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.
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.
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.
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.
Loraine Torres-Castro et al 2024 J. Electrochem. Soc. 171 020520
The rate of electric vehicle (EV) adoption, powered by the Li-ion battery, has grown exponentially; largely driven by technological advancements, consumer demand, and global initiatives to reduce carbon emissions. As a result, it is imperative to understand the state of stability (SoS) of the cells inside an EV battery pack. That understanding will enable the warning of or prevention against catastrophic failures that can lead to serious injury or even, loss of life. The present work explores rapid electrochemical impedance spectroscopy (EIS) coupled with gas sensing technology as diagnostics to monitor cells and packs for failure markers. These failure markers can then be used for onboard assessment of SoS. Experimental results explore key changes in single cells and packs undergoing thermal or electrical abuse. Rapid EIS showed longer warning times, followed by VOC sensors, and then H2 sensors. While rapid EIS gives the longest warning time, with the failure marker often appearing before the cell vents, the reliability of identifying impedance changes in single cells within a pack decreases as the pack complexity increases. This provides empirical evidence to support the significant role that cell packaging and battery engineering intricacies play in monitoring the SoS.
Chang-Hui Chen et al 2020 J. Electrochem. Soc. 167 080534
Presented here, is an extensive 35 parameter experimental data set of a cylindrical 21700 commercial cell (LGM50), for an electrochemical pseudo-two-dimensional (P2D) model. The experimental methodologies for tear-down and subsequent chemical, physical, electrochemical kinetics and thermodynamic analysis, and their accuracy and validity are discussed. Chemical analysis of the LGM50 cell shows that it is comprised of a NMC 811 positive electrode and bi-component Graphite-SiOx negative electrode. The thermodynamic open circuit voltages (OCV) and lithium stoichiometry in the electrode are obtained using galvanostatic intermittent titration technique (GITT) in half cell and three-electrode full cell configurations. The activation energy and exchange current coefficient through electrochemical impedance spectroscopy (EIS) measurements. Apparent diffusion coefficients are estimated using the Sand equation on the voltage transient during the current pulse; an expansion factor was applied to the bi-component negative electrode data to reflect the average change in effective surface area during lithiation. The 35 parameters are applied within a P2D model to show the fit to experimental validation LGM50 cell discharge and relaxation voltage profiles at room temperature. The accuracy and validity of the processes and the techniques in the determination of these parameters are discussed, including opportunities for further modelling and data analysis improvements.
Yuriy V. Tolmachev 2023 J. Electrochem. Soc. 170 030505
We present a quantitative bibliometric study of flow battery technology from the first zinc-bromine cells in the 1870's to megawatt vanadium RFB installations in the 2020's. We emphasize, that the cost advantage of RFBs in multi-hour charge-discharge cycles is compromised by an inferior energy efficiency of these systems, and that there are limits on the efficiency improvement due to internal cross-over and the cost of power (at low current densities) and due to an acceptable pressure drop (at high current densities). Differences between lithium-ion and vanadium redox flow batteries (VRFBs) are discussed from the end-user perspective. We conclude, that the area-specific resistance, cross-over current and durability of contemporaneous VRFBs are appropriate for commercialization in multi-hour stationary energy storage markets, and the most import direction in the VRFB development today is the reduction of stack materials and manufacturing costs. Chromium-iron RFBs should be given a renewed attention, since it seems to be the most promising durable low-energy-cost chemistry.
Peter M. Attia et al 2022 J. Electrochem. Soc. 169 060517
Lithium-ion batteries can last many years but sometimes exhibit rapid, nonlinear degradation that severely limits battery lifetime. In this work, we review prior work on "knees" in lithium-ion battery aging trajectories. We first review definitions for knees and three classes of "internal state trajectories" (termed snowball, hidden, and threshold trajectories) that can cause a knee. We then discuss six knee "pathways", including lithium plating, electrode saturation, resistance growth, electrolyte and additive depletion, percolation-limited connectivity, and mechanical deformation—some of which have internal state trajectories with signals that are electrochemically undetectable. We also identify key design and usage sensitivities for knees. Finally, we discuss challenges and opportunities for knee modeling and prediction. Our findings illustrate the complexity and subtlety of lithium-ion battery degradation and can aid both academic and industrial efforts to improve battery lifetime.
