Battery research depends upon up-to-date information on the cell characteristics found in current electric vehicles, which is exacerbated by the deployment of novel formats and architectures. This necessitates open access to cell characterization data. Therefore, this study examines the architecture and performance of first-generation Tesla 4680 cells in detail, both by electrical characterization and thermal investigations at cell-level and by disassembling one cell down to the material level including a three-electrode analysis. The cell teardown reveals the complex cell architecture with electrode disks of hexagonal symmetry as well as an electrode winding consisting of a double-sided and homogeneously coated cathode and anode, two separators and no mandrel. A solvent-free anode fabrication and coating process can be derived. Energy-dispersive X-ray spectroscopy as well as differential voltage, incremental capacity and three-electrode analysis confirm a NMC811 cathode and a pure graphite anode without silicon. On cell-level, energy densities of 622.4 Wh/L and 232.5 Wh/kg were determined while characteristic state-of-charge dependencies regarding resistance and impedance behavior are revealed using hybrid pulse power characterization and electrochemical impedance spectroscopy. A comparatively high surface temperature of ∼70 °C is observed when charging at 2C without active cooling. All measurement data of this characterization study are provided as open source.
The Electrochemical Society (ECS) was founded in 1902 to advance the theory and practice at the forefront of electrochemical and solid state science and technology, and allied subjects.
ISSN: 1945-7111
JES is the flagship journal of The Electrochemical Society. Published continuously from 1902 to the present, JES remains one of the most highly-cited journals in electrochemistry and solid-state science and technology.
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Manuel Ank et al 2023 J. Electrochem. Soc. 170 120536
Yuliya Preger et al 2020 J. Electrochem. Soc. 167 120532
Energy storage systems with Li-ion batteries are increasingly deployed to maintain a robust and resilient grid and facilitate the integration of renewable energy resources. However, appropriate selection of cells for different applications is difficult due to limited public data comparing the most commonly used off-the-shelf Li-ion chemistries under the same operating conditions. This article details a multi-year cycling study of commercial LiFePO4 (LFP), LiNixCoyAl1−x−yO2 (NCA), and LiNixMnyCo1−x−yO2 (NMC) cells, varying the discharge rate, depth of discharge (DOD), and environment temperature. The capacity and discharge energy retention, as well as the round-trip efficiency, were compared. Even when operated within manufacturer specifications, the range of cycling conditions had a profound effect on cell degradation, with time to reach 80% capacity varying by thousands of hours and cycle counts among cells of each chemistry. The degradation of cells in this study was compared to that of similar cells in previous studies to identify universal trends and to provide a standard deviation for performance. All cycling files have been made publicly available at batteryarchive.org, a recently developed repository for visualization and comparison of battery data, to facilitate future experimental and modeling efforts.
George E. Blomgren 2017 J. Electrochem. Soc. 164 A5019
This year, the battery industry celebrates the 25th anniversary of the introduction of the lithium ion rechargeable battery by Sony Corporation. The discovery of the system dates back to earlier work by Asahi Kasei in Japan, which used a combination of lower temperature carbons for the negative electrode to prevent solvent degradation and lithium cobalt dioxide modified somewhat from Goodenough's earlier work. The development by Sony was carried out within a few years by bringing together technology in film coating from their magnetic tape division and electrochemical technology from their battery division. The past 25 years has shown rapid growth in the sales and in the benefits of lithium ion in comparison to all the earlier rechargeable battery systems. Recent work on new materials shows that there is a good likelihood that the lithium ion battery will continue to improve in cost, energy, safety and power capability and will be a formidable competitor for some years to come.
Peter Keil et al 2016 J. Electrochem. Soc. 163 A1872
In this study, the calendar aging of lithium-ion batteries is investigated at different temperatures for 16 states of charge (SoCs) from 0 to 100%. Three types of 18650 lithium-ion cells, containing different cathode materials, have been examined. Our study demonstrates that calendar aging does not increase steadily with the SoC. Instead, plateau regions, covering SoC intervals of more than 20%–30% of the cell capacity, are observed wherein the capacity fade is similar. Differential voltage analyses confirm that the capacity fade is mainly caused by a shift in the electrode balancing. Furthermore, our study reveals the high impact of the graphite electrode on calendar aging. Lower anode potentials, which aggravate electrolyte reduction and thus promote solid electrolyte interphase growth, have been identified as the main driver of capacity fade during storage. In the high SoC regime where the graphite anode is lithiated more than 50%, the low anode potential accelerates the loss of cyclable lithium, which in turn distorts the electrode balancing. Aging mechanisms induced by high cell potential, such as electrolyte oxidation or transition-metal dissolution, seem to play only a minor role. To maximize battery life, high storage SoCs corresponding to low anode potential should be avoided.
