Battery research depends upon up-to-date information on the cell characteristics found in current electric vehicles, which is exacerbated by the deployment of novel formats and architectures. This necessitates open access to cell characterization data. Therefore, this study examines the architecture and performance of first-generation Tesla 4680 cells in detail, both by electrical characterization and thermal investigations at cell-level and by disassembling one cell down to the material level including a three-electrode analysis. The cell teardown reveals the complex cell architecture with electrode disks of hexagonal symmetry as well as an electrode winding consisting of a double-sided and homogeneously coated cathode and anode, two separators and no mandrel. A solvent-free anode fabrication and coating process can be derived. Energy-dispersive X-ray spectroscopy as well as differential voltage, incremental capacity and three-electrode analysis confirm a NMC811 cathode and a pure graphite anode without silicon. On cell-level, energy densities of 622.4 Wh/L and 232.5 Wh/kg were determined while characteristic state-of-charge dependencies regarding resistance and impedance behavior are revealed using hybrid pulse power characterization and electrochemical impedance spectroscopy. A comparatively high surface temperature of ∼70 °C is observed when charging at 2C without active cooling. All measurement data of this characterization study are provided as open source.
The Electrochemical Society (ECS) was founded in 1902 to advance the theory and practice at the forefront of electrochemical and solid state science and technology, and allied subjects.
ISSN: 1945-7111
JES is the flagship journal of The Electrochemical Society. Published continuously from 1902 to the present, JES remains one of the most highly-cited journals in electrochemistry and solid-state science and technology.
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Manuel Ank et al 2023 J. Electrochem. Soc. 170 120536
George E. Blomgren 2017 J. Electrochem. Soc. 164 A5019
This year, the battery industry celebrates the 25th anniversary of the introduction of the lithium ion rechargeable battery by Sony Corporation. The discovery of the system dates back to earlier work by Asahi Kasei in Japan, which used a combination of lower temperature carbons for the negative electrode to prevent solvent degradation and lithium cobalt dioxide modified somewhat from Goodenough's earlier work. The development by Sony was carried out within a few years by bringing together technology in film coating from their magnetic tape division and electrochemical technology from their battery division. The past 25 years has shown rapid growth in the sales and in the benefits of lithium ion in comparison to all the earlier rechargeable battery systems. Recent work on new materials shows that there is a good likelihood that the lithium ion battery will continue to improve in cost, energy, safety and power capability and will be a formidable competitor for some years to come.
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.
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.
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.
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.
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.
Meng Yue et al 2024 J. Electrochem. Soc. 171 050515
N-methyl-2-pyrrolidone (NMP) is the most common solvent used in coating positive electrode materials on aluminum foil during the manufacturing of lithium-ion batteries. NMP is a strongly polar aprotic solvent that effectively dissolves the polyvinylidene difluoride binder. While the majority of NMP typically evaporates during the electrode baking process, trace amounts may persist, particularly in positive electrodes containing nano-sized and highly-porous active materials. We noted residual NMP in the positive electrodes of Li-ion pouch cells containing LiMn0.8Fe0.2PO4 due to the extremely high surface area of the material and we wanted to determine the impact of this residual NMP. Therefore, a control electrolyte was purposely spiked with varying amounts of NMP and used in NMC532/graphite pouch cells to investigate the impact of residual NMP on lithium-ion battery performance. Experimental results indicate that NMP has the potential not only to neutralize the electrolyte additive ethylene sulfate but also to independently increase cathode impedance, leading to a higher rate of capacity loss during charge-discharge cycling. It is crucial to establish the appropriate procedure for baking electrodes containing NMP, both in laboratory and industrial settings, to mitigate these effects.