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Enli Wang et al 2024 J. Electrochem. Soc. 171 040544
Optimizing interfacial contact between electrolyte and electrode is one of key factors to achieve stable all solid-state lithium batteries (ASSLBs). In this work, UV curving technique is reported to produce ASSLBs by in situ constructing integrated interface between PESF-LLZTO composite solid electrolytes (CSEs) and LiFePO4 (LFP) cathode. Benefiting from the integral structure and ultrastable properties of the as-prepared CSE/LFP interface, the obtained ASSLBs delivers an initial discharge specific capacities of 162.8 mAh g−1 at 0.1 C and 30 °C, and successfully runs over 520 cycles at 0.5 C with a discharge capacity retention ratio of 96.3%.
Zhuoxiang Li et al 2024 J. Electrochem. Soc. 171 040543
To accurately predict the State of Health (SOH) of lithium-ion batteries under the continuously changing charging and discharging conditions in practical applications, this study proposes a hybrid modeling approach that integrates a Fractional Order Equivalent Circuit Model (F-ECM) with the AutoGluon automatic machine learning framework. By leveraging Electrochemical Impedance Spectroscopy (EIS) to capture battery frequency response characteristics, F-ECM accurately fits EIS data to extract detailed internal state parameters. The integration of AutoGluon automates the machine learning process, enhancing the precision of SOH predictions. Through testing and analysis on real battery datasets, this method has demonstrated superior prediction precision and computational efficiency compared to existing mainstream modeling approaches. Specifically, the hybrid method achieved a Root Mean Square Error (RMSE) of 2.12% and a Mean Absolute Error (MAE) of 1.67%. This study presents a highly accurate, interpretable, and adaptable predictive framework for lithium-ion battery health assessment, offering valuable insights for battery health management system development.
Highlights
F-ECM integrated with AutoML for enhanced Li-ion battery health estimation.
F-ECM was used to extract feature parameters from impedance spectroscopy.
Data-driven model was built using AutoML framework AutoGluon.
Hybrid approach balanced predictive accuracy with computational feasibility.
Xiaoxiao Zhang et al 2024 J. Electrochem. Soc. 171 040542
This study explores the improvement of sodium-ion batteries by presodiating hard carbon anodes, with the goal of reducing initial capacity loss and enhancing the overall electrochemical performance of full cells. Using Na-biphenyl for presodiation and exploring its effects under various conditions—such as electrolyte composition and electrode loading—alongside two different cathode configurations (Na-stoichiometry Na3V2(PO4)3 and Na-deficient Na0.44MnO2), we seek to elevate the overall electrochemical performance of sodium-ion batteries. Our findings reveal the significance of finely tuning presodiation conditions leading to significant improvements in both initial Coulombic Efficiency and the cycling stability of full cells. Furthermore, a comparative analysis of the solid electrolyte interface formed through both chemical and electrochemical presodiation methods reveals significant similarities in impedance characteristics. This research provides valuable insights into the impact of presodiation on hard carbon anodes, offering a pathway to enhance the practical application of presodiation technology for sodium-ion batteries.
Saloua Merazga et al 2024 J. Electrochem. Soc. 171 040541
The thermal annealing effect on the morphological, structural and electrochemical properties of hydrothermal synthesized Li4Ti5O12 / TiO2 has been studied. Lithium titanate (Li4Ti5O12) nanopowders are successfully synthesized by hydrothermal method using titanuim tetrabutyl and lithium hydroxide followed by thermal annealing process at different temperatures: 500 °C, 800 °C and 900 °C. The X-ray diffraction (XRD) patterns indicates the appearance of the Li4Ti5O12 phase at a temperature above 800 °C formed after the reaction of the two phases: TiO2 and Li2TiO3 which appear at 500 °C. Though, the prepared electrode by the powder annealed at 800 °C shows an initial capacity of about 173.1 mAh g−1 (0.1 C), which retained at 75.6 mAh g−1 after 100 cycles.