Jorn M. Reniers et al 2019 J. Electrochem. Soc. 166 A3189
The maximum energy that lithium-ion batteries can store decreases as they are used because of various irreversible degradation mechanisms. Many models of degradation have been proposed in the literature, sometimes with a small experimental data set for validation. However, a comprehensive comparison between different model predictions is lacking, making it difficult to select modelling approaches which can explain the degradation trends actually observed from data. Here, various degradation models from literature are implemented within a single particle model framework and their behavior is compared. It is shown that many different models can be fitted to a small experimental data set. The interactions between different models are simulated, showing how some of the models accelerate degradation in other models, altering the overall degradation trend. The effects of operating conditions on the various degradation models is simulated. This identifies which models are enhanced by which operating conditions and might therefore explain specific degradation trends observed in data. Finally, it is shown how a combination of different models is needed to capture different degradation trends observed in a large experimental data set. Vice versa, only a large data set enables to properly select the models which best explain the observed degradation.
Weilong Ai et al 2020 J. Electrochem. Soc. 167 013512
Whilst extensive research has been conducted on the effects of temperature in lithium-ion batteries, mechanical effects have not received as much attention despite their importance. In this work, the stress response in electrode particles is investigated through a pseudo-2D model with mechanically coupled diffusion physics. This model can predict the voltage, temperature and thickness change for a lithium cobalt oxide-graphite pouch cell agreeing well with experimental results. Simulations show that the stress level is overestimated by up to 50% using the standard pseudo-2D model (without stress enhanced diffusion), and stresses can accelerate the diffusion in solid phases and increase the discharge cell capacity by 5.4%. The evolution of stresses inside electrode particles and the stress inhomogeneity through the battery electrode have been illustrated. The stress level is determined by the gradients of lithium concentration, and large stresses are generated at the electrode-separator interface when high C-rates are applied, e.g. fast charging. The results can explain the experimental results of particle fragmentation close to the separator and provide novel insights to understand the local aging behaviors of battery cells and to inform improved battery control algorithms for longer lifetimes.
Mark E. Orazem and Burak Ulgut 2024 J. Electrochem. Soc. 171 040526
Recent battery papers commonly employ interpretation models for which diffusion impedances are in series with interfacial impedance. The models are fundamentally flawed because the diffusion impedance is inherently part of the interfacial impedance. A derivation for faradaic impedance is presented which shows how the charge-transfer resistance and diffusion resistance are functions of the concentration of reacting species at the electrode surface, and the resulting impedance model incorporates diffusion impedances as part of the interfacial impedance. Conditions are identified under which the two model formulations yield the same results. These conditions do not apply for batteries.
Chang-Hui Chen et al 2020 J. Electrochem. Soc. 167 080534
Presented here, is an extensive 35 parameter experimental data set of a cylindrical 21700 commercial cell (LGM50), for an electrochemical pseudo-two-dimensional (P2D) model. The experimental methodologies for tear-down and subsequent chemical, physical, electrochemical kinetics and thermodynamic analysis, and their accuracy and validity are discussed. Chemical analysis of the LGM50 cell shows that it is comprised of a NMC 811 positive electrode and bi-component Graphite-SiOx negative electrode. The thermodynamic open circuit voltages (OCV) and lithium stoichiometry in the electrode are obtained using galvanostatic intermittent titration technique (GITT) in half cell and three-electrode full cell configurations. The activation energy and exchange current coefficient through electrochemical impedance spectroscopy (EIS) measurements. Apparent diffusion coefficients are estimated using the Sand equation on the voltage transient during the current pulse; an expansion factor was applied to the bi-component negative electrode data to reflect the average change in effective surface area during lithiation. The 35 parameters are applied within a P2D model to show the fit to experimental validation LGM50 cell discharge and relaxation voltage profiles at room temperature. The accuracy and validity of the processes and the techniques in the determination of these parameters are discussed, including opportunities for further modelling and data analysis improvements.
