TY - JOUR A1 - Hoffmann, V. A1 - Uhlemann, M. A1 - Richter, Silke A1 - Pfeifer, jens T1 - Calibration capacity of hot-pressed hydrogen standards for glow discharge optical emission and mass spectrometry N2 - Mixed copper and titanium hydride powder was hot-pressed and characterized by Carrier Gas Hot Extraction, XRay Diffraction, Thermal Gravimetric Analysis coupled with Mass Spectrometry, and Scanning Electron Microscopy. The hot-pressed and five conventional samples were applied for calibration of hydrogen in Glow Discharge Optical Emission and Mass Spectrometry. Up to the introduction of 15 ng/s hydrogen the Emission yield model is useful in Glow Discharge Optical Emission Spectrometry. A correlation between saturation and even reversal of the emission yield of the spectral lines H121, H486 and H656 and low sputtering rates was found. Hydrogen effects exist for the spectral lines of Cu(II) 219 and Ti(I) 399. In Glow Discharge Mass Spectrometry, a linear dependency of the 1H ion current on the sputtered mass per time exists over the total range of hydrogen content investigated. Hydrogen effects also exist for the sensitivity of 48Ti and 63Cu. The sputtering rate of two-phase materials depends linearly on the sputtered mass per time of one phase, which allows the sputtering rate of two-phase materials with known composition to be predicted. KW - Hot-pressing KW - GD-OES KW - GD-MS KW - Calibration KW - Hydrogen KW - Titanium hydride KW - Sputtering KW - Two-phase system PY - 2021 DO - https://doi.org/10.1016/j.sab.2020.106039 VL - 176 SP - 106039 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-52074 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Battistella, Beatrice T1 - A Dual Glow Discharge Optical Emission Spectroscopic and Mass Spectrometric Study of Manufacturing and Aging in Lithium-Ion Batteries N2 - Lithium-ion batteries (LIBs) are extensively employed to power small electric and stationary devices as well as electric vehicles (EVs), due to their high energy density, long cycle life, and relatively low self discharge. The rapid expansion of the EV market is expected to increase significantly the global demand for LIBs, with sales projected to reach 245 million units by 2030, according to the International Energy Agency. In order to meet this demand, it is essential to reduce manufacturing scrap rates and extend battery life. [1,2] Production efficiency can be increased by limiting production failures and detecting process deflections at early stages of manufacturing chain, for example through rigorous control of the electrode homogeneity. On the other hand, the prolongation of a battery life assumes deep knowledge of the degradation processes, such as dendrite formation and electrolytes degradation, directly correlated with a change in the elemental distribution inside the battery. [3] As techniques capable of in-depth elemental analysis at scales from a few nm to 100 μm, Glow Discharge Optical Emission Spectroscopy (GD-OES) and Glow Discharge Mass Spectrometry (GD-MS) are suited for investigating both the homogeneity of the cathodic material in the manufacturing phase, as well as changes in its elemental distribution caused by aging. Focus has been given to lithium and fluorine distribution, whose migration inside the battery is correlated to the cycling and the electrolyte and binder degradation, respectively. A few previous reports described depth profiling of positive and negative electrodes in LIBs using GD OES. [4 6] In this work, GD-OES spectroscopic analysis has been performed on self-made cathodes for LIBs to gain insight into the quality of the manufacturing process, targeting a standardized electrodes production. With the same cathode material, coin cells have been built and artificially aged. Post mortem analysis conducted by GD-OES with the use of an argon/neon mixture as discharge gas, helped correlating the variation of fluorine distribution with the battery state of health (SOH). GD MS analysis was employed to gain insight into battery degradation phenomena upon aging, such as transition metal dissolution from the positive electrode and lithium isotopic fractionation [3,7]. This work marks GD-techniques as versatile and efficient tools to study LIBs, unveiling significant application in both academical research and industrial manufacture. T2 - 20th European Winter Conference on Plasma Spectrochemistry CY - Berlin, Germany DA - 02.03.2025 KW - Lithium-Ion Battery KW - GD-OES KW - GD-MS PY - 