Highlights
Li4Ti5O12/TiO2 nanopowders are successfully Synthesized by low temperature hydrothermal method.
Studying the effect of Thermal annealing on the morphological, structural and electrochemical properties of hydrothermal synthesized Li4Ti5O12/ TiO2.
X-ray diffraction patterns confirmed that high-purity Li4Ti5O12 can be successfully obtained after thermal annealing ≤ 800 °C.
Annealed powder at 800 °C shows high initial discharge capacity of 173.1 mAh g−1 at 0.1 C, which retained at 75.6 mA h g−1 after 100 cycles.
Md Wahidul Hasan et al 2024 J. Electrochem. Soc. 171 040540
Lithium-sulfur (Li-S) batteries are identified as one of the most promising next-generation battery technologies owing to their high theoretical specific energy, sustainability, and affordability. However, the commercialization of Li-S batteries has been hindered by severe technical challenges, including the lithium polysulfide (PS) dissolution/shuttling effect, a major cause of fast capacity degradation over cycling. We demonstrated that, for the first time, nanolayer polymer coated high surface area porous carbons (NPCs) were coated directly on sulfur electrodes (NPC-S), which led to a high specific capacity of ∼1,600 mAh g−1 approaching the theoretical specific capacity limit in the NPC-S based Li-S batteries. The NPC-S based Li-S batteries maintained their large initial specific capacity gain compared with the Baseline-S based Li-S batteries (control) over extended cycles. A follow-on study indicated that the NPC-S approach is a necessary and critical step to boost the near-theoretical specific capacity while being stabilized over long cycles with a synergistic strategy. Our experimental and computational results suggest that NPC coated on sulfur electrodes provides not only an effective and strong PS-trapping power but also an increased redox reaction kinetics for sulfur ↔ PS's conversions during battery charge and discharge, rendering the realization of near-theoretical discharge specific capacity in the NPC-S based Li-S batteries. The findings presented in this study may inspire a new, simple, low-cost, and commercially scalable approach, without adding any appreciable dead weight or volume to the batteries, in the effort to tackle the technical challenges facing SOA Li-S batteries.
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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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Gogoi et al
Vinylene carbonate (VC) is the most commonly applied performance-enhancing electrolyte additive 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.
Hangarter et al
Electrodeposition and microstructure of thin films close to Pt75Ni25 and Pt25Ni75 stoichiometry are described and their catalytic oxygen reduction reaction performance, dealloying, and strain evolution detailed. Multiple techniques are used to characterize the morphology, crystalline structure, and chemical homogeneity of as-deposited and dealloyed films. A fine-scale percolating network of lower-density regions is evident in the as-deposited Pt74Ni26 films while the as-deposited Pt26Ni74 films are more homogenous and compact. Electrodeposition is accompanied by development of significant in-plane tensile stress that increases at more negative applied growth potentials to reach 1.28 GPa for as-deposited Pt26Ni74. Dealloying of the near-surface regions of Pt74Ni26 is accompanied by limited expansion or opening of the low-density regions while massive dealloying of the highly stressed Pt26Ni74 results in shrinkage, extensive cracking, and formation of a bi-continuous nanoporous structure with an average pore diameter close to 5 nm. Relative to electrodeposited Pt, the alloy films exhibit enhanced area-specific oxygen reduction reaction activity (at 0.95 V vs. RHE, iR-corrected) that amounts to a factor of 3.4 for dealloyed Pt74Ni26 and 5.1 for dealloyed Pt26Ni74 while the Pt-based mass activity increased by a factor of 5.1 and 12.3, for the respective films.
Matsui et al
Thermo-electrochemical conversion systems can convert abundant low-grade heat into electricity. In particular, thermally-regenerative flow batteries (TRFBs) have gained significant attention owing to their high power density compared to other thermo-electrochemical conversion systems. However, the variety of redox species is limited in previous studies. To provide an alternative option for the redox species, we newly propose using Fe, and investigate the performance of an Fe-based TRFB called the solvation difference flow battery (SDFB). In this study, the SDFB uses [Fe(CN)6]4-/3- as the redox species and can be recharged by the distillation of acetone. The maximum power density was 40 W m-2 and the thermal efficiency was estimated to be 0.20% at an average power density of 16 W m-2. In addition, we discuss the challenges for future improvements. The cell voltage should be enhanced by optimizing the electrolyte components, such as solvents and counterions. For the cell design, the cell resistance is reduced by improving the flow fields of the electrolytes to enhance the mass-transfer properties. Moreover, a membrane that satisfies both a high ion conductivity and low crossover rate of the solvents is required. This study provides new options for the redox species in TRFBs.