Yuriy V. Tolmachev 2023 J. Electrochem. Soc. 170 030505
We present a quantitative bibliometric study of flow battery technology from the first zinc-bromine cells in the 1870's to megawatt vanadium RFB installations in the 2020's. We emphasize, that the cost advantage of RFBs in multi-hour charge-discharge cycles is compromised by an inferior energy efficiency of these systems, and that there are limits on the efficiency improvement due to internal cross-over and the cost of power (at low current densities) and due to an acceptable pressure drop (at high current densities). Differences between lithium-ion and vanadium redox flow batteries (VRFBs) are discussed from the end-user perspective. We conclude, that the area-specific resistance, cross-over current and durability of contemporaneous VRFBs are appropriate for commercialization in multi-hour stationary energy storage markets, and the most import direction in the VRFB development today is the reduction of stack materials and manufacturing costs. Chromium-iron RFBs should be given a renewed attention, since it seems to be the most promising durable low-energy-cost chemistry.
Peter M. Attia et al 2022 J. Electrochem. Soc. 169 060517
Lithium-ion batteries can last many years but sometimes exhibit rapid, nonlinear degradation that severely limits battery lifetime. In this work, we review prior work on "knees" in lithium-ion battery aging trajectories. We first review definitions for knees and three classes of "internal state trajectories" (termed snowball, hidden, and threshold trajectories) that can cause a knee. We then discuss six knee "pathways", including lithium plating, electrode saturation, resistance growth, electrolyte and additive depletion, percolation-limited connectivity, and mechanical deformation—some of which have internal state trajectories with signals that are electrochemically undetectable. We also identify key design and usage sensitivities for knees. Finally, we discuss challenges and opportunities for knee modeling and prediction. Our findings illustrate the complexity and subtlety of lithium-ion battery degradation and can aid both academic and industrial efforts to improve battery lifetime.
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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.
Ritu Sahore et al 2024 J. Electrochem. Soc. 171 050505
Li loss during cycling at the solid electrolyte∣anode interface strongly determines the cycle life of anode-free solid-state batteries (SSBs). Here, this loss is probed electroanalytically for polymer electrolyte (PE)-based SSBs in anode-free coin cells with practical pressures. A wide range of parameters expected to impact the measured average coulombic efficiency (CE) were explored to estimate the expected range of performance. These factors include PE type, cycling profiles, current collector type, and the presence of a thin Li seed layer. Low CE values in the ∼50%–85% range are observed for all electrolytes and test conditions. Other than the electrolyte type, a strong dependence of the CE on the electrochemical cycling profile and the type of metallic current collector is observed. Compared to the anode-free setup, the presence of a thin (5 μm) Li seed layer did not improve the average CE for two out of three PEs, suggesting its presence to be a weak contributor in minimizing the Li loss. This work provides baseline data on the Li losses in low-pressure anode-free configuration cells with PEs.
Yohei Matsui et al 2024 J. Electrochem. Soc. 171 050504
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.
Highlights
Iron was newly used as a redox species of the thermally regenerative flow battery.
The iron-based flow battery can be recharged by distillation of acetone.
Maximum power density reached 40 W m−2.
Technical challenges for the electrolyte and cell designs were discussed.
Debbie Zhuang et al 2024 J. Electrochem. Soc. 171 050510
Industry-standard diagnostic methods for rechargeable batteries, such as hybrid pulse power characterization (HPPC) tests for hybrid electric vehicles, provide some indications of state of health (SoH), but lack a physical basis to guide protocol design and identify degradation mechanisms. We develop a physics-based theoretical framework for HPPC tests, which are able to accurately determine specific mechanisms for battery degradation in porous electrode simulations. We show that voltage pulses are generally preferable to current pulses, since voltage-resolved linearization more rapidly quantifies degradation without sacrificing accuracy or allowing significant state changes during the measurement. In addition, asymmetric amounts of information gain between charge /discharge pulses are found from differences in electrode kinetic scales. We demonstrate our approach of physics-informed HPPC on simulated Li-ion batteries with nickel-rich cathodes and graphite anodes. Multivariable optimization by physics-informed HPPC rapidly determines kinetic parameters that correlate with degradation phenomena at the anode, such as solid-electrolyte interphase (SEI) growth and lithium plating, as well as at the cathode, such as oxidation-induced cation disorder. If validated experimentally, standardized voltage protocols for HPPC tests could play a pivotal role in expediting battery SoH assessment and accelerating materials design by providing new electrochemical features for interpretable machine learning of battery degradation.
