purposely spiked with varying amounts of NMP and used in NMC532/graphite pouch cells to investigate the impact of residual NMP on lithium-ion battery performance. Experimental results indicate that NMP has the potential not only to neutralize the electrolyte additive ethylene sulfate but also to independently increase cathode impedance, leading to a higher rate of capacity loss during charge-discharge cycling. It is crucial to establish the appropriate procedure for baking electrodes containing NMP, both in laboratory and industrial settings, to mitigate these effects.
Huayang Zhu et al 2024 J. Electrochem. Soc. 171 050512
This paper implements a highly efficient algorithm to extract electrochemical impedance spectra (EIS) from physics-based battery models (e.g., a P2D model). The mathematical approach is different from how EIS is practiced experimentally. Experimentally, the voltage (current) is harmonically perturbed over a wide range of frequencies and the amplitude and phase shift of the corresponding current (voltage) is measured. The experimental approach can be implemented in simulation software, but is computationally expensive. The approach here is to determine locally linear state-space models from the full physical model. The four Jacobian matrices that are the basis of the state-space models can be derived by numerical differentiation of the physical model. The EIS is then extracted from the state-space model using computationally efficient matrix-manipulation techniques. The algorithm can evaluate the full EIS at an instant in time during a transient, independent of whether the battery is in a stationary state. The approach is also able to separate the full-cell impedance to evaluate partial EIS, such as for a battery anode alone. Although such partial EIS is difficult to measure experimentally, the partial EIS provides valuable insights in interpreting the full-cell EIS.
Isaac Squires et al 2024 J. Electrochem. Soc.
Modelling lithium-ion battery behaviour is essential for performance prediction and design improvement. However, this task is challenging due to processes spanning many length scales, leading to computationally expensive models. Reduced order models have been developed to address this, assuming a "separation of scales" between micro- and macroscales. This study compares two approaches: direct microstructure-resolved 3D domain electrochemical modelling and a simplified 1D homogenized model, similar to the Doyle-Fuller-Newman model. 

The research investigates the validity of the scale separation assumption in continuum electrode-level models by varying scale separation factors, boundary conditions, and geometries. The findings reveal that in 3D models, more tortuous, less porous microstructures deviate more from 1D predictions, especially under higher discharge rates. However, under realistic conditions, with an electrode featuring eight particles across its thickness and typical transport properties, the 3D model predicts only a slight (2%) increase in current compared to the 1D model at a high rate of 7C (approximately 350 A/m²).

These results suggest that the separation of scales assumption in the DFN model is generally suitable for a wide range of operating conditions. However, 1D models may overlook local variations in electrolyte concentration and potential, crucial for understanding degradation mechanisms.
Matthias Riegraf et al 2024 J. Electrochem. Soc. 171 054504
The currently ongoing scale-up of high-temperature solid oxide electrolysis (SOEL) requires an understanding of the underlying dominant degradation mechanisms to enable continuous progress in increasing stack durability. In the present study, the degradation behavior of SOEL stacks of the type “MK35x” with chromium-iron-yttrium (CFY) interconnects and electrolyte-supported cells (ESC) developed at Fraunhofer IKTS was investigated. For this purpose, the initial electrochemical performance of a 10-cell stack was characterized in various operating conditions in both fuel cell and electrolysis mode. Degradation was evaluated during galvanostatic steady-state steam electrolysis operation for more than 3000 h at an oxygen side outlet temperature of 816 °C and a current density of −0.6 A cm−2 and showed an average voltage evolution rate of −0.3%/kh demonstrating high stability. Initial and final characterization at the part load operating point at −0.39 A cm−2 and 800 °C led to the determination of a positive overall degradation rate of 0.4%/kh showing a considerable impact of the operating conditions on the degradation rate. By means of electrochemical impedance spectroscopy analysis it was shown that the stack’s ohmic resistance increased whereas the polarization resistance decreased most likely due to an enhancement in LSMM’/ScSZ oxygen electrode performance.
Neeha Gogoi et al 2024 J. Electrochem. Soc. 171 050506
Vinylene carbonate (VC) is the most commonly applied performance-enhancing electrolyte additives in Li-ion batteries to date. Despite numerous studies, there is a lack of consensus regarding the various reaction pathways of VC and their implications. VC has primarily been observed to either polymerize forming poly(vinylene carbonate) (poly(VC)) or decompose releasing major amounts of CO2, two seemingly contradictory processes. Herein, we present evidence of additional reaction pathways of VC highlighting its role as a H2O scavenging agent. In contrast to the typical electrolyte solvent ethylene carbonate, VC reacts much more rapidly with water impurities, especially when in contact with hydroxides, forming products less likely to influence cell performance. Efficient removal of water and hydroxides is essential to preserve the stability of Li-ion electrolyte solvent and salt, hence guaranteeing a long lifetime of the battery. Model studies pinpointing reaction pathways of electrolytes and additives, as presented herein, are critical not only to improve modern Li-ion cells but also to establish design principles for future battery chemistries.