Gadow et al
Ferrite nanoparticles are interesting materials given their unique physical and chemical properties and wide applications. A novel electrochemical sensor based on a series of chromium-nano-ferrites {Fe3+[Fe2+Fe3+(1-x)Cr3+x]O4; x (0.0 – 1.0} was fabricated for determination of Asenapine maleate (ASE.M). X-ray diffraction revealed the formation of crystallite nano-particles of lattice constant of (8.299-8.345 Å) with a single phase of cubic inverse spinel structures. Particle size and specific surface area were (9.10-27.60 nm) and (60-175 m2g-1) using tunneling electron microscopy and Brunnauer-Emmett-Teller (BET) analysis, respectively. Among this CrxFe(3-x)O4 series, (CrFe2O4; x=1) was appeared to get the smallest particles size and highest BET surface area. The charge transfer resistance (RCT) of (2220, 1680, 765, and 490 Ω) were achieved for CrxFe(3-x)O4 NPs/CPE (x = 0.0, 0.4, 0.8, and 1.0), respectively. CrFe2O4 performance was then improved via incorporation of 2D-graphene atomic crystals in a new ferrite-graphene nanocomposite of [0.25%(w/w) CrFe2O4 NPs : 7%(w/w) graphene nanosheets]. The feasibility of this sensor is achieved for determination of ASE.M in brand Saphris® and local Asenapine pharmaceutical products. In addition, a wide linear concentration range of (6.5×10-9 - 1.0×10-6 M) with LOD value of 8.88×10−10 M were achieved in human plasma.
Wu et al
We employed density functional theory to investigate Co-N4/Gra single-atom catalysts, focusing on the modification of axial ligand (X=-F, -CN and -C3H4N2) and examined the influence of ligand field and electric potential on eNORR. Our results demonstrate that Co-N4[X]/Gra exhibit favorable thermodynamic adsorption (ΔG*NO < 0) and remarkable activation activity toward NO molecules. Co-N4/Gra demonstrates a limiting potential of -0.13 V with the potential-determining step (PDS) of *NH3 → * + NH3(g). Notably, under the introduction of ligands, Co-N4[F]/Gra achieves the most favorable overpotential of -0.07 V, superior to most of NORR electrocatalysts, and meanwhile shows an exceptional selectivity of 99.99% for eNORR compared to competitive hydrogen evolution reaction. Under the solvent environment, Co-N4/Gra features the triggering potentials of -0.33V for a pH of 1, -0.71V for a pH of 7, and -1.10V vs RHE for a pH of 13, respectively. Additionally, the potential reduces the desorption energy and adsorption energy of NH3, facilitating the accessibility of the NH3 desorption step (PDS) and promoting NO reduction. Thus, under realistic conditions, the Co ion's active site displays variable valence electrons and forms a dynamic interplay with the ligand field effect, rendering a crucial effect on the adsorption of reaction species during the eNORR
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Caitlin Trejo et al 2024 J. Electrochem. Soc. 171 040539
Aluminum foil anodes have the potential to significantly improve the energy density, safety, cost, and sustainability of Li-ion batteries (LIB). However, their adoption is limited by their notoriously poor cycle life, and the dramatic structural transformations of Al foil anodes during formation and cycling remain poorly understood. In this work, we investigate how the nucleation and growth kinetics of LiAl control the microstructural evolution and cycle life of Al foil anodes. First, we demonstrate the unique sensitivity of Al foil anodes to the cell design and cycling conditions and emphasize the necessity of electrochemical testing in practical full cells. Operando electrochemical impedance spectroscopy (EIS) is combined with scanning electron microscope (SEM) imaging of the lithiated foils to elucidate the relationships between LiAl nucleation kinetics and the resulting LiAl microstructure. Particularly, we investigate the effects of annealing the pristine foils, and controlling the overpotential and temperature during formation, showing that as-rolled foils lithiated at high overpotentials give a columnar LiAl microstructure. Finally, we show that uncontrolled LiAl nucleation during cycling quickly destroys this favorable columnar structure, and a significant improvement in cycle life of LiFePO4 || Al full cells is achieved by limiting the depth-of-discharge to <75%.