Svenja B. Seiffert et al 2024 J. Electrochem. Soc. 171 050509
Lithium-nickel-manganese-cobalt-oxides (NCMs) represent a preeminent class of cathode active materials for employment in commercially available lithium-ion battery applications. To realize large-scale production of the respective NCM precursors, coprecipitation is often conducted in continuous stirred-tank reactors (CSTR). However, precursors coming from CSTR processes show broad particle size distributions and undesired compositional differences within and between particles. To quantify this phenomenon, it is necessary to develop analytical tools to access quantitative data on particle composition depending on their size. Here, we demonstrate a novel application of single particle laser ablation-inductively coupled plasma-mass spectrometry to determine particle size-dependent elemental compositions by exemplary investigation of CSTR-based NCM precursors. An enrichment of Ni in larger particles with a concomitant enrichment of Co and Mn in smaller particles was identified. This compositional differences between particles persisted after calcination of the precursors with lithium hydroxide. The observed particle size-dependent concentration differences by spLA-ICP-MS were validated by scanning electron microscopy with energy-dispersive X-ray analysis.
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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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Neidhart et al
Thick electrode production is a key enabler for realizing high energy density Lithium-ion batteries. Therefore, the investigation of tortuosity as a crucial limiting parameter was conducted in this work. A thickness threshold (>150 μm) for a drastic increase in tortuosity for aqueous processed LiNi0.8Mn0.1Co0.1O2 (NMC811) electrodes was determined. Symmetrical cells, under blocking conditions, were analyzed via electrochemical impedance spectroscopy. To counteract this phenomenon, multi-layer coated electrodes with varying binder concentrations were investigated. This novel coating method, combined with the reduction of binder material, leads to a tortuosity decrease of more than 80 %, when compared to high-loading electrodes (>8.5mAhcm-2) coated with the conventional doctor-blade technique. Additionally, a simplified transmission line model is opposed to a linear fitting method for analyzing the impedance data.
Mitra et al
The commercial feasibility of silicon (Si) anodes (≥ 30 %) in full-cell systems is constrained by poor cyclic stability and capacity balancing due to continuous active lithium (Li) consumption in each cycle. We proposed a capacity balancing approach by adding additional Li at the cathode side (i.e., ratio of capacity at negative to positive electrode (N/P)~0.9) and anode side (i.e., pre-lithiated Si) before full-cell fabrication. This approach provided a capacity-balanced full-cell with 91.7 % of initial Coulombic efficiency (ICE) and stability up to 50 cycles. In-situ electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analysis have been utilized to examine the interface of bare and balanced full cells. In a large format cell, electrolyte wettability is an issue and it has been investigated even at high temperature (50°C). The post-cycle investigation also indicates the Si particles retained their integrity after cycling. A 110 mAh pouch cell has been constructed, and the pouch cell demonstrated exceptional cyclic stability up to 200 cycles, with a capacity retention of 83.2 % at a current rate of 0.1 C. These findings present a capacity balancing approach for high-loading silicon-based anodes that eventually can scale up to high-quality and long-cycle life lithium-ion batteries.
Zou et al
It is popular to choose the cubic phase Li7La3Zr2O12(c-LLZO) to synthesize the PEO-based complex membrane in all-solid-state battery. In this work, Ba/Nb elements were selected to achieve Li6.75La3Zr1.75Nb0.25O12 (LLZNO) and Li7La2.75Ba0.25Zr1.75Nb0.25O12 (LLBZNO) with high ion conductivity, which effectively enhance the electrochemical properties of the complex solid membrane and the all-solid-state battery. The higher ion mobility of LLBZNO compared to that of LLZNO and LLZO is calculated by ab-initio molecular dynamics (AIMD) simulation and further confirmed by experiments. Results show that the cubic phase of LLBZNO is more stable than that of LLZNO. The complex membrane of LLBZNO@ polyethylene oxide (PEO) (CPE-2-x wt%) exhibits the better electrochemical properties than LLZNO@PEO (CPE-1-x wt%) complex membrane. In detail, the CPE-2-10 wt% has the outstanding lithium transfer number (t_(〖Li〗^+ )) of 0.63, as well as the excellent compatibility with lithium metal anode. In addition, at 0.1 mA∙cm−2, the lithium/CPE-2-10 wt%/lithium symmetric cell remains stable after 1000 h. It is LLBZNO that makes LLBZNO@PEO composite polymer electrolyte(CPE) the potential for the application in all-solid-state lithium battery.