John G. Petrovick et al 2023 J. Electrochem. Soc. 170 114519
Anion-exchange membranes (AEMs) are a possible replacement for perfluorosulfonic-acid membranes in energy-conversion devices, primarily due to the hydroxide mobile ion allowing the devices to operate in alkaline conditions with less expensive electrocatalysts. However, the transport properties of AEMs remain understudied, especially electro-osmosis. In this work, an electrochemical technique, where the open-circuit voltage is measured between two ends of a membrane maintained at different relative humidities, is used to determine the water transport number of various ionomers, including Versogen and Sustainion AEMs and Nafion cation-exchange membrane (CEM), as a function of water content and temperature. In addition, the CEMs and AEMs are examined in differing single-ion forms, specifically proton and sodium (CEM) and hydroxide and carbonate (AEM). Carbonate-form AEMs have the highest transport number (∼11), followed by sodium-form CEMs (∼8), hydroxide-form AEMs (∼6), and proton-form CEMs (∼3). Finally, a multicomponent transport model based on the Stefan-Maxwell-Onsager framework of binary interactions is used to develop a link between water transport number and water-transport properties, extracting a range for the unmeasured membrane water permeability of Versogen as a function of water content.
Sarah F. Zaccarine et al 2022 J. Electrochem. Soc. 169 064502
Polymer electrolyte membrane water electrolyzers (PEMWEs) are devices of paramount importance, enabling the large-scale storage of hydrogen from intermittent renewable energy sources such as wind and solar. But a transition towards lower noble metal catalyst loadings and intermittent operation is needed for the widespread utilization of this technology. Although kinetic losses tend to dominate in membrane electrode assembly (MEA) results, it has been suggested that morphological changes and interfaces between the catalyst, ionomer, and membrane will also contribute to overall degradation. Moreover, the combination of degradation to the catalyst layer (CL) constituents will further lead to structural changes that have not been widely explored. The multitude and complexity of degradation mechanisms, which likely occur simultaneously, require a characterization approach that can explore surfaces and interfaces at a range of length-scales to probe chemical, morphological, and structural changes of constituents within the catalyst later. This paper presents a comprehensive characterization approach that features scanning electron microscopy (SEM), scanning transmission electron microscopy with energy-dispersive X-Ray spectroscopy (STEM/EDS), X-Ray photoelectron spectroscopy (XPS), X-Ray absorption spectroscopy (XAS), and transmission X-Ray microscopy (TXM) with X-Ray absorption near-edge structure (XANES) chemical mapping to study degradation of the catalyst layer with a focus on MEAs after intermittent and steady-state operation. Catalyst changes including dissolution, oxidation, and agglomeration were observed, as well as redistribution and dissociation of the ionomer. These smaller-scale changes were found to have a large influence on overall stability of the electrodes: they caused the formation of voids and segregation of constituents within regions of the film. Delamination and collapse of the overall catalyst layer were observed in some instances. Greater changes were observed after an extended 2 V hold compared to IV cycling, but similar degradation mechanisms were detected, which suggests the larger issues would likely also be experienced during intermittent PEMWE operation. These findings would not be possible without such a systematic, multi-scale, multi-technique characterization approach, which highlights the critical importance of detailed analysis of catalyst layer degradation to propose mitigation strategies and improve long-term PEM water electrolyzer performance.
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Bingbin Wu et al 2024 J. Electrochem. Soc. 171 050542
Silicon-dominant anodes are of great interest because of their potential to boost the cell-level energy of state-of-the-art Li-ion batteries. While silicon materials have been extensively studied, understanding interactions at the electrode level has recieved little attention, especially the coating process of Si particles, which plays an equally important role in unlocking the full potential of silicon anodes. Herein, the electrode processing of a Si-dominated anode (52.8 wt%, 3.5–4.5 mAh cm−2) is being investigated to understand the relationship of processing on the morphology and properties of Si anodes at the electrode level. It has been found that almost-undetectable Si agglomerates easily form during electrode processing, which grow into largeprotrusions after lithiation and trigger potential internal shorting and self-discharge problems. A facile slurry filtration step is proposed to homogenize the particle distribution within Si-dominant electrodes which improves the electrochemical performance and storage stability of Si-based Li ion batteries.