Neeha Gogoi et al 2024 J. Electrochem. Soc.
Vinylene carbonate (VC) is the most commonly applied performance-enhancing electrolyte additive 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.
Masaki Deguchi et al 2024 J. Electrochem. Soc. 171 040536
The electrolyte in current automotive lithium-ion batteries is a mixture of ethylene carbonate (EC), which has a high dielectric constant, and ethyl methyl carbonate or dimethyl carbonate, which have a low viscosity. However, the flash point of these mixed solvents is as low as 25 °C, so safety precautions must be taken. On the other hand, if only EC or propylene carbonate with a high flash point is used, the flash point will be 120 °C or higher. However, the high dielectric constant solvent cannot wet the hydrophobic separator whose material is polyethylene and/or polypropylene. Therefore, there is a problem that the battery does not work. In 1999, we proposed a "functional electrolyte" in which a small amount of an additive with a new function is added to the electrolyte, and many additives have since been commercialized. In recent work, we focused on a low viscosity linear carboxylic acid esters, designed an electrolyte with a flash point above 120 °C that provides wettability to the separator even in an electrolyte with a high dielectric constant solvent.
Ziwei Ye et al 2024 J. Electrochem. Soc. 171 040522
This study examines the influence of electrolyte salts and solvents on the performance of O3 layered oxide NaMn0.39Fe0.31Ni0.22Zn0.08O2/hard carbon sodium-ion pouch cells with polyethylene terephthalate (PET) jellyroll tape. A significant enhancement in cell performance between 2.0 and 3.8 V was observed across various temperatures (20, 40, and 55 °C) by substituting NaPF6 with NaFSI, including reduced impedance growth, minimized gas generation, and supressed jellyroll tape decomposition. Ultra-high precision coulometry revealed that the use of NaPF6 resulted in increased unwanted parasitic reactions associated with tape decomposition, e.g., capacity fade and charge endpoint capacity slippage. Teardown of sodium-ion pouch cells after cycling in DMC-based electrolytes revealed a severe decomposition of the PET tape with NaPF6 but not with NaFSI. Gas chromatography shows significantly more electrolyte decomposition products with NaPF6 as opposed to NaFSI. DEC-based electrolyte showed less capacity fade, less electrolyte decomposition products, and less tape decomposition after cycling than DMC-based electrolyte. The electrolyte additive DTD can prevent parasitic reactions in DMC- and NaPF6-based electrolyte. Overall, the choice of salts and linear carbonates in alkyl carbonate electrolytes plays a crucial role in determining the overall cycling performance of the layered oxide/hard carbon sodium-ion cells with PET jellyroll tape.
Frendi Maulana et al 2024 J. Electrochem. Soc. 171 046505
This work investigates the potential of N, Ni, and N-Ni-doped ZnO as photocatalysts for hydrogen production through water splitting. Sonochemical techniques were used to synthesize these materials. In contrast to undoped or singly-doped ZnO, N-Ni-double-doped ZnO demonstrated a significantly narrower band gap (2.89 eV) and smaller crystallites (21.60 nm). This led to a remarkable doubling in the hydrogen production rate under UV-visible light irradiation. The combined effect of N and Ni doping effectively promotes efficient charge separation and enhanced light absorption, resulting in significantly increased photocatalytic activity. Furthermore, N-Ni-ZnO demonstrates exceptional stability, retaining over 95% of its initial activity after five cycles. This work paves the way for the development of cost-effective and scalable photocatalysts for sustainable solar hydrogen production.