Ezzedine et al
Lithium-sulfur technology garners significant interest due to sulfur’s higher specific capacity, cost-effectiveness, and environmentally-friendly aspects. However, sulfur’s insulating nature and poor cycle life hinder practical application. To address this, a simple modification to the traditional sulfur electrode configuration is implemented, aiming to achieve high capacity, long cycle life, and rapid charge rates. Binder-free sulfur cathode materials are developed using vertically-aligned carbon nanotubes (CNTs) decorated with sulfur and a lithium sulfate barrier layer. The aligned CNT framework provides high conductivity for electron transportation and short lithium-ion pathways. Simultaneously, the sulfate barrier layer significantly suppresses the shuttle of polysulfides. The S@VACNTs with Li2SO4 coating exhibit an extremely stable reversible areal capacity of 0.9 mAh cm-2 after 1600 cycles at 1C with a capacity retention of 80% after 1200 cycles, over three times higher than lithium iron phosphate cathodes cycled at the same rate. Considering safety concerns related to the formation of lithium dendrite, a full cell Si-Li-S is assembled, displaying good electrochemical performances for up to 100 cycles. The combination of advanced electrode architecture using 1D conductive scaffold with high-specific-capacity active material and the implementation of a novel strategy to suppress polysulfides drastically improves the stability and the performance of Li-S batteries.
Yokoyama et al
There is a demand for low-melting-point molten-salt electrolytes with high thermal and electrochemical stability for the development of high-performance sodium-ion batteries. Mixing sodium bis(fluorosulfonyl)amide (NaFSA) and sodium (fluorosulfonyl)(trifluoromethylsulfonyl)amide (NaFTA) results in a large depression in their melting points. In this study, the phase behavior and Na+ transport properties of binary mixtures of NaFSA and NaFTA were investigated. The mixture of NaFSA and NaFTA with a molar ratio of 8:2 has a melting temperature (Tm) of 363 K, successfully achieving an ionic liquid consisting of single cationic (Na+) salts. This mixture easily forms a super-cooled liquid. The ionic conductivity (σ) of Na[(FSA)0.8(FTA)0.2] continuously varied from above Tm to below Tm, obeying the Vogel–Tamman–Fulcher equation, which coincides with its super-cooling nature. The ionic conductivity and apparent Na+ transference number (tNa+) under anion-blocking conditions at Tm approached 10−3 S cm−1 and 0.92, respectively.
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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.
Debbie Zhuang et al 2024 J. Electrochem. Soc. 171 050510
Industry-standard diagnostic methods for rechargeable batteries, such as hybrid pulse power characterization (HPPC) tests for hybrid electric vehicles, provide some indications of state of health (SoH), but lack a physical basis to guide protocol design and identify degradation mechanisms. We develop a physics-based theoretical framework for HPPC tests, which are able to accurately determine specific mechanisms for battery degradation in porous electrode simulations. We show that voltage pulses are generally preferable to current pulses, since voltage-resolved linearization more rapidly quantifies degradation without sacrificing accuracy or allowing significant state changes during the measurement. In addition, asymmetric amounts of information gain between charge /discharge pulses are found from differences in electrode kinetic scales. We demonstrate our approach of physics-informed HPPC on simulated Li-ion batteries with nickel-rich cathodes and graphite anodes. Multivariable optimization by physics-informed HPPC rapidly determines kinetic parameters that correlate with degradation phenomena at the anode, such as solid-electrolyte interphase (SEI) growth and lithium plating, as well as at the cathode, such as oxidation-induced cation disorder. If validated experimentally, standardized voltage protocols for HPPC tests could play a pivotal role in expediting battery SoH assessment and accelerating materials design by providing new electrochemical features for interpretable machine learning of battery degradation.