2025 AN - OPUS4-62820 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - What does GD-OES reveal about the aging and manufacturing processes of lithium-ion batteries? N2 - Glow-Discharge Optical Emission Spectroscopy (GD-OES), a powerful analytical technique, sheds light on the two critical aspects of lithium-ion batteries (LIBs): manufacturing and aging 1, 2. We optimized cell production in manufacturing by adjusting parameters, including cathode doping, electrolyte concentration, and pressing force. GD-OES provided in-depth elemental composition and homogeneity analysis, which is crucial for identifying optimal manufacturing conditions. These findings were validated by electrochemical impedance spectroscopy, confirming the quality of the manufactured batteries. Shifting the focus to aging, we use GD-OES for fluorine depth profiling, a key element in understanding polymer and electrolyte degradation. However, fluorine presents analytical challenges. We addressed this by substituting argon with a neon:argon mixture, which significantly enhanced fluorine detection sensitivity. This advancement not only improves accuracy but also holds the potential to guide sustainable and cost-efficient manufacturing strategies. Through its versatility, GD-OES has proven to be a powerful tool for not only optimizing LIB manufacturing processes but also gaining deeper insights into their aging mechanisms. This research extends beyond academic interest, offering tangible benefits for the industry by translating into improved battery quality, extended lifespan, and overall performance. T2 - The 6th International Glow Discharge Spectroscopy Symposium CY - Liverpool, United Kingdom DA - 21.04.2024 KW - GD-OES KW - Depth profiles KW - Lithium KW - Battery KW - Fluorine KW - Aging KW - Manufacturing KW - Glow-discharge PY - 2024 AN - OPUS4-59945 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Fluorine Depth Profiling in Lithium-Ion Battery Materials by GD-OES N2 - Lithium-ion batteries are a key technology for tackling challenges in energy and climate crisis, but up to 30 % are discarded right after production. Quality is closely related to the homogeneity of the used materials and coatings. Fluorine compounds, both in the polymer and from degradation of the electrolyte, are of special interest for the formation and aging of LIBs. Glow-discharge optical emission spectroscopy (GD-OES) emerged as a fast and convenient method for depth-profiling of battery materials. However, fluorine remains a spectroscopic challenge due to a high excitation energy and only few strong emission lines in the UV/Vis spectral range. We investigated the partial substitution of argon with neon in the plasma gas. The main emission line at 685.603 nm was monitored by both photo multiplier tube (PMT) with Czerny-Turner monochromator at 20 µm slit-size, and charge-coupled device (CCD) with 1200 lines/mm grating. For calibration, we used a set of hot-pressed copper cylinders with varying calcium fluoride amount fraction, ranging from 1.6 % to 4.4 %. Plasma gas mixtures with a mole fraction of 5 %, 10 % and 20 % neon in argon were used. Sensitivity in comparison to pure argon was increased by factor 4, 7 and 14, respectively. In general, PMT detection was more sensitive than CCD. As expected, sputter rates decreased with higher neon content in the plasma gas. Depth-profiling of the cathodes was performed in pulsed mode at constant voltage and pressure, which resulted in stable plasma conditions. We achieve matrix-independent quantitative information on fluorine distribution by correction based on sputter rates. This advancement in GD-OES provides a more accurate analytical approach for evaluating the homogeneity of lithium-ion battery materials, potentially leading to more sustainable and cost-effective manufacturing processes. T2 - 6th International Glow Discharge Spectroscopy Symposium CY - Liverpool, United Kingdom DA - 21.04.2024 KW - Lithium Ion Batteries KW - GD-OES KW - depth-profiling KW - fluorine PY - 2024 AN - OPUS4-60200 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Hoffmann, V. A1 - Morcillo, Dalia A1 - Agudo Jácome, Leonardo A1 - Leonhardt, Robert A1 - Winckelmann, Alexander A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Investigation of aluminum current collector degradation in lithium-ion batteries using glow discharge optical emission spectrometry N2 - In this work, we employed glow discharge optical emission spectrometry (GD-OES) depth profiling