Maria Escamilla et al 2024 J. Electrochem. Soc. 171 040533
In this paper, we describe the synthesis and characterization of alkoxylated TEMPO, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, radicals with potential application in organic non-aqueous redox flow batteries. The behavior of a series of TEMPO derivatives with varying lengths of alkoxy chain is analyzed in acetonitrile solutions using electrochemical techniques, electron paramagnetic resonance (EPR) spectroscopy, and measurements of permeability through three different membranes. Electrochemical redox potentials are only weakly dependent on the substituent, but, in contrast, exchange current densities derived from the data do depend on the substitution. EPR lends further insight into these properties via the determination of hyperfine splitting constant and rotational correlation time. There is a negligible effect of the substituents on those parameters among the modified TEMPO radicals. Finally, permeation rates of modified TEMPO derivatives through membranes depend significantly on both the membrane and the substitution of TEMPO, providing insights into capacity fade measurements in the literature.
Ido Ben-Barak and M. N. Obrovac 2024 J. Electrochem. Soc. 171 040535
Oxides in the NixMn0.5-x/2Co0.5-x/2-O system were investigated as precursors in the all-dry synthesis of NMC622 (LiNi0.6Mn0.2Co0.2O2). Single-phase spinel precursors in this system were found to have the highest compositional homogeneity. To synthesize NMC, NixMn0.5-x/2Co0.5-x/2-O precursors were heated with Li2CO3 and NiO (to attain the correct NMC stoichiometry) in air or oxygen. This represents a different strategy in NMC synthesis compared to conventional hydroxide precursors that have the same composition as the final NMC. The most homogeneous and best performing NMC (171.9 mAh g−1 with 90% after 183 cycles) were obtained by using precursors that were essentially single-phase cubic spinel (0.070 ≤ x ≤ 0.091 in NixMn0.5-x/2Co0.5-x/2-O) even though such precursors had compositions that had significantly less Ni content than the target NMC622 composition. These findings demonstrate an alternate route for obtaining compositional homogeneity in NMC all-dry synthesis.
Martins Sarma et al 2024 J. Electrochem. Soc. 171 040531
This paper presents the cycling of a novel low-cost Na-Zn liquid metal battery. Its 600 °C operating temperature presents multiple challenges that must be overcome to achieve commercial viability, both from a structural and electrochemical perspective. To enable long-term cycling of the Na-Zn battery in a realistic environment, we have developed a reusable, hermetically sealed, high temperature and sufficiently corrosion resistant cell concept. The design as well as various approaches for assembling and filling the cell are presented. The factors considered when selecting specific components are documented and explained. The active volume of the cell design can be up to 40 ml, corresponding to a nominal capacity of 1 A h, while the entire cell body weighs around 800 g and costs approximately €200 ($215). The performance of the cell is demonstrated in terms of longevity (1000 h) and high discharge current density (100 mA cm-2). The manuscript not only presents the first long-term cycling performance of the novel Na-Zn chemistry achieving Coulombic efficiency of up to 80%, but also demonstrates the design's versatility with in situ dynamic neutron radiography of the cell.
Erno Kemppainen et al 2024 J. Electrochem. Soc. 171 044507
Understanding the physical and chemical basis of device operation is important for their development. While hydrogen fuel cells are a widely studied topic, direct ammonia fuel cells (DAFCs) are a smaller field with fewer studies. Although the theoretical voltage of a DAFC is approximately equal to that of a hydrogen fuel cell, the slow kinetics of the ammonia oxidation reaction hamper cell performance. Therefore, development of anode catalysts is especially needed for practical viability of the DAFCs. To study DAFC operation, specifically interactions between reaction kinetics and different transport phenomena, we developed a one-dimensional model of a DAFC and performed a sensitivity analysis for several parameters related to the cell operating conditions (e.g., temperature, relative humidity) and properties (e.g., catalyst loading). As expected, temperature and relative humidity were very important for cell power. However, while faster reaction kinetics improved the cell performance, simply increasing the catalyst loading did not always produce a comparable enhancement. These and other observations about the relative importance of the operating parameters should help to prioritize and guide future development of and research on DAFCs. Further studies are needed to understand and optimize e.g. humidity management in different scenarios.
Matthias Riegraf et al 2024 J. Electrochem. Soc.
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.