John C. Bernard et al 2024 J. Electrochem. Soc. 171 050502
This study introduces a framework for modeling the aqueous Zn/MnO2 rechargeable battery. A reaction system and a physics-based continuum model are proposed based on two reaction types, one involving insertion and the second related to dissolution and deposition of a solid reaction product. The model, fitted to empirical data, predicts voltage behavior and capacity limitations during cycling, identifying electrolytic zinc depletion as a limiting mechanism, depending on the original cell construction. The research suggests the need for further material characterization and reaction analysis, which will advance our understanding and facilitate the development of grid-scale energy storage solutions.
Highlights
Introduced a novel physics-based continuum model for Zn/MnO2 rechargeable batteries, enhancing understanding of electrolytic zinc depletion.
Validated model predictions with empirical data, showcasing accurate voltage behavior and capacity limitations during battery cycling.
Revealed electrolytic zinc depletion as a key mechanism limiting cell capacity, guiding future design improvements.
Emphasized the model’s role in advancing grid-scale energy storage solutions by optimizing aqueous battery chemistries.
Suggested further material characterization and reaction analysis to refine the model and improve battery performance.
Matthew Newman and Vicky Doan-Nguyen 2024 J. Electrochem. Soc. 171 055503
Free-standing conducting polymer films, polypyrrole doped with dodecylbenzene sulfonate, were obtained with electrochemical delamination by using redox cycling to delaminate electropolymerized film from the substrate. The use of electrochemical delamination to obtain thinner films than mechanical peeling and the effect of different electropolymerization substrates was investigated. The free-standing films were characterized with electrochemical filling efficiency and scanning electron microscopy. Electrochemical delamination allowed thin free-standing films <10 μm and <1 μm thick to be obtained from 304 stainless steel and gold substrates, respectively. The thinnest films obtainable from 304 stainless steel were limited by the electropolymerization charge density needed for complete film growth and not by electrochemical delamination. The filling efficiency of the films did not appear to be decreased by electrochemical delamination. These findings show the utility of electrochemical delamination to obtain thin free-standing films that also have the benefits of electropolymerization.
Lukas Neidhart et al 2024 J. Electrochem. Soc.
Thick electrode production is a key enabler for realizing high energy density Lithium-ion batteries. Therefore, the investigation of tortuosity as a crucial limiting parameter was conducted in this work. A thickness threshold (>150 μm) for a drastic increase in tortuosity for aqueous processed LiNi0.8Mn0.1Co0.1O2 (NMC811) electrodes was determined. Symmetrical cells, under blocking conditions, were analyzed via electrochemical impedance spectroscopy. To counteract this phenomenon, multi-layer coated electrodes with varying binder concentrations were investigated. This novel coating method, combined with the reduction of binder material, leads to a tortuosity decrease of more than 80 %, when compared to high-loading electrodes (>8.5mAhcm-2) coated with the conventional doctor-blade technique. Additionally, a simplified transmission line model is opposed to a linear fitting method for analyzing the impedance data.
Yoshiki Yokoyama et al 2024 J. Electrochem. Soc.
There is a demand for low-melting-point molten-salt electrolytes with high thermal and electrochemical stability for the development of high-performance sodium-ion batteries. Mixing sodium bis(fluorosulfonyl)amide (NaFSA) and sodium (fluorosulfonyl)(trifluoromethylsulfonyl)amide (NaFTA) results in a large depression in their melting points. In this study, the phase behavior and Na+ transport properties of binary mixtures of NaFSA and NaFTA were investigated. The mixture of NaFSA and NaFTA with a molar ratio of 8:2 has a melting temperature (Tm) of 363 K, successfully achieving an ionic liquid consisting of single cationic (Na+) salts. This mixture easily forms a super-cooled liquid. The ionic conductivity (σ) of Na[(FSA)0.8(FTA)0.2] continuously varied from above Tm to below Tm, obeying the Vogel–Tamman–Fulcher equation, which coincides with its super-cooling nature. The ionic conductivity and apparent Na+ transference number (tNa+) under anion-blocking conditions at Tm approached 10−3 S cm−1 and 0.92, respectively.
Silian Yanev et al 2024 J. Electrochem. Soc.