as a fast and semi-quantitative method to investigate the aluminum (Al) current collector degradation in commercial lithium cobalt oxide (LCO) pouch cells with no Al2O3 pretreatment. After battery aging, a heterogeneous deposit was found on the surface of the cathode. Gray hotspot areas within an extensive pale white region were formed. Consistent with energy dispersive X-ray (EDX) analysis of micro-cross sections milled via targeted focused ion beam (FIB), an Al-containing layer of approximately 3 µm can be observed using GD-OES. We attribute one main cause of this layer is the degradation of the Al current collector. The nonuniform growth of this layer was investigated by performing GD-OES depth profiling at different in-plane positions. We found that the gray area has a higher mass concentration of Al, probably in metallic form, whereas the white area was probably covered more homogeneously with Al2O3, resulting from the inhomogeneous distribution of the pitting positions on the current collector. Compared to FIB-EDX, GD-OES enables a faster and more convenient depth profile analysis, which allows the more productive characterization of lithium-ion batteries (LIBs), and consequently benefits the development of preferable battery materials. KW - GD-OES KW - depth profiles KW - Li-ion battery KW - battery aging mechanism KW - current collector corrosion PY - 2023 DO - https://doi.org/10.1016/j.sab.2023.106681 SN - 0584-8547 VL - 205 SP - 106681 PB - Elsevier B.V. CY - Amsterdam, Netherlands AN - OPUS4-57383 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Improvement of manufacturing processes of Li-ion batteries by Glow Discharge Optical Emission Spectroscopy N2 - Manufacturing lithium-ion coin cells (LIBs) for scientific research demands reproducibility, precision, and thorough metrology to ensure consistent quality and performance. Glow-discharge optical emission spectroscopy (GD-OES) emerges as a crucial analytical technique in this context, providing detailed insights into elemental composition and material homogeneity [1,2]. This study focuses on using GD-OES to optimize and standardize the manufacturing processes of LIBs, emphasizing metrology and traceability to develop reproducible and high-quality batteries for research purposes. We refined cell production by adjusting key parameters such as cathode doping, electrolyte concentration, and calendar pressing. GD-OES facilitated depth analysis of elemental composition and distribution, which is essential for identifying and maintaining optimal manufacturing conditions. Validation was achieved through electrochemical impedance spectroscopy (EIS), ensuring the quality and consistency of the manufactured batteries. GD-OES analysis revealed critical insights into elemental uniformity and impurities, guiding adjustments significantly improving cell performance and reproducibility. The method proved fast and effective in detecting and correcting variations in the manufacturing process, leading to enhanced battery quality. To understand the aging mechanisms, GD-OES was employed for fluorine depth profiling, which is crucial for studying polymer and electrolyte degradation. We significantly enhanced fluorine detection sensitivity by substituting the argon plasma with a neon/argon mixture, providing a more accurate aging analysis. By demonstrating the versatility and efficacy of GD-OES in optimizing LIB manufacturing processes and gaining deeper insights into aging mechanisms, this research has significant practical implications. It not only advances lab research but also offers tangible industrial benefits, including improved battery quality, extended lifespan, and enhanced performance. By ensuring metrology and traceability, GD-OES contributes to developing a robust method for the reproducible manufacturing of Li-ion coin cells, boosting innovation and sustainability in battery technology. T2 - SciX 2025 CY - Covington, KY, USA DA - 05.10.2025 KW - GD-OES KW - Battery analysis KW - Depth profile KW - Lithium-ion battery PY - 2025 AN - OPUS4-64878 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Battistella, Beatrice T1 - Glow discharge techniques applied to lithium ion battery analysis N2 - Glow Discharge Techniques Applied to Lithium-Ion Battery Analysis Beatrice Battistella, V. Hoffmann, A. Revill, S. Richter, S. Recknagel, C. Abad Seit ihrer Einführung haben Lithium-Ionen-Batterie (LIB) Technologien die Welt der tragbaren Elektronik und der nachhaltigen Mobilität