Anuj Vats et al 2024 J. Electrochem. Soc. 171 053504
Shaped tube electrolytic drilling (STED) is an electrochemical machining variant that employs a tubular tool electrode to produce holes with a high aspect ratio on hard-to-machine materials. The tubular electrodes with a diameter below 1 mm produce undesired residue (center-peak) at the machining surface that hampers the machining rate. Therefore, this study attempts to improve the electrolyte flow and enhance the electrochemical dissolution through tool modification. The performance enhancement of the STED process in terms of material removal rate and average diametral overcut has been explored. The issues related to the limitations in material removal in the STED process are brought forth with the technique to resolve those difficulties. The experiments were conducted with the modified tubular tool, and the length of slits on the tool was selected based on the simulation insights and pilot study. The effects of input process parameters (applied voltage, tool feed rate, electrolyte concentration, and tool slit length) on the output responses obtained from the STED process are elaborated. Holes with diameters in the range 0.89–0.97 mm and 12 mm depth were fabricated. Further optimization of the process parameters in the design space is also presented to obtain sustainable process performance.
Theophile Niyitanga et al 2024 J. Electrochem. Soc. 171 056508
Seawater electrocatalysis holds significant promise as a technology for hydrogen production. A simple and low-cost impregnation-hydrothermal and thermal reduction strategy was used to synthesize in situ constructed three-dimensional porous trimetallic (Pd, Fe, and Co) anchored on a cheap and high-conducting carbon paper (CP) electrode for water electrolysis in alkaline media. The fabricated PdFeCo1−xONPs@CP electrode had super-hydrophilic and superaerophobic properties, allowing for the efficient removal of oxygen bubbles from the electrode surface due to the close interaction between the electrode and electrolyte. Furthermore, the synergistic effect of trimetallics and CP-fibers significantly increased OER intrinsic activity. PdFeCo1−xONPs@CP catalyst demonstrated critical low overpotentials of 220 and 300 mV, resulting in an extraordinarily high current density of 100 mA cm−2. For the full cell overall water splitting performance, cell overpotentials as low as 140 and 151 mV were needed to drive 10 mA cm−2 in seawater and alkaline solution electrolytes.
Highlights
PdFe and Co1−xONPs grown on CP exhibits efficient catalytic performance for OER.
PdFeCo1−xONPs@CP showed strong metal-metal interactions with efficient synergistic.
Efficient synergistic effect was presented for the optimal catalyst.
Demonstrated improved electrical conductivity and excellent stability.
Cell overpotential of 151 mV needed to drive 10 mA cm−2 in 1 M KOH seawater.
Ye-ba Yan et al 2024 J. Electrochem. Soc. 171 050541
Due to a lack of portable flexible power supply, flexible electronic products can still not be applied in a large scale, particularly in the high energy density devices. To resolve this issue, flexible solid-state lithium batteries with a high safety, excellent mechanical property, and high energy densit,is proposed. In this paper, a flexible solid-state lithium-manganese battery is developed, which is assembled with a lithium cloth composite anode, a composite solid-state electrolyte poly (vinylidene fluoride)-hexafluoropropylene (PVDF-HFP)/Li6.4La3Zr1.4Ta0.6O12 (LLZTO), and a composite cathode (Fe ion-doped MnO2-carbon cloth). To improve the conductivity and stability of cathode, a mixture of conductive carbon black (Super P) and sodium alginate (SA) is employed. To ensure the high capacity and low price, the MnO2-based cathode is used.The obtained solid state batteries can deliver an initial capacity of 275.9 mAh g−1 at a current density of 1 C and a capacity retention of 57.9% (159.7 mAh g−1) after 1000 cycles. Also the produced flexible punch cell can light up the light-emitting diode(LED), and its capacity is 0.58 mAh cm−2 after 100 cycles at current density of 0.2 C.
Feng Han et al 2024 J. Electrochem. Soc. 171 054515
Electrolyte supported Solid Oxide Cells (ESCs) with advanced thin-film Gd-doped ceria diffusion barrier layers between electrolyte and electrodes were assembled and electrochemically investigated in steam electrolysis mode in a so-called "rainbow" stack with 30 repeat units (RUs). The barrier layers were deposited onto the electrolyte supports via electron-beam physical evaporation deposition (EB-PVD) method at 600 °C. In this paper, the investigation mainly focuses on the electrochemical characteristics of RUs containing the EB-PVD thin-film GDC layers. At the initial stage of the SOEC operation, the stack reached a high performance with an electrical efficiency of 99.65% at 75% steam conversion and a total power input of 1.98 kW. A long-term stack test was performed in SOEC mode for over 5000 h and demonstrated a low voltage degradation of approx. +11.3 mV·kh–1 per RU (+0.9% kh–1). The RUs with EB-PVD GDC thin-films revealed similar initial performance and degradation rate to the state-of-the-art cells with screen printed GDC layers.
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Minh Quang Nguyen et al 2024 J. Electrochem. Soc. 171 057507
Aquaculture, driven by increasing demands for animal proteins and fats, faces multifaceted challenges stemming from environmental factors such as climate change and pollution, alongside issues like disease susceptibility and limited therapeutic tools. However, the emergence of nanotechnology (NNT) offers a promising solution across various aquaculture domains. Nano-enhanced feed has been shown to improve fish growth rates, while nanomaterials are reducing the treatment economy by effectively eliminating contaminants. Genetic manipulation methods combined with nanobiotechnology have revolutionized fish ancestry studies, with advancements such as nanosensors and DNA-based vaccines significantly impacting fish life and immune systems. Moreover, nanotechnology plays a crucial role in enhancing fish processing, enabling sterile packaging and precise flavoring. Utilizing fishery waste through bio-nano-engineering and green nanoparticles offers new post-harvesting practices. Despite ongoing exploration, NNT presents versatile applications, prospects, and challenges in aquaculture, as detailed in this review. This paper provides an in-depth analysis of current trends, challenges, and prospects of NNT applications in aquaculture.
Durgalakshmi Dhinasekaran et al 2024 J. Electrochem. Soc. 171 057505
Uric acid (UA) is an important biomarker in blood to diagnosis diseases linked with hyperuricemia. Although several detection methods exist for UA sensing, electrochemical method has emerged as a promising alternative. For effective performance of a biosensor, the choice of electroactive material plays a crucial role. The developed electrodes are enzymatic and non-enzymatic with modified nano-structures of metal oxides, ferrites and carbon-based materials. Several combinations of nanocomposites using metal oxides with carbon-based compounds show promising results for biosensor applications. This is attributed to its functional groups, higher surface area and porous nature that can improve the sensing performance as it requires only quick-time processing with inexpensive and direct detection methods. The electrochemical method uses anodic peak current which is the analytical signal to sense the electrochemical oxidation of UA. This technique paves a new way to make electrodes for point-of-detection devices in near future. It could be the next generation of non-invasive analysis for food hygiene as well as biomedical and clinical applications. This review focuses on materials used in electrochemical sensing of UA and discusses on the application of different electrochemical techniques in UA detection.
Jiashuai Wang et al 2024 J. Electrochem. Soc. 171 040527
The growing demand for energy storage application has facilitated the development of Li-ion rechargeable batteries (LIBs). As such, there is an urgent need to design electrodes with a high specific energy and long cycle life. The evolution of conventional LIBs cathode materials in past 30 years has arrived at a bottleneck. Fortunately, the finding of the lithium-rich cation disordered rocksalt (DRXs) has largely broadened the element ranges of the promising cathode in the past several years. Compared with the classical cation-ordered oxides, the DRXs display a large charge storage capacity based on both transition metal and oxygen redox capacity. In addition, their wide compositional space and cobalt-free characteristic would greatly reduce production costs in promoting the commercialization process. Herein, we make an overview of the recent progress for DRXs materials, in terms of their compositions and structure, Li diffusion, charge storage mechanisms, and different redox centra-based system. The key challenges to practical application are also discussed. Last but not least, in order to design high-performance DRXs, we outlined perspectives in developing DRXs for the next generation of LIB cathodes.
Pooja Saxena and Prashant Shukla 2024 J. Electrochem. Soc. 171 047504
Wearable sensors offer a non-invasive, continuous, and personalized approach to monitor various physiological and environmental parameters. Among the various materials used in the fabrication of wearable sensors, polymers have gained significant attention due to their versatile properties, low cost, and ease of integration. We present a comprehensive review of recent advances and challenges in the development of polymer-based wearable sensors. We begin by highlighting the key characteristics of wearable sensors, emphasizing their potential applications and advantages. Subsequently, we delve into the various types of polymers employed for sensor fabrication, such as conductive polymers, elastomers, and hydrogels. The unique properties of each polymer and its suitability for specific sensing applications are discussed in detail. We also address the challenges faced in the development of polymer-based wearable sensors and describes the mechanism of action in these kinds of wearable sensor-capable smart polymer systems. Contact lens-based, textile-based, patch-based, and tattoo-like designs are taken into consideration. Additionally, we paper discuss the performance of polymer-based sensors in real-world scenarios, highlighting their accuracy, sensitivity, and reliability when applied to healthcare monitoring, motion tracking, and environmental sensing. In conclusion, we provide valuable insights into the current state of polymer-based wearable sensors, their fabrication techniques, challenges, and potential applications.
Bianca-Maria Tuchiu et al 2024 J. Electrochem. Soc. 171 047502
Topical treatments rely on drugs that play a crucial role in addressing skin and mucous membrane disorders. Therefore, it is highly needed to utilize accurate analytical techniques that can determine the concentration of these chemicals in various sample matrices, including pharmaceuticals, food, and water. Currently, electrochemical sensors are predominantly used in specific fields such as biomedical, industrial, and environmental monitoring, while they have not yet been incorporated into the pharmaceutical manufacturing industry. However, electrochemical methods employing an expanding range of sensors provide a reliable, cost-effective, and efficient substitute for classical analytical methods. Their potential is highly favorable, offering possibilities for simultaneous determination, miniaturization, and real-time on-site monitoring. This work covers numerous sensors designed between 2020 and 2023 for the determination of topical drugs, highlighting their respective benefits and drawbacks while illuminating emerging trends. Moreover, it discusses the correlation between the used materials and the ease of manufacturing, to the achieved results, including dynamic range, detection limit, sensitivity, and selectivity. This work aims to serve as a valuable resource for researchers, engineers, and policymakers in the evolving field of electrochemical sensing by providing guidance and facilitating decision-making, which could lead to significant innovations in sensor technology.
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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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Sivaji et al
Developing a precise and effective method to detect Nilutamide (NIL) is essential due to its contamination of the environment, which poses significant risks to human health and the biosphere. In this study, we employed a simple hydrothermal technique to create a nanocomposite of CuCo2O4 (copper cobalt oxide) and multi-walled carbon nanotube (MWCNT), which was then anchored onto a glassy carbon electrode for NIL detection. Various spectroscopic techniques were employed to confirm the structure of the nanomaterial, and its electrochemical properties were examined using cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. The CuCo2O4/MWCNT nanocomposite-modified electrode exhibited a wide linear detection range from 0.01 to 170 µM, a high sensitivity of 1.50 μA μM−1 cm−2, a low detection limit of 0.01 μM, outstanding stability, repeatability, and practical applicability for NIL detection.
Cao et al
Cadmium (Cd(II)) is highly toxic to environmental, and while many approaches have been developed to measure cumulative Cd(II) concentration over time, online monitoring of spatiotemporal changes remains challenging. To address this, an electrochemical sensor for determination of ultra-trace Cd(II) was developed, based on gold/graphene oxide/copper oxide (Au/GO/CuO) nanomaterials modifying glassy carbon electrode. CuO nanoparticles were prepared by a green synthesis method using plant extract, and the Au nanoparticles were deposited on the GO/CuO nanosubstrates by an in-situ electrochemical method. The prepared nanocomposites were characterized by field-emission scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The CuO nanoparticles are layered flower-like with an average particle size of 200-500 nm. Au/GO/CuO nanocomposites with high specific surface area and excellent electronic transmission capability enhanced the electrochemical signal of the sensor. Owing to the synergistic effect of Au/GO/CuO, the sensor exhibited good performance to Cd(II) in the ultra-wide range of 5×10-11 - 5×10-7 M with a detection limit of 2×10-11 M. The sensor was successfully quantified for determining Cd(II) with desirable recovery, displaying outstanding long-term stability, high sensitivity, and reproducibility. After validating its accuracy, this sensor was successfully used for detection of Cd (II) in water and cosmetic samples.
Liu et al
Water electrolysis has been used to produce green hydrogen, for which identifying optimum operation parameters is crucial to improve its energy efficiency and energy consumption. This paper used a commercial proton exchange membrane (PEM) water electrolyser stack (180 W) to demonstrate the correlation between operating current change, temperature, and water flow rate and their impact on the thermal and electrical performance of the stack. It was found that the current control regime and temperature control can offset the voltage ageing in a long-term operating electrolyser with no negative impact on the H2 production rate. For a controlled decreasing current path, in the medium range of operating current, the stack’s energy efficiency was improved by 5%, and 3.7% specific energy consumption can be saved comparing to the standard operation (57.8 kWh·kg-1H2). The results provide insights into the potential optimisation in operation conditions to further increase cell energy efficiency and reduce energy consumption. This new finding sheds light on developing an energy- and cost-saving operating method for long-term green hydrogen production via water electrolysis.
R et al
Immunosensors have emerged as vital tools in cancer diagnostics, providing simplified and rapid detection of biomarkers that are necessary for timely diagnosis. The objective of using an electrochemical immunosensor is to detect cancers at early stages, so that obtained biological information can be analyzed using artificial intelligence (AI) for deciding an appropriate treatment, avoiding false diagnosis, and preventing patient fatalities. The focus of this article is on four major reproductive cancers—breast, ovarian, cervical, and prostate cancers. Specifically, it explores the identification and optimization of biomarkers crucial for precise detection in these cancers. Examining a decade of research, the review delves into nanotechnology-assisted electrochemical immunosensors (affinity biosensors), outlining advancements and emphasizing their potential in reproductive cancer diagnostics. Furthermore, the review contemplates avenues for enhancing sensor characteristics to pave the way for their application in field diagnosis, with a forward-looking perspective on AI-assisted diagnostics for the next generation of personalized healthcare. In navigating the landscape of reproductive cancer diagnostics, the integration of advanced technologies promises to transform our approach, offering improved accuracy and outcomes for patients.
Stamenkovic et al
Unveiling the electrochemistry of solid-state Li2ZrCl6 halide electrolyte, we reveal its dual function as both an ion conductor and a supplementary electron source/sink. This groundbreaking discovery leads to a remarkable long-term enhancement of the specific capacity of industry-relevant heavily loaded LiFePO4 electrodes by several tens of percent, while significantly amplifying that of Si-based or anode-less full cells through effective compensation for side reactions. We show that these effects can potentially be tuned by adjusting the initial xLiCl-ZrCl4 composition of the solid electrolyte, which may thus become a new and mighty parameter for balancing the two electrodes.
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Bingbin Wu et al 2024 J. Electrochem. Soc. 171 050542
Silicon-dominant anodes are of great interest because of their potential to boost the cell-level energy of state-of-the-art Li-ion batteries. While silicon materials have been extensively studied, understanding interactions at the electrode level has recieved little attention, especially the coating process of Si particles, which plays an equally important role in unlocking the full potential of silicon anodes. Herein, the electrode processing of a Si-dominated anode (52.8 wt%, 3.5–4.5 mAh cm−2) is being investigated to understand the relationship of processing on the morphology and properties of Si anodes at the electrode level. It has been found that almost-undetectable Si agglomerates easily form during electrode processing, which grow into largeprotrusions after lithiation and trigger potential internal shorting and self-discharge problems. A facile slurry filtration step is proposed to homogenize the particle distribution within Si-dominant electrodes which improves the electrochemical performance and storage stability of Si-based Li ion batteries.
Feng Han et al 2024 J. Electrochem. Soc. 171 054515
Electrolyte supported Solid Oxide Cells (ESCs) with advanced thin-film Gd-doped ceria diffusion barrier layers between electrolyte and electrodes were assembled and electrochemically investigated in steam electrolysis mode in a so-called “rainbow” stack with 30 repeat units (RUs). The barrier layers were deposited onto the electrolyte supports via electron-beam physical evaporation deposition (EB-PVD) method at 600 °C. In this paper, the investigation mainly focuses on the electrochemical characteristics of RUs containing the EB-PVD thin-film GDC layers. At the initial stage of the SOEC operation, the stack reached a high performance with an electrical efficiency of 99.65% at 75% steam conversion and a total power input of 1.98 kW. A long-term stack test was performed in SOEC mode for over 5000 h and demonstrated a low voltage degradation of approx. +11.3 mV·kh–1 per RU (+0.9% kh–1). The RUs with EB-PVD GDC thin-films revealed similar initial performance and degradation rate to the state-of-the-art cells with screen printed GDC layers.
Mingjie Tu et al 2024 J. Electrochem. Soc. 171 050539
Silicon oxide (SiO) is a promising anode material for high-energy lithium-ion batteries, as it is made from low-cost precursors, has a potential close to that of Li, and has high theoretical specific capacity. However, the applications of SiO are limited by the intrinsic low electrical conductivity, large volume change, and low coulombic efficiency, which often lead to poor cycling performance. A common strategy to address these shortcomings is to blend SiO with graphite active materials to form a composite anode for better capacity retention. In this work, we derive a reduced order model (ROM1) using perturbation theory. We employ the multi-site, multi-reaction (MSMR) framework of a composite porous electrode blend consisting of two lithium-host materials, SiO and graphite. The ROM1 model employs a single-particle model (SPM) approach as the leading-order solution and involves the numerical analysis of a single, nonlinear partial differential equation for each host material that describes diffusion by means of irreversible thermodynamics, wherein chemical-potential gradients are the driving forces for the diffusion. The first-order correction treats losses other than that of the SPM.
Isaac Squires et al 2024 J. Electrochem. Soc. 171 050536
Modelling lithium-ion battery behavior is essential for performance prediction and design improvement. However, this task is challenging due to processes spanning many length scales, leading to computationally expensive models. Reduced order models have been developed to address this, assuming a “separation of scales” between micro- and macroscales. This study compares two approaches: direct microstructure-resolved 3D domain electrochemical modelling and a simplified 1D homogenized model, similar to the Doyle-Fuller-Newman model. The research investigates the validity of the scale separation assumption in continuum electrode-level models by varying scale separation factors, boundary conditions, and geometries. The findings reveal increases in deviation between the 3D models and 1D models for more tortuous, less porous microstructures, especially under higher discharge rates. However, under realistic conditions, with an electrode featuring eight particles across its thickness and typical transport properties, the 3D model predicts only a slight (2%) increase in current compared to the 1D model at a high rate of 7C (approximately j ≈ 350 Am−2). These results suggest that the separation of scales assumption in the DFN model is generally suitable for a wide range of operating conditions. However, 1D models may overlook local variations in electrolyte concentration and potential, crucial for understanding degradation mechanisms.
Alastair Hales and James Bulman 2024 J. Electrochem. Soc. 171 050535
Lithium-ion batteries generate heat, degrading faster and becoming unsafe at high temperature. Yet many battery models do not consider the contribution of reversible, entropic heating when evaluating the rate of heat generation from a cell or battery pack. This leads to temperature prediction errors in battery management systems, increased safety risk, and reduced lifetime of the battery pack. Here, a standardised potentiometric method is proposed, allowing anyone with access to a typical battery lab to reliably and accurately extract the entropy coefficient for any electrochemical cell, the key parameter for the inclusion of reversible heating in a battery model. The proposed method takes 7.4 days to complete, representing a reduction of 90% compared to some methods proposed in the literature. Results highlight the importance of moving away from the multiple temperature steps, and the temperature step increases that dominate the existing literature. These arguments are justified through the observation and introduction of voltage relaxation following both kinetic and thermal excitation. These phenomena are termed post-kinetic-potentialisation and post-thermalisation-potentialisation. Post-thermalisation-potentialisation is not discussed in any published literature yet represents an important behavioural trait for any lithium-ion cell with a non-negligible length scale and thermal diffusivity.
Y. Liu et al 2024 J. Electrochem. Soc. 171 054514
The microstructural integrity of Ni-based fuel electrodes is important for long-term solid oxide fuel cell (SOFC) operation. Degradation due to microstructural changes such as Ni-agglomeration, coarsening, and densification must be prevented by an appropriate microstructure. Here, the performance of four types of nickel-ceria-based fuel electrodes, which differ concerning layer sequence and manufacturing processes, was evaluated by electrochemical impedance spectroscopy at the nominal operating temperature of 600 °C. Electrodes produced through screen-printed GDC exhibited an acceptable polarization resistance (0.260 Ωcm2), whereas electrodes with an additional printed Ni/GDC layer demonstrated inferior performance (0.550 Ωcm2). Electrodes formed through infiltration of GDC into the printed GDC-layer displayed unreproducible performance values ranging from 0.16 to 1.20 Ωcm2 despite similar processing. Conversely, electrodes with an extra layer of GDC infiltrated into the Ni-backbone exhibited good performance (0.195 Ωcm2) and stability. Accelerated degradation tests under OCV at increased operating temperatures of 700 and 900 °C were performed on the sample based on a GDC infiltrated Ni-backbone that performed best among reproducible samples. The polarization resistance at 600 °C recorded at the beginning and the end of life increased by up to 100%. Microstructural analysis of the electrodes at different aging states revealed strong microstructural changes of fine-infiltrated GDC structures and Ni agglomeration at higher operating temperature.
Jingjing Liu et al 2024 J. Electrochem. Soc.
Water electrolysis has been used to produce green hydrogen, for which identifying optimum operation parameters is crucial to improve its energy efficiency and energy consumption. This paper used a commercial proton exchange membrane (PEM) water electrolyser stack (180 W) to demonstrate the correlation between operating current change, temperature, and water flow rate and their impact on the thermal and electrical performance of the stack. It was found that the current control regime and temperature control can offset the voltage ageing in a long-term operating electrolyser with no negative impact on the H2 production rate. For a controlled decreasing current path, in the medium range of operating current, the stack’s energy efficiency was improved by 5%, and 3.7% specific energy consumption can be saved comparing to the standard operation (57.8 kWh·kg-1H2). The results provide insights into the potential optimisation in operation conditions to further increase cell energy efficiency and reduce energy consumption. This new finding sheds light on developing an energy- and cost-saving operating method for long-term green hydrogen production via water electrolysis.
Benedikt Stumper et al 2024 J. Electrochem. Soc. 171 059002
Jack W. Walton et al 2024 J. Electrochem. Soc. 171 051503
Aluminum alloy, AlSi10Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8% sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi10Mg surface produced a porous oxide layer with a thickness of 5 μm. The oxide coating weight was 698 ± 29 mg/ft2. The oxide coating forms in the aluminum cells that are isolated from one another by the silicon eutectic phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (Rp) values increased by 279× after anodization. The corrosion current density values (jcorr) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.
L. Neidhart et al 2024 J. Electrochem. Soc. 171 050532
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 (>8.5 mAhcm−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.