Increasing the specific capacity and rate performance of thiophosphate composite cathodes is a major challenge in solid-state battery development. Understanding the charge transport kinetics and rate-limiting mechanisms within the cathode is key towards efficient optimization. Herein, we use quantitative analysis of chronoamperometric rate performance data to differentiate between resistive and diffusive rate limitations of NCM811 – Li6PS5Cl cathodes with different morphology and composition. We substantiate our findings with separate measurements of the effective ionic conductivity and Li+ diffusion coefficients using impedance spectroscopy and GITT techniques, respectively. Increasing the active material to solid electrolyte ratio is found to increase diffusive limitations, which originate from the small contact area between the active material and solid electrolyte. The diffusive limitation is especially pronounced for single crystal NCM811 cathodes at over 84% AM. Employing fine particle catholyte significantly increases the contact area, alleviates the diffusive limitation, and increases rate performance. These results provide guidelines towards bringing the solid-state battery performance levels closer to practical targets.
Hussein Hijazi et al 2024 J. Electrochem. Soc.
This study explores the impact of simple electrolyte additives on the performance of layered oxide/hard carbon sodium-ion pouch cells. The cycle life of these cells between 2.0 and 3.8 V is assessed at various temperatures (20, 40, and 55°C) with different solvent systems based on ethylene carbonate, diethyl carbonate, and dimethyl carbonate. A particular challenge in these cells is gas generation at high temperature. Pouch bag experiments which separate the charged electrodes to measure their gas generation from reactions with the electrolyte show that hard carbon generates no gas, but the sodium layered oxide produces large amounts of gas. Isothermal microcalorimetry corroborates these results with parasitic heat flow measurements of pouch bags and full pouch cells. A crosstalk mechanism is revealed which lowers gas generation and reduces parasitic heat flows in full cells. The electrolyte additives prop-1-ene-1,3-sultone, sodium difluorophosphate, and 1,3,2-dioxathiolane-2,2-dioxide (DTD) are effective at reducing gas generation and heat flow from the positive electrode. They also reduce self-discharge in elevated temperature storage tests. Overall, 1M NaFSI in EC:DMC (15:85) with 2% DTD is the best electrolyte for the sodium-ion pouch cells in this work. Eventually, the performance of these cells is compared to optimized LiFePO4/graphite cells.
Louis V. Morris et al 2024 J. Electrochem. Soc. 171 050501
We have explored a set of structurally related fluorinated and non-fluorinated organosilicon additives and quantified their rates of reaction with the superoxide radical anion O2•−. using rapid-scan cyclic voltammetry. Absolute reaction rate measurements in acetonitrile solvent show that O2•− reacts with the fluorinated OS compounds with bimolecular rate constants kBM more than 1000x larger than kBM for the reaction between O2•− and ethylene carbonate. We further identified the products of reaction of a model OS compound using multiple nuclear magnetic resonance (NMR) methods and with gas chromatography/mass spectroscopy. Chemical analysis measurements show that addition of potassium superoxide KO2 to a model fluorinated OS compound produces only one product. Our results indicate that that OS compounds improve battery performance by rapidly scavenging O2•− in a way that produces a stable product and reduces or eliminates the competing chemical pathways associated with carbonate breakdown. These results provide new insights into how chemical structure impacts critical chemical reactions and may guide the design of new additives that further improve battery safety and stability.
Lilian Danielle de Moura Torquato et al 2024 J. Electrochem. Soc. 171 055502
The development of bioelectrochemical systems requires careful selection of both their biotic and abiotic components to obtain sustainable devices. Herein, we report a biophotoelectrode obtained with polyhydroxybutyrate (PHB), a biopolymer, which purple non-sulphur bacteria produce as an energy stock under specific environmental conditions. The electrode was obtained by casting a mixture composed of PHB and carbon fibers in a 3:2 mass ratio. Following, the composite material was modified with polydopamine and thermally treated to obtain a hydrophilic electrode with improved electrochemical behavior. The bio-based electrode was tested with metabolically active cells of Rhodobacter capsulatus embedded in a biohybrid matrix of polydopamine. The system achieved enhanced catalytic activity under illumination, with an 18-fold increase in photocurrent production compared to biophotoelectrodes based on glassy carbon, reaching a current density of 12 ± 3 μA cm−2, after 30 min of light exposure at +0.32 V. The presented biocompatible electrode provides a sustainable alternative to metal-based and critical raw material-based electrodes for bioelectrochemical systems.
Highlights
Biobased electrode for microbial electrochemical systems.
Bacteria-produced polymer for devices with enhanced colonization.
Improved biofilm formation and photocurrent generation.