revolutioniert [1] und sind dank ihrer langen Lebensdauer und ihrer unübertroffenen Energiedichte in vielen Bereichen nach wie vor unersetzlich. Angesichts des kontinuierlich wachsenden Marktvolumens der LIBs [2,3] und der begrenzten Verfügbarkeit der für ihre Herstellung benötigten Ressourcen ist die Entwicklung verbesserter Batterien der nächsten Generation erforderlich. Eine wesentliche Voraussetzung für diese Entwicklung ist ein tieferes Verständnis der Degradationsmechanismen in LIB-Zellen, das jedoch häufig durch die Komplexität der Systeme und die gleichzeitig ablaufenden Prozesse, die zum Versagen beitragen, erschwert wird. In diesem Zusammenhang zeigt unsere Arbeit, wie Glimmentladungstechniken dazu beitragen können, grundlegende Fragestellungen in der LIB-Analyse zu beantworten. Einerseits hat sich die GD OES als wertvolles Werkzeug zur Qualitätskontrolle bei der Elektrodenherstellung erwiesen und zeigt Potential bei der Analyse von Fluor für diagnostische Zwecke an Zellen. Andererseits wurde die GD MS in Post-Mortem-Analysen eingesetzt, um die Korrelation zwischen Veränderungen in der elementaren und isotopischen Verteilung an den Elektroden und der elektrochemischen Leistung der Zellen zu untersuchen. Insbesondere ermöglichte der Einsatz von GD-MS bei LIBs die Detektion und Lokalisierung einer Lithium-Isotopenfraktionierung innerhalb der Elektroden und setzte damit einen neuen Maßstab für die Untersuchung der Grenzflächen zwischen Elektrode und Elektrolyt. _____________________________ Since their introduction, lithium-ion battery (LIB) technologies have revolutionized the world of portable electronics and sustainable mobility [1], and they remain irreplaceable in several sectors thanks to their long cycle life and unmatched energy density. In view of the continuously growing LIB market [2,3] and the limited availability of the resources required for their manufacture, the development of improved next-generation batteries is needed. This requires a deeper understanding of degradation pathways in LIB cells, which is often hindered by the complexity of these systems and the concurrent processes that contribute to failure. In this context, our work demonstrates how glow discharge techniques can help address fundamental questions in LIB analysis. On one hand, GD-OES has proven to be a valuable tool for quality control in electrode manufacturing, showing potential in the analysis of fluorine for cell diagnostics. On the other hand, GD-MS applied in post-mortem analysis enabled correlation of changes in elemental and isotopic distributions within electrodes and the electrochemical performance of the cells. In particular, GD-MS analysis on LIBs allowed detection and depth localization of lithium isotope fractionation in the electrodes, establishing a new benchmark for the study of electrode-electrolyte interfaces. T2 - 20th GD-Users Meeting, TAZ GmbH CY - Aichach, Germany DA - 01.10.2025 KW - GD-MS KW - GD-OES KW - Lithium-Ion Battery PY - 2025 AN - OPUS4-64392 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Investigation of degradation of the aluminum current collector in lithium-ion batteries by glow-discharge optical emission spectroscopy N2 - Lithium-ion batteries (LIBs) are one technology to overcome the challenges of climate and energy crisis. They are widely used in electric vehicles, consumer electronics, or as storage for renewable energy sources. However, despite innovations in batteries' components like cathode and anode materials, separators, and electrolytes, the aging mechanism related to metallic aluminum current collector degradation causes a significant drop in their performance and prevents the durable use of LIBs. Glow-discharge optical emission spectroscopy (GD-OES) is a powerful method for depth-profiling of batteries' electrode materials. This work investigates aging-induced aluminum deposition on commercial lithium cobalt oxide (LCO) batteries' cathodes. The results illustrate the depth-resolved elemental distribution from the cathode surface to the current collector. An accumulation of aluminum is found on the cathode surface by GD-OES, consistent with results from energy-dispersive X-ray spectroscopy (EDX) combined with focused ion beam (FIB) cutting. In comparison to FIB-EDX, GD-OES allows a fast and manageable depth-profiling. Results from different positions on an aged cathode indicate an inhomogeneous aluminum film growth on the surface. The conclusions from these experiments can lead to a better understanding of the degradation of the aluminum current collector, thus leading to higher lifetimes of LIBs. T2 - Adlershofer Forschungsforum 2022 CY - Berlin, Germany DA - 11.11.2022 KW - Lithium Ion Batteries KW - GD-OES KW - FIB KW - SEM KW - EDX PY - 2022 AN - OPUS4-56246 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Chemical characterization of aging processes in high energy-density lithium-ion batteries N2 - Introduction Lithium-ion batteries (LIBs) are one key technology to overcome the climate crisis and energy transition challenges. Demands of electric vehicles on higher capacity and power drives research on innovative cathode and anode materials. These high energy-density LIBs are operated at higher voltages, leading to increased electrolyte decay and the current collectors' degradation. Even though this fundamental corrosion process significantly affects battery performance, insufficient research is being done on the aluminum current collector. Fast and convenient analytical methods are needed for monitoring the aging processes in LIBs. Methods In this work glow-discharge optical emission spectrometry (GD-OES) was used for depth profile analysis of aged cathode material. The measurements were performed in pulsed radio frequency mode. Under soft and controlled plasma conditions, high-resolution local determination (in depth) of the elemental composition is possible. Scanning electron microscopy (SEM) combined with a focused ion beam (FIB) cutting and energy dispersive X-ray spectroscopy (EDX) was used to confirm GD-OES results and obtain additional information on elemental distribution. Results The aging of coin cells manufactured with different cathode materials (LCO, LMO, NMC111, NMC424, NMC532, NMC622, and NMC811) was studied. GD-OES depth profiling of new and aged cathode materials was performed. Quantitative analysis was possible through calibration with synthetic standards and correction by sputter rate. Different amounts of aluminum deposit on the cathode surface were found for different materials. The deposit has its origin in the corrosion of the aluminum current collector. The results are compatible with results from FIB-EDX. However, GD-OES is a faster and less laborious analytical method. Therefore, it will accelerate research on corrosion processes in high energy-density batteries. Innovative aspects - Quantitative depth profiling of cathode material -Monitoring of corrosion processes in high energy-density lithium-ion batteries - Systematic investigation of the influence of different cathode materials T2 - ANAKON 2023 CY - Vienna, Austria DA - 11.04.2023 KW - Lithium Ion Batteries KW - GD-OES KW - Depth-profiling PY - 2023 AN - OPUS4-58586 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Investigation of degradation of the aluminum current collector in lithium-ion batteries by GD-OES N2 - Lithium-ion batteries (LIBs) are one technology to overcome the challenges of climate and energy crisis. They are widely used in electric vehicles, consumer electronics, or as storage for renewable energy sources. However, despite innovations in batteries' components like cathode and anode materials, separators, and electrolytes, the aging mechanism related to metallic aluminum current collector degradation causes a significant drop in their performance and prevents the durable use of LIBs. Glow-discharge optical emission spectroscopy (GD-OES) is a powerful method for depth-profiling of batteries' electrode materials. This work investigates aging-induced aluminum deposition on commercial lithium cobalt oxide (LCO) batteries' cathodes. The results illustrate the depth-resolved elemental distribution from the cathode surface to the current collector. An accumulation of aluminum is found on the cathode surface by GD-OES, consistent with results from energy-dispersive X-ray spectroscopy (EDX) combined with focused ion beam (FIB) cutting. In comparison to FIB-EDX, GD-OES allows a fast and manageable depth-profiling. Results from different positions on an aged cathode indicate an inhomogeneous aluminum film growth on the surface. The conclusions from these experiments can lead to a better understanding of the degradation of the aluminum current collector, thus leading to higher lifetimes of LIBs. T2 - Empa Group Meeting CY - Dübendorf, Switzerland DA - 22.11.2022 KW - Lithium Ion Batteries KW - GD-OES KW - FIB KW - SEM KW - EDX PY - 2022 AN - OPUS